TW201343708A - 可固化樹脂組合物及短固化方法 - Google Patents

可固化樹脂組合物及短固化方法 Download PDF

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TW201343708A
TW201343708A TW102106781A TW102106781A TW201343708A TW 201343708 A TW201343708 A TW 201343708A TW 102106781 A TW102106781 A TW 102106781A TW 102106781 A TW102106781 A TW 102106781A TW 201343708 A TW201343708 A TW 201343708A
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epoxy resin
curing
temperature
resin composition
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Jonathan E Meegan
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Abstract

本文揭示一種利用低溫固化反應所生成之放熱能量達成原本在所選工具溫度下在能量上無法達成之高溫固化反應，藉此產生性質與彼等經由高溫固化反應產生者非常接近但經由短固化時間及低固化溫度而達成之固化樹脂基質之方法。本文亦揭示短固化樹脂組合物，其含有：(a)至少一種具有大於1之環氧官能度之多官能環氧樹脂；(b)硬化劑組合物，其含有：(i)至少一種每一分子具有一或多個胺基之脂肪族或環脂族胺固化劑；(ii)至少一種每一分子具有一或多個胺基之芳香族胺固化劑；及視情況(iii)作為固化加速劑之咪唑。此樹脂組合物之改良性質包括可在≦120℃之溫度下經少於10分鐘之時間段固化，以達成高於自僅具有分離之(i)脂肪族/環脂族胺或(ii)芳香族胺之相同組合物得到者之固化程度。

Description

可固化樹脂組合物及短固化方法
熱固性環氧樹脂已廣泛用於高級複合材料之生產中，其中用由環氧樹脂及固化劑組成之調配物浸漬強化纖維(例如碳纖維或玻璃纖維)，且然後將其固化以形成纖維樹脂基質複合材料。已發現，具有高強度重量比之經強化環氧樹脂複合物廣泛用於航太工業以及期望高強度、耐腐蝕性及輕載之其他應用中。例如，纖維樹脂基質材料已在現代航空器之一級及二級結構中代替鋁及其他金屬。諸如網球拍及高爾夫球棍等體育設備亦已成功採用纖維樹脂材料。由於纖維樹脂基質材料之出現，故已在改良其性質及特徵方面作出許多努力，包括許多不同固化系統之研發。
本文揭示利用低溫固化反應所生成之放熱能量(即熱量)激活原本在所選固化溫度下在能量上無法達成之高溫固化反應之方法。應用該方法產生固化樹脂基質，其係在與較低固化溫度(<120℃)反應相當之工具溫度下獲得。工具溫度係指用於固化樹脂系統之工具或模具之溫度。
本文亦揭示樹脂組合物，其含有：(a)至少一種具有大於1之環氧官能度之多官能環氧樹脂；(b)至少一種每一分子具有一或多個胺基之脂肪族或環脂族胺固化劑；(c)至少一種每一分子具有一或多個胺基之芳香族胺固化劑；及視情況(d)作為固化加速劑之咪唑。此樹脂 組合物之改良性質包括在等於或小於120℃之溫度下固化小於10分鐘或在一些實施例中5分鐘之時間段即可達成大於90%、較佳大於95%之固化程度。
圖1係圖解說明本揭示內容之能量轉移概念之示意圖。
圖2係闡述於圖1中之概念之例示性實施例。
