TW201627396A - 用於複合材料之環氧基樹脂組合物 - Google Patents
用於複合材料之環氧基樹脂組合物 Download PDFInfo
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Abstract
本發明揭示一種可固化的環氧基樹脂組合物，其可與加強纖維組合且接著經固化以形成韌性極佳並展現高開孔拉伸(OHT)強度之固化產物。根據一個實施例，該樹脂組合物含有雙酚F雙官能環氧樹脂、蒽基化合物、三官能環氧樹脂、熱塑性聚合物及含胺固化劑。
Description
本申請案主張2014年12月16日申請之美國臨時專利申請案第62/092448號之權益，該申請案之揭示內容以全文引用之方式併入。
聚合物基質複合(PMC)材料廣泛用於多個應用中。舉例而言，此類複合材料作為高強度、低重量材料愈來愈多地用於諸如飛機及汽車之部件的高效能航空結構中以替換金屬。PMC材料含有嵌入聚合基質材料中之加強纖維，諸如，碳纖維、玻璃纖維及芳族聚醯胺纖維。PMC材料展現良好機械特性(例如，強度、硬度、韌性)，而且允許較寬的處理溫度窗及易製性，從而使其極適合航空應用。
用於生產纖維加強型複合材料之方法包括藉由用未經固化之基質樹脂浸漬片狀加強纖維而形成預浸體之方法。此方法常被稱作「預浸」方法。層壓、固結及隨後固化預浸體之多個積層以形成複合部件。替代地，複合部件可使用樹脂轉注成形(RTM)方法形成，該方法涉及將液體樹脂注入至安置於模具中或模具上之加強纖維的預成型體中及隨後加熱樹脂灌注之預成型體來固化樹脂。
作為用於PMC材料中之基質樹脂，熱固性樹脂由於其高耐溶劑性及耐熱性而被主要使用。由於環氧樹脂與加強纖維之間的黏附性以及所獲得的複合材料之機械特性(諸如強度及硬度)而常使用環氧樹
脂。
可控制預浸體特性及所得複合結構之品質以操縱由該等預浸體製成之所得複合結構的品質及特性。
視表徵所考慮複合材料之應力狀態、幾何結構及邊界條件而定，於複合材料之製造中可使用不同設計考慮因素。一種此類設計考慮因素為缺口特性。缺口特性在經設計之複合部件含有用於接納扣件之孔時極為重要。缺口特性量測一旦在複合材料自身之負荷承載區域上鑽出一孔時，給定複合材料承載負荷之能力。一種用於量測此類缺口特性之方法為開孔拉伸(OHT)強度測試(例如，ASTM D5766)，其為經確立的用於測定孔對纖維加強型聚合物複合物之拉伸強度的作用之靜態方法。
開孔拉伸特性主要受碳纖維之強度影響，且有輕微影響來自於經固化之樹脂基質。開孔壓縮的情況則相反，在開孔壓縮中經固化之樹脂基質占主導。對於給定纖維，可操縱經調配之樹脂基質特性以增加OHT或OHC，但鮮少可改良此等特性中之一者而對另一者無不利影響。
在許多複合部件中，OHT與OHC兩者均重要，因此，降低一種特性來達成另一特性係不合需要的。在複合部件經彎曲之情況下，一側將處於張力下且另一側受壓縮，諸如具有上下機翼蒙皮之飛機。增加拉伸強度至關重要之另一實例為在內側受壓之複合儲槽中。
本文揭示一種可固化的環氧基樹脂組合物，其可與加強纖維組合且接著經固化以形成韌性極佳並展現高OHT之固化產物/結構，從而使其尤其適合用於航空應用。將此組合物併入複合結構中允許OHT
特性之增加而對OHC特性無負面效應。
根據本發明之一個實施例，環氧基樹脂組合物含有：(A)環氧樹脂組份，其包括：(i)由以下結構(I)表示之雙酚F雙官能環氧樹脂：
(ii)由以下結構(II)表示之蒽基化合物：