圖3顯示實例中所闡述之兩種複合層板之所選擇機械測試數據。
術語「固化」(「curing」或「cure」)係指藉由聚合物鏈之化學交聯而使聚合物材料硬化。術語「可固化」意指組合物能夠經受使組合物處於固化或熱固狀態或條件之條件。
使用用於聚環氧樹脂之芳香族二胺固化劑使得能夠形成與脂肪族胺固化劑相比具有較高玻璃轉變溫度(Tg)及通常優越性質之交聯聚合物(熱固樹脂)。然而，通常需要高固化溫度、長固化時間(通常1小時至3小時)及固化後長期加熱來達成該等較高性能特徵。
對於胺/環氧系統之快速、低溫固化而言，脂肪族胺由於烷基主鏈對位於胺官能基上之孤對電子具有正誘導效應且與環氧基團之反應性增加(此效應係與芳香族胺分子相比)而被使用。然而，含有脂肪族胺之環氧調配物由於其增加之反應性及相關之放熱傾向而通常不適於在接近或高於反應起始溫度之溫度下固化大量樹脂。
在胺-環氧系統中已使用咪唑作為在約100℃或更高之溫度下快速固化(例如少於1小時)之加速劑/固化劑，然而，所得固化樹脂之Tg通常較低，從而使得該等樹脂系統更適於黏附劑應用。另外，該等樹脂系統在散裝中亦傾向於放熱反應。
已發現，在低溫下發生之固化反應生成之放熱能量可用以激活原本在能量上無法達成之反應(其顯示更高之固化起始溫度)，且所得 固化樹脂之性質可受高溫固化系統影響而非僅代表較低固化溫度反應；此概念繪示於圖1中，水平軸代表發生固化之工具之溫度，且垂直軸代表所生成之放熱能量。圖1顯示，低溫反應之反應起始溫度低於較高溫度反應，且工具溫度不會引發較高溫度反應之起始。相反，使用重疊區來引發較高溫度反應。本文所使用之高溫固化反應係指藉由在等於或大於130℃之溫度下施加熱量而引發之熱固樹脂與固化劑之固化反應(即交聯)。低溫固化反應係指藉由在30℃-100℃範圍內之溫度下施加熱量而引發之熱固樹脂與固化劑之固化反應。
已基於上述能量轉移概念設計出利用自固化環氧樹脂系統釋出之放熱能量來產生固化樹脂基質之實踐方法，該固化樹脂基質之性質受高溫固化反應之性質影響但係經由短固化時間(<30分鐘，在一些情形下<10分鐘)在低於高固化溫度反應之起始溫度之固化溫度下孤立地達成。此短固化方法包括選擇環氧樹脂與固化劑之特定組合：至少一種多官能環氧樹脂、脂肪族或環脂族胺、芳香族胺及視情況作為固化加速劑之咪唑。脂肪族或環脂族胺固化劑能夠在低固化溫度下固化多官能環氧樹脂。芳香族胺固化劑能夠在高固化溫度下固化多官能環氧樹脂。然後，將各組份混合以形成可固化樹脂組合物，隨後以足以引發低溫固化反應之聚合反應之量或溫度向樹脂組合物施加熱量。在聚合階段期間，低溫固化反應生成放熱能量，其一部分足以引發高溫固化反應之聚合反應。在目前情形下，環氧樹脂、脂肪族或環脂族胺與咪唑之反應係生成放熱能量之低溫固化反應，且環氧樹脂、芳香族胺與咪唑之反應係高溫固化反應。
根據較佳實施例，基於上述能量轉移概念之短固化樹脂組合物係由以下各項組成：(a)至少一種具有大於1之環氧官能度之多官能環氧樹脂；及(b)硬化劑組合物，其含有兩個不同類型之固化劑：(i)至少一種每一分子具有一或多個胺基之脂肪族或環脂族胺固化劑；(ii) 至少一種每一分子具有一或多個胺基之芳香族胺固化劑；及視情況(iii)作為固化加速劑之咪唑。
短固化樹脂組合物之固化起始溫度小於100℃，較佳小於50℃(例如45℃)，如藉由DSC以5℃/分鐘之速率所量測，且其可在等於或小於120℃、例如110℃-120℃之溫度範圍內固化經少於10分鐘(在一些實施例中5分鐘，在其他實施例中3分鐘)之時間段以達成高於自僅具有分離之(i)脂肪族/環脂族胺或(ii)芳香族胺之相同組合物得到者之固化程度。當經由(例如)樹脂轉注成型(RTM)製程使用此短固化樹脂組合物在模具中浸漬樹脂來浸漬纖維強化材料時，可在120℃或更低溫度下固化少於5分鐘(例如3分鐘)之後達成大於95%之固化程度或大於97%之固化程度。本文所論述之固化程度係藉由DSC以5℃/分鐘之速率量測。