；及(iii)三官能環氧樹脂；(B)熱塑性聚合物；及(C)含胺固化劑，其中，三官能環氧樹脂以每100重量份之環氧組份中小於30份，較佳為20至29份之量存在，且雙官能環氧樹脂以大於蒽基化合物之量的量存在。
蒽基化合物為具有兩個環氧官能基之獨特單體且類似環氧樹脂。已發現，此蒽基化合物可在恰當的應用及條件下改變經固化樹脂及由該經固化樹脂形成之經固化複合材料的機械特性。意料之外的發現為在組份(A)至(C)之特定化學計量下OHT將增加。
根據一個實施例，環氧組份(A)在每100重量份之環氧組份中含有：49至51份雙官能環氧樹脂，
24至26份蒽基化合物，及23至25份三官能環氧樹脂。
熱塑性聚合物(B)係以每100份環氧組份中20至60份，更佳地為25至35份之量存在，且在一個實施例中，以每100份環氧組份中30份之量存在。
在較佳實施例中，組合物中之胺固化劑(D)的量為總環氧當量之70%至90%，更佳地為75%至80%。或換言之，含胺固化劑與環氧組份之比率為使得對於每一莫耳之環氧基團存在0.7至0.9莫耳，較佳地0.75至0.8莫耳的胺-氫基[亦即，環氧樹脂係與低於化學計量之胺組合]。
在大多數情況下，反應物環氧基之量係經設計為以1：1比率利用相同量之反應物胺基進行固化。此係為了確保最快反應速率以及最大環氧轉化率(epoxy conversion)。利用較少量胺硬化劑或較低的化學計量，過量環氧樹脂仍將藉由同元聚合(亦即，自固化)以較慢速率固化。因此，已發現，與具有較高的胺/環氧樹脂化學計量比之對照相比，本發明之環氧樹脂組合物在較低的胺/環氧樹脂化學計量比下產生較好的OHT結果。
合適的三官能環氧樹脂(含有三個環氧基)包括：
4-縮水甘油基氧基-N,N-二縮水甘油基苯胺(可作為Araldite® MY0510購自Huntsman Advanced Materials)；
3-縮水甘油基氧基-N,N-二縮水甘油基苯胺(可作為Araldite® MY0610購自Huntsman Advanced Materials)。
將熱塑性樹脂組份添加至環氧基樹脂組合物以給予較高級韌性，諸如衝擊後壓縮強度(CAI)及G1c破裂韌性。破裂韌性可經定量為應變能釋放率(Gc)，其為在破裂期間每單位新產生之破裂表面積耗散之能量。Gc包括G1c(模式1--開口模式)。下標「1c」指示模式I裂縫開口，其在垂直於裂縫之正拉伸應力之下形成。
合適的熱塑性聚合物可選自聚醚碸(PES)、聚醚醚碸(PEES)、具有端胺基之PES-PEES共聚物及其組合。在一個實施例中，將具有端胺官能基之PES-PEES共聚物用作熱塑性組份。美國專利第6,437,080號中揭示此PES-PEES共聚物之製造。已發現此PES-PEES共聚物之使用為樹脂組合物賦予經改良黏度，其允許較好的處理、製造能力及預浸體處置。
合適的胺固化劑(或熟化劑)包括芳胺(諸如二胺基二苯碸，包括3,3-二胺基二苯碸(3,3'-DDS)及4,4'-二胺基二苯碸(4,4'-DDS))；及茀胺(諸如9,9-雙(3-氯-4-胺基苯基)氟(CAF))及其組合。
如本文所論述，樹脂組合物可進一步包含少量添加劑，其影響未經固化或經固化之樹脂之機械、流變、電氣、光學、化學及/或熱特性中之一或多者。此類添加劑可進一步包含與環氧樹脂進行化學反應、與其中之組份相互作用或對該等組份不起反應的材料。添加劑之
實例可包括(但不限於)韌化顆粒(諸如，熱塑性或彈性顆粒、核殼橡膠顆粒)、阻燃劑、紫外線(UV)安定劑、抗氧化劑、著色劑及無機填充劑(例如，二氧化矽、氧化鋁、碳酸鈣、滑石、金屬顆粒)以增強損壞容忍度、韌性、耐磨性中之一或多者。