在120℃或更低之固化溫度下固化少於10分鐘(在一些實施例中5分鐘)之後，短固化樹脂組合物產生具有110℃-150℃或115℃-120℃範圍內之玻璃轉變溫度(Tg)之固化樹脂基質，如藉由DSC所量測。固化樹脂基質係化學上均勻的網絡相。
上述樹脂組合物使得短固化時間能夠與相對低固化起始溫度組合。此短固化樹脂組合物內之該等期望性質與使用第二較高溫度固化反應自圖解說明於圖1中之第一較低溫度固化反應吸收放熱能量相關。
上述能量轉移概念之例示性實施例顯示於圖2中。圖2顯示雙酚F環氧樹脂與異佛爾酮二胺(isophorone diamine)之反應性(低溫反應)及雙酚F環氧樹脂與3,3'-胺基二苯碸之反應性(高溫反應)之DSC跡線。異佛爾酮二胺係環脂族胺，且3,3'-胺基二苯碸係芳香族胺。低溫反應及高溫反應之跡線與圖1中所闡述之概念密切匹配。第三跡線顯示與雙酚F環氧樹脂化學計量平衡之異佛爾酮二胺及3,3'-胺基二苯碸之等莫 耳組合，且說明組合之兩種固化劑具有驚人且期望之效應。
環氧樹脂
如本文所使用，術語「多官能環氧樹脂」係指具有大於1之環氧官能度且能夠固化為聚合狀態之化合物。適用於本揭示內容中之環氧樹脂係可用於與胺固化劑反應之每一分子具有1個以上環氧化物基團之聚環氧化物化合物。一般而言，多官能樹脂可為具有環氧官能度之飽和、不飽和、環狀或非環狀、脂肪族、脂環族、芳香族或雜環分子。舉例而言，適宜多官能環氧樹脂包括基於以下各項者：酚及甲酚環氧酚醛清漆、酚醛加合物之縮水甘油醚；二脂肪族二醇之縮水甘油醚；二縮水甘油醚；二乙二醇二縮水甘油醚；芳香族環氧樹脂；二脂肪族三縮水甘油醚、脂肪族聚縮水甘油醚；環氧化烯烴；溴化樹脂；芳香族縮水甘油胺；雜環縮水甘油基醯亞胺及醯胺(heterocyclic glycidyl imidines and amides)；縮水甘油醚；氟化環氧樹脂。
適宜環氧化物之實例包括聚縮水甘油醚，其係藉由在鹼金屬存在下環氧氯丙烷或環氧溴丙烷與多酚之反應來製備。因此，適宜多酚係(例如)間苯二酚、鄰苯二酚、對苯二酚、雙酚A(雙(4-羥基苯基)-2,2-丙烷)、雙酚F(雙(4-羥基苯基)甲烷)、雙酚S、雙(4-羥基苯基)-1,1-異丁烷、茀4,4'-二羥基二苯基酮、雙(4-羥基苯基)-1,1-乙烷、雙酚Z(4,4'-亞環己基雙酚)及1,5-羥基-萘。多元醇、胺基苯酚或芳香族二胺之聚縮水甘油醚亦適宜。
其他實例包括：多價酚之聚縮水甘油醚，例如鄰苯二酚；間苯二酚、對苯二酚；4,4'-二羥基二苯基甲烷；4,4'-二羥基-3,3'-二甲基二苯基甲烷；4,4'-二羥基二苯基二甲基甲烷；4,4'-二羥基二苯基甲基甲烷；4,4'-二羥基二苯基環己烷；4,4'-二羥基-3,3'-二甲基二苯基丙烷；4,4'-二羥基二苯基碸；或參(4-羥基苯基)甲烷；上述二酚之氯化及溴化產物之聚縮水甘油醚；酚醛清漆(即，在酸觸媒存在下，一羥基或 多羥基酚與醛(具體而言甲醛)之反應產物)之聚縮水甘油醚。
環氧樹脂之其他實例包括以下各項之二縮水甘油醚：經二烯改質之酚類酚醛清漆、多官能環脂族羧酸與環氧氯丙烷之反應產物、環脂族環氧化物、環脂族環氧醚及環脂族環氧酯及諸如此類。
適宜多官能環氧樹脂可包括二官能環氧樹脂、三官能環氧樹脂與四官能環氧樹脂之任一組合。二官能環氧樹脂之實例包括雙酚A(例如來自Dow Chemical公司之EponTM 828(液體環氧樹脂)、DER 331、DER 661(固體環氧樹脂)、來自Dyne Chemical公司之EJ-190、來自Huntsman Advanced Materials之Tactix 123)之二縮水甘油醚、雙酚F之二縮水甘油醚(DGEBF，例如，來自Huntsman Advanced Materials之PY306、EpikoteTM 158(來自Momentive)。三官能環氧樹脂之實例包括胺基苯酚(例如由Huntsman Advanced Materials供應之Araldite® MY 0510、MY 0500、MY 0600、MY 0610)之三縮水甘油醚。四官能環氧樹脂之實例包括亞甲基二苯胺(例如來自Huntsman Advanced Materials之Araldite® MY 9655)之四縮水甘油醚、四縮水甘油基二胺基二苯基甲烷(例如，由Huntsman Advanced Materials供應之Araldite® MY 721、MY 720、MY 725、MY 9663、MY 9634、MY 9655)。
具有基於縮水甘油胺或縮水甘油醚或兩者之官能基之多官能環氧樹脂尤其適宜。具有縮水甘油胺及縮水甘油醚官能基二者之多官能環氧樹脂更佳。在某些實施例中，用於本文所揭示之短固化樹脂組合物之多官能環氧樹脂可選自由以下結構代表之環氧樹脂之群：
亞甲基雙(N,N-二縮水甘油基苯胺
雙酚F二縮水甘油醚
三(4-羥基苯基)甲烷三縮水甘油醚
3-氧化縮水甘油-N,N-二縮水甘油基苯胺
應注意，結構(I)含有縮水甘油胺官能基，結構(II)及(III)含有縮水甘油醚官能基，且結構(IV)及(V)含有縮水甘油胺及縮水甘油醚官能基二者。
固化劑及加速劑
適宜脂肪族或環脂族胺固化劑係具有1個以上胺-氫官能基且能夠在30℃-100℃範圍內之溫度下固化多官能環氧樹脂者。例示性脂肪族胺包括(但不限於)：三乙胺、二乙胺、三伸乙四胺(TETA)、二乙基甲苯二胺(DETDA)、聚醚胺(例如以商標Jeffamine購自Huntsman公司者)。例示性環脂族胺包括(但不限於)：異佛爾酮二胺、薄荷烷二胺、1,2-二胺基環己烷、1,3-二胺基環己烷、1,4-二胺基環己烷、1,3-二(胺 基甲基)環己烷、4,4'-亞甲基二環己胺、4,4'-二胺基二環己基甲烷、3,3'-二甲基-4,4'二胺基二環己基-甲烷及其組合。
適宜芳香族胺固化劑係具有1個以上胺-氫官能基且能夠在120℃或更高、更佳130℃或更高之溫度下固化該多官能環氧樹脂者。例示性芳香族胺包括(但不限於)：3,3'-二胺基二苯碸(3,3'DDS)、4,4'-二胺基二苯碸(4,4'DDS)；4,4'-亞甲基-雙-(3-氯-2,6-二乙基苯胺)(MCDEA)；4,4'-亞甲基-雙-(2,6-二乙基苯胺)(MDEA)；2,6-二乙基苯胺(DEA)；諸如亞甲基二苯胺(MDA)等二苯胺、9,9-雙(3-氯-4-胺基苯基)-9H-茀(CAF)。
已發現，咪唑與上述脂肪族及芳香族胺固化劑中之至少一者之組合引起較早固化起始溫度且增強反應性。適宜咪唑加速劑包括(但不限於)咪唑、甲基咪唑、乙基甲基咪唑、乙基甲基咪唑丙腈、氰基乙基苯基雙甲基咪唑。
樹脂組合物之製備
一般而言，藉由混合一或多種環氧樹脂與含有胺及視情況咪唑之硬化劑組合物來製備基於本揭示內容之能量轉移概念之可固化樹脂組合物。硬化劑組合物之製備可包括：施加熱量將芳香族胺溶解於脂肪族胺中，隨後冷卻，之後添加咪唑。若需要，可預加熱環氧樹脂，以在使其與胺混合之前降低其黏度。環氧樹脂-胺混合物之化學計量係基於0.1：2、較佳1：1之胺基團對環氧基團之當量比。可端視所選擇胺改變芳香族胺對脂肪族胺之重量比以達成期望之化學計量比。咪唑基於樹脂組合物之總重量可以小於2.0重量%之量存在。