本文所描述之環氧基樹脂組合物適合用於製造複合材料，具體而言，預浸體。在此上下文中之複合材料係指纖維加強型樹脂複合物，其由嵌入於基質樹脂中之加強纖維構成。如本文所使用之術語「預浸體」係指已用可固化基質樹脂浸漬之纖維材料層。纖維加強材料可呈編織物層或非編織物層或單向帶之形式。「單向帶」係指加強纖維層，該等加強纖維在片狀組態中在同一方向上對準。如本文所用之術語「預浸體疊層」係指複數個已經放置在堆疊配置中之預浸體層。作為實例，預浸體層之數目可為2至100個層或10至50個層。
可手動地或藉由諸如自動鋪帶(ATL)之自動化製程將複數個可固化預浸體層放置在堆疊配置中。可將疊層內的該等預浸體層定位在相對於彼此之所選擇的定向上。舉例而言，預浸體疊層可包含具有單向纖維架構之預浸體層，其中該等纖維相對於該疊層之最大維度(諸如長度)以所選角度θ(例如0°、45°或90°)定向。應進一步理解，在某些實施例中，預浸體可具有纖維架構之任何組合，諸如單向對準纖維、多向纖維及編織物。
預浸體可藉由用本文所揭示之可固化樹脂組合物灌注或浸漬連續單向纖維或編織物從而產生可彎及膠黏之材料片而製造。此通常被稱作預浸製程。亦可根據需求指定每平方公尺之纖維量。纖維面積重量(FAW)以每平方公尺克數(gsm)量測。對於一些實施例而言，塗覆於織物之每一面上之樹脂薄膜可具有10至200gsm之薄膜重量，且該織物可具有100至600gsm之織物面積重量(FAW)。
術語「浸漬」係指將可固化基質樹脂材料引入加強纖維中以便藉由樹脂部分或完全囊封纖維。用於製造預浸體之基質樹脂可呈樹脂薄膜或液體之形式。此外，在黏結之前，基質樹脂係處於可固化/未經固化狀態。可藉由施加熱量及/或壓力促進浸漬。
作為一實例，浸漬方法可包括：(1)連續地移動纖維通過熔融浸漬基質樹脂組合物之(經加熱之)槽以完全或實質上完全浸濕該等纖維；或(2)將頂部及底部樹脂薄膜按壓在平行配置之連續單向纖維或織物層上，同時在80℃至300℃之範圍內的溫度下施加熱量。
複合基板(例如預浸體)中之加強纖維可呈短切纖維、連續纖維、絲狀纖維、纖維束、集束、薄片、層及其組合之形式。連續纖維可進一步採用單向(在一個方向上對準)、多向(在不同方向上對準)、非編織、編織、針織、縫合、捲繞及編結組態以及捲曲纖維墊、毛氈墊及短切墊結構中之任一者。編織纖維結構可包含複數個編織纖維束，每一纖維束由複數個絲狀纖維(例如數千個絲狀纖維)構成。在另外的實施例中，可藉由交叉纖維束縫合、投緯針織縫合或少量諸如熱塑性樹脂之樹脂黏合劑將該等纖維束固持在適當位置。
纖維材料包括(但不限於)玻璃(包括電氣玻璃或E玻璃)、碳、石墨、芳族聚醯胺、聚醯胺、高模數聚乙烯(PE)、聚酯、聚對伸苯基苯并噁唑(PBO)、硼、石英、玄武岩、陶瓷及其組合。
就諸如用於航空及汽車應用之彼等者之高強度複合材料之製造而言，較佳的是，加強纖維具有大於3500MPa之拉伸強度。
環氧樹脂組合物係根據下表1中所示之調配物製備。組份A至E之量為重量份。
1由Huntsman Advanced Materials供應
2 由Mitsubishi Chemical Corporation供應
3 由Huntsman Advanced Materials供應
使用表1之樹脂調配物製備預浸體樣品。混合環氧樹脂A、B、C並將其加熱至大約150℉。接著添加熱塑性塑膠D，分散及藉由加熱該混合物至255℉溶解。一旦熱塑性塑膠溶解，則將混合物冷卻至165℉。接著將熟化劑組份D淤漿至混合物中。冷凍樹脂以使樹脂擴鏈降至最低。使用傳統熱熔處理設備進行薄膜塗佈及預浸體處理。對於此等實驗性運轉而言，使用雙薄膜製程，其中在180℉(82℃)下將單一樹脂調配物薄膜塗佈至剝離型紙上並將其分裂成兩個相等長度之薄膜。藉由使用熱熔預浸設備，將樹脂薄膜同時頂部及底部塗覆至單向碳纖維腹板。用於碳纖維之目標FAW為145gsm且目標樹脂含量為33%。熱熔預浸設備包括具有捲筒之移動滑板，該等捲筒在230℉(130℃)熱板上方來回移動。其之後為3次後續夾壓(nip)以幫助固結所得預浸體。複合面板如下製成：根據定向[+/90/-/0]3S放置24個預浸體層產生14×14吋面板，在高壓釜中在真空下於350℉(176.7℃)下固化3小時。
藉由自14×14吋之經固化面板切割12×1.5吋樣品而形成OHT測試樣品。在每一測試樣品之中心鑽出0.25吋的孔。裝載或夾緊樣品且在
室溫下以每分鐘0.5吋之速度測試該等樣品。
為獲得用於開孔壓縮(OHCq-HW 180℉)之資料，如上文所描述製成經固化之複合材料之12×1.5吋測試樣品。在每一測試樣品之中心鑽出0.25吋的孔。在潮濕箱中調節樣品，在160℉下浸泡於水中達14天。接著裝載樣品且在室溫下及在180℉下以每分鐘0.5吋之速度測試該等樣品。
與對照調配物1至3相比，調配物4產生最高OHT強度。對照3及調配物之結果展示，與並不含有蒽基二環氧基樹脂(組份B)之對照1及2相比，組份A及B兩者之存在產生較高OHT強度。然而，對照3具有高含量的三官能環氧樹脂(組份C)及高熟化劑/環氧樹脂化學計量，從而產生比調配物4低的OHT強度，其表示經改良及較佳之組合物。
為了比較，藉由上文在實例1中所描述之相同方法使用表2中揭示之樹脂調配物來製備預浸體樣品。組份B至E之量為重量份。
3,4 由Huntsman Advanced Materials供應
5 由Sumika Excel供應
表2之樹脂調配物並不含有如表1之樹脂調配物中之雙酚-F雙官能
環氧樹脂(組分A)，且熟化劑/環氧樹脂化學計量較高。應注意，樹脂調配物5至7之OHT數目並不與針對得自表1之配方4之經固化複合物所獲得之OHT數目一樣高。
Claims (12)
- 一種可固化環氧基樹脂組合物，該組合物包含：(A)環氧組份，其包含：(i)由以下結構(I)表示之雙酚F雙官能環氧樹脂：
- 如請求項1之可固化環氧基樹脂組合物，其中該三官能環氧樹脂係由以下結構(III)表示：
- 如請求項1之可固化環氧基樹脂組合物，其中該含胺固化劑為二胺基二苯碸(DDS)或茀胺。
- 如請求項1之可固化環氧基樹脂組合物，其中蒽基化合物與雙官能環氧樹脂之重量比為0.4至0.6。
- 如請求項1之可固化環氧基樹脂組合物，其在每100重量份之該環氧組份中包含：49至51份雙官能環氧樹脂，24至26份蒽基化合物，及23至25份三官能環氧樹脂。
- 如請求項1之可固化環氧基樹脂組合物，其中該熱塑性聚合物為具有端胺基之PES-PEES共聚物。
- 如請求項1之可固化環氧基樹脂組合物，其中該三官能環氧樹脂係以在20至29份範圍內之量存在。
- 一種包含加強纖維之複合材料，該等加強纖維係嵌入如請求項1之可固化環氧基樹脂組合物中或灌注有如請求項1之可固化環氧基樹脂組合物。
- 如請求項8之複合材料，其中該等加強纖維係選自碳纖維、芳族聚醯胺纖維及玻璃纖維。
- 一種包含單向纖維的預浸體，該等單向纖維係經如請求項1之可固化環氧基樹脂組合物浸漬。
- 如請求項10之預浸體，其中該等單向纖維係選自碳纖維、芳族 聚醯胺纖維及玻璃纖維。
- 一種包含以堆疊配置進行配置之複數個預浸體的複合層合物，每一預浸體包含經如請求項1之可固化環氧基樹脂組合物浸漬之單向纖維。
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