在一個實施例中，短固化樹脂含有100份數之多官能環氧樹脂、10-90份數之固化劑混合物及0-10份數咪唑。
應用
如上所述，可固化樹脂組合物適於使用習用樹脂浸漬技術浸漬 (或浸漬)纖維強化材料以形成複合材料及結構。所揭示樹脂組合物尤其適於(但不限於)2部分樹脂轉注成型(RTM)，其中低黏度樹脂系統較為重要。RTM係將低黏度樹脂組合物引入含有乾燥纖維預形成物之密閉模具中之製程。纖維預形成物係由強化纖維組成，該等強化纖維可採用連續纖維層或織物之形式。可使纖維預形成物成型為適於製作複合部分之期望之三維組態。可藉由組合部分A(環氧樹脂組合物)及部分B(硬化劑組合物)來製備樹脂組合物。然後，將經調配且經預混合之樹脂組合物注射至模具中，該模具係在低壓或真空下維持。期望注射溫度下之樹脂黏度較低以獲得最佳充模及纖維潤濕。在充模之後，依照適當固化方案將其加熱。然後，可將所得經模製部分自模具移出，且若需要進行後固化。為在RTM處理期間達成良好纖維浸漬及低空隙含量，高度期望樹脂黏度在約50℃至100℃之注射溫度下低於約1泊。另外，樹脂系統必須使此低黏度維持足以完全充模且浸漬纖維預形成物之時間段。對於RTM處理而言，該時間經常以樹脂之適用期方面量測，其可定義為樹脂達到5泊所需要之時間。
用於製造複合結構之強化纖維可採用連續纖維、短纖或織物之形式。纖維材料可選自(但不限於)碳、石墨、芳香族聚醯胺(Kevlar)、聚(苯并噻唑)及聚(苯并咪唑)、聚(苯并噁唑)(PBO)、氧化鋁、二氧化鈦、石英、玻璃、聚芳醯胺、聚乙烯、聚酯、碳化矽及其組合。纖維強化類型之選擇係藉由對複合結構之性能要求來確定。對於許多高強度及低重量至關重要之航空器應用而言，高模數碳或石墨纖維係較佳增強物。
可如預期應用所指示改變複合材料內之纖維增強物及樹脂基質之相對比例。在高級複合物應用之一個實施例中，存於複合物內之纖維增強物之重量分數基於複合物之總重量可在介於約50重量%至70重量%之間之範圍內，較佳為69%。
可在樹脂浸漬之前將一或多種功能性添加劑添加至可固化樹脂組合物中，以為未經固化之組合物或經固化之複合結構賦予某些性質。功能性添加劑可經添加以影響經固化或未經固化之環氧組合物之機械、流變、電、光學、化學、防焰性及/或熱性質中之一或多者。添加劑之實例可包括(但不限於)滯焰劑、紫外線(UV)穩定劑、無機填充劑、導電顆粒或薄片。
實例
以下非限制性實例闡釋基於上述能量轉移概念之短固化方法及樹脂組合物，且不應將其理解為以任何方式限制該短固化方法及樹脂組合物之範圍。
實例1
如表1中所揭示製備5個調配物，且使用微差掃描熱量法分析。調配物5涵蓋上述能量轉移概念。在表1中，PY306係雙酚F二縮水甘油醚，CN或庫拉美CN(Curamid CN)係2-乙基-4-甲基-1H-咪唑-1-丙腈(固化加速劑)，3,3'DDS係3,3'二胺基二苯碸(芳香族胺)，IDA係異佛爾酮二胺(脂肪族胺)。所有量皆係以克表示。
使用DSC(TA儀器Q2000)分析該等調配物，且結果顯示於表2中。
如自表2可看出，調配物5具有最低之固化起始溫度，且在5分鐘固化期間產生與其他調配物相比顯著更少之放熱能量。
實例2
基於揭示於表3中之調配物製備短固化樹脂組合物。
將調配物分成兩部分，部分A含有環氧組份，且部分B含有胺及咪唑組份。部分A係藉由將DGEBF(70℃)升溫直至獲得澄清流體為止來製備。向此流體中添加三縮水甘油基間胺基苯酚(室溫)，並使用風管混合該等組份直至均勻為止。部分B係藉由以下來製備：在攪拌下將3,3'DDS溶解於異佛爾酮二胺(80℃)中，使混合物冷卻至室溫，之後添加咪唑。
將部分A及部分B單獨脫氣(30℃，-1 atm)15分鐘，之後使用風管攪拌以2.2：1(A：B)之質量比將其合併在一起，以達成均勻性。然後，將混合物再次迅速脫氣，以去除在脫氣階段(30℃，-1 atm)期間所引入之空氣。將10 g經合併之部分A及B轉移至鋁盤中，並在油浴(110℃)中加熱5分鐘，之後移出盤並使其冷卻至室溫。
為進行比較，使用以下市售RTM環氧樹脂製備固化樹脂試樣：CYCOM 890、CYCOM 823、PRISM EP2400。然後，使用以下測試方法/儀器表徵固化樹脂試樣：
結果顯示於表4中。
該等結果顯示，短固化樹脂可在遠遠較短之5分鐘固化時間內達成相對於其他市售樹脂系統相當之機械性質。
實例3
如表5中所詳述來製備短固化調配物。
表6顯示在2-3分鐘固化時間內達成大於95%之固化程度之試驗運行。
對於每一運行而言，部分A及部分B皆係基於顯示於表5中之樹脂調配物來製備。藉由在室溫下使用風管將經預加熱之PY306(70℃)與 MY0610混合直至獲得可視的均勻混合物為止來製備部分A。藉由將3,3' DDS溶解於異佛爾酮二胺(IDA)(80℃)中並保持10分鐘直至溶解為止來製備部分B。然後，將混合物冷卻至50℃，之後邊攪拌邊添加0.2 g咪唑以使其分配。
在室溫下將部分A及部分B脫氣，之後基於揭示於表6中之比率及混合溫度將其合併。將10 g經合併之部分A及B轉移至鋁盤中，並根據揭示於表6中之固化溫度在油浴中加熱，然後記錄固化時間。
實例4
取來自實例3之樹脂，並經由高壓RTM處理將其引入由12k IMS65單向纖維製成且具有196 gsm之單位面積重量之碳纖維預形成物中，使用在120℃下3分鐘之固化週期來產生具有49%之體積分數之層板。
為進行比較，使用CYCOM 977-2環氧基樹脂(購自Cytec Engineered Materials公司)及180℃下3 hr之固化週期製備相同層板。兩種層板之正規化為50%之特徵概述於圖3中。
該等結果顯示，自短固化樹脂得到之碳纖維層板之機械性能可與已知用於高性能航太應用中且通常使用顯著更長之固化時間及更高之固化溫度固化之樹脂系統之機械性能相當。

Claims (20)

  1. 一種可固化環氧樹脂組合物，其包含：(a)至少一種具有大於1之環氧官能度之多官能環氧樹脂，且該官能度係基於縮水甘油胺或縮水甘油醚或二者；(b)硬化劑組合物，其包含：i.至少一種脂肪族或環脂族胺固化劑，其每一分子具有一或多個胺基，且能夠在30℃至100℃範圍內之溫度下固化該至少一種多官能環氧樹脂；ii.至少一種芳香族胺固化劑，其每一分子具有一或多個胺基，且能夠在120℃或更高之溫度下固化該至少一種多官能環氧樹脂；其中該環氧樹脂組合物具有<50℃之固化起始溫度，如藉由微差掃描熱量法(DSC)以5℃/分鐘之速率所量測；且可在120℃或更低之溫度下經少於10分鐘之時間段固化，以達成高於自僅具有分離之(i)脂肪族或環脂族胺或(ii)芳香族胺之相同組合物得到者之固化程度。
  2. 如請求項1之可固化環氧樹脂組合物，其中該硬化劑組合物進一步包含咪唑作為固化加速劑。
  3. 如請求項1之可固化環氧樹脂組合物，其中該脂肪族或環脂族胺固化劑係選自由以下組成之群：異佛爾酮二胺(isophorone diamine)、三乙胺、二乙胺、三伸乙四胺(TETA)、二乙基甲苯二胺(DETDA)、聚醚胺；其中該芳香族多胺固化劑係選自但不限於由以下組成之群：3,3'二胺基二苯碸、4,4'-二胺基二苯碸；4,4'-亞甲基-雙-(3-氯-2,6-二乙基苯胺)(MCDEA)、4,4'-亞甲基-雙-(2,6-二乙基苯胺) (MDEA)、2,6-二乙基苯胺(DEA)、二苯胺。
  4. 如請求項3之可固化環氧樹脂組合物，其中該硬化劑組合物包含異佛爾酮二胺及3,3'-二胺基二苯碸。
  5. 如請求項1之可固化環氧樹脂組合物，其中該芳香族胺固化劑能夠在130℃或更高之溫度下固化該多官能環氧樹脂。
  6. 如請求項1之可固化環氧樹脂組合物，其中該至少一種多官能環氧樹脂包含二官能環氧樹脂與三官能或四官能環氧樹脂之組合。
  7. 如請求項1之可固化環氧樹脂組合物，其可經5分鐘或更短時間段固化。
  8. 如請求項1之可固化環氧樹脂組合物，其中該環氧樹脂組合物中胺基團對環氧基團之當量比為0.1：2。
  9. 如請求項8之可固化環氧樹脂組合物，其中胺基團對環氧基團之當量比為1：1。
  10. 如請求項1之可固化環氧樹脂組合物，其中該多官能環氧樹脂係選自由以下組成之群：
  11. 如請求項1之可固化環氧樹脂組合物，其中該多官能環氧樹脂含有縮水甘油胺及縮水甘油醚官能基二者。
  12. 一種固化環氧樹脂系統之方法，該方法包含：(a)選擇以下組份： i.至少一種多官能環氧樹脂，其具有大於1之環氧官能度，該官能度係基於縮水甘油胺及縮水甘油醚中之至少一者；ii.脂肪族或環脂族胺固化劑，其能夠在30℃至100℃範圍內之溫度下固化該多官能環氧樹脂；iii.芳香族胺固化劑，其能夠在120℃或更高之溫度下固化該多官能環氧樹脂；及iv.咪唑，其係作為固化加速劑；(b)將該等組份混合以形成可固化樹脂組合物；及(c)以足以引發組份(i)+(ii)+(iv)之聚合反應之量向該樹脂組合物施加熱量，其中組份(i)+(ii)+(iv)之該反應生成放熱能量，且一部分該放熱能量即足以引發組份(i)+(iii)+(iv)之聚合反應。
  13. 如請求項12之方法，其中步驟(c)係在120℃或更低之溫度下實施5分鐘以產生具有110℃至150℃範圍內之玻璃轉變溫度(Tg)之固化樹脂。
  14. 如請求項12之方法，其中步驟(c)係實施3分鐘。
  15. 如請求項12之方法，其中該固化樹脂具有115℃至120℃範圍內之玻璃轉變溫度(Tg)。
  16. 一種製作複合結構之方法，其包含：製備包含以下之可固化樹脂組合物：i.至少一種多官能環氧樹脂，其具有大於1之環氧官能度；ii.脂肪族或環脂族胺固化劑，其能夠在30℃至100℃範圍內之溫度下固化該多官能環氧樹脂；iii.芳香族胺固化劑，其能夠在120℃或更高之溫度下固化該多官能環氧樹脂；及 iv.咪唑，其係作為固化加速劑；用該可固化樹脂組合物浸漬纖維強化材料；及在120℃或更低之溫度下將該經浸漬纖維強化材料固化5分鐘或更短時間，以產生具有110℃至150℃範圍內之玻璃轉變溫度(Tg)之經固化複合結構。
  17. 如請求項16之方法，其中該可固化樹脂組合物進一步包含咪唑作為固化加速劑。
  18. 如請求項16之方法，其中該纖維強化材料之該浸漬係在模具中經由樹脂轉注成型(RTM)製程實施，且使該經樹脂浸漬之纖維強化材料固化短於5分鐘以達成>95%之固化程度。
  19. 如請求項16之方法，其中該纖維強化材料包含複數個乾燥纖維層。
  20. 如請求項16之方法，其中該纖維強化材料包含由選自由以下組成之群之材料製成之乾燥纖維：碳、石墨、芳香族聚醯胺、聚(苯并噻唑)及聚(苯并咪唑)、聚(苯并噁唑)(PBO)、氧化鋁、二氧化鈦、石英、玻璃、聚芳醯胺、聚乙烯、聚酯、碳化矽及其組合。
TW102106781A 2012-02-27 2013-02-26 可固化樹脂組合物及短固化方法 TWI557150B (zh)

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CN103946264A (zh) 2014-07-23
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