TWI437037B - 用於高玻璃轉化溫度(tg)應用之以不含鹵素之苯并為主之可固化組合物 - Google Patents
用於高玻璃轉化溫度(tg)應用之以不含鹵素之苯并為主之可固化組合物 Download PDFInfo
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Description
本發明在美國能源部授予協議號DE-FG36-07G017012下由美國政府支持完成。因此,美國政府對本發明具有一定的權利。
本發明係關於一種以苯并為主之不含鹵素之組合物,其可經固化形成不可燃且顯示增強的熱性質之聚合網絡結構。以苯并為主之不含鹵素之可固化組合物可用於多種應用,包括汽車、航空、電及工業應用。
本發明主張2008年2月21日申請之美國專利申請案第60/030,366號之優先權,其以引用之方式併入本文中。
藉由浸滲操作及浸漬製程,業界己應用苯并化合物以製造預成形體、層壓物、PWB、模製化合物、密封劑、燒結粉末、澆鑄物件、結構性複合物零件及電氣與電子元件。為製備包含苯并化合物之組合物,可以添加阻燃劑、含溴、磷或氯之化合物及/或填料(參見如,EP 0458739、EP 356379、US 5,200,452、US 5,152,939、EP 1366053或JP2001220455)。然而,此等添加劑之使用具有若干缺點。例如,其等不溶於溶劑且因此在加工方面引起問題;其等在高溫下顯示不佳的氧化安定性;其等提供之固化樹脂通常具有不佳的物理性質;及其當與火接觸時,尤其當在鹵化化合物存在下,會燃燒形成有毒氣體。因此,需要製造一種未顯示此等缺點且可在高溫環境下使用的以苯并為主之組合物。
本發明提供一種不含鹵素之可固化組合物,其包含:(a)結構式(I)之苯并單體
其中R各自獨立,代表烯丙基、未經取代或經取代之苯基、未經取代或經取代之C1
-C8
烷基或未經取代或經取代之C3
-C8
環烷基;(b)至少一種環氧樹脂;(c)觸媒;(d)增韌劑;及(e)溶劑。
不含鹵素之可固化組合物可用於多種應用,包括彼等要求該組合物固化時可展現高玻璃轉化溫度者。因此,該不含鹵素之可固化組合物尤其適合在通常需要高玻璃轉化溫度之汽車或航空應用中,用作塗覆物或模製物。
一般而言,本發明提供一種不含鹵素之可固化組合物,其包括(a)苯并單體;(b)環氧樹脂;(c)觸媒;(d)增韌劑;及(e)溶劑。本發明之可固化組合物經固化而提供具有極佳平衡之機械與化學性質之固化物,此等性質包括例如高玻璃轉化溫度(Tg
)、分解溫度(Td
)、高拉伸強度、低熱膨脹係數、良好的可撓性及阻燃性。
本發明之不含鹵素之可固化組合物相對每100重量份之不含鹵素之可固化組合物包括約10-90重量份、較佳約30-50重量份、更佳約35-45重量份之苯并單體。如文中所用,術語「苯并單體」指具有至少一個經取代或未經取代之苯并基團之單體。苯并單體可為單官能、雙官能或三官能苯并化合物。而且,術語「苯并單體」所用處,應理解為可一起使用一種或多種苯并單體。
苯并單體可由如下通式表示:
其中b為0至3之間之整數;R為經取代或未經取代之C1
-C20
烷基、經取代或未經取代之C2
-C20
烯基、經取代或未經取代之C6
-C20
芳基、經取代或未經取代之C2
-C20
雜芳基、經取代或未經取代之C4
-C20
碳環基、經取代或未經取代之C2
-C20
雜環基或C3
-C8
環烷基;R1
為氫、烷基或烯基;及Z為直接鍵結(當b=2時)、經取代或未經取代之C1
-C20
烯基、經取代或未經取代之C6
-C20
芳烯基、經取代或未經取代之C2
-C20
雜芳烯基或C=O。
在一個實施例中,苯并單體為通式(I)之化合物:
其中R各自獨立,代表烯丙基、未經取代或經取代之苯基、未經取代或經取代之C1
-C8
烷基或未經取代或經取代之C3
-C8
環烷基。R基團上之適宜取代基包括胺基、C1
-C4
烷基及烯丙基。R-基團上可存在1至4個取代基。R-基團較佳為相同且更佳為苯基。
可自多種來源購得苯并單體,包括Huntsman Advanced Materials Americas Inc.、Georgia Pacific Resins Inc.及Shikoku化學製品公司。在移除水的條件下,令酚類化合物(例如:雙酚A或酚酞)與醛(例如:甲醛)及第一胺反應,亦可獲得苯并單體。酚類化合物與醛之莫耳比可為約1:3至1:10,較佳約1:4至1:7,更佳約1:4.5至1:5。酚類化合物與第一胺反應物之莫耳比可為約1:1至1:3,較佳約1:1.4至1:2.5,更佳約1:2.1至1:2.2。第一胺之實例包括:芳族單或二胺、脂肪胺、環脂族胺及雜環單胺;例如,苯胺、鄰-、間-及對-苯二胺、聯苯胺、4,4'-二胺基聯苯甲烷、環己胺、丁胺、甲胺、己胺、烯丙基胺、糠胺、乙二胺及丙二胺。胺類可在其等各別的碳部分經C1
-C8
烷基或烯丙基取代。較佳的第一胺係根據通式Ra
NH2,其中Ra
為烯丙基、未經取代或經取代之苯基、未經取代或經取代之C1
-C8
烷基或未經取代或經取代之C3
-C8
環烷基。Ra
基團上之適宜取代基包括胺基、C1
-C4
烷基及烯丙基。一般而言,Ra
基團上可存在1至4個取代基。Ra
基團較佳為苯基。
本發明之不含鹵素之可固化組合物亦相對每100重量份之不含鹵素之可固化組合物包括約2-60重量份、較佳約20-40重量份之至少一種環氧樹脂。該環氧樹脂之實例包括聚縮水甘油基環氧化合物、非縮水甘油基環氧化合物、環氧甲酚酚醛清漆及環氧酚酚醛清漆化合物。
第5,639,413號中,其以引用方式併入文中。其他尚包括含一個或多個環氧己烷基團與包含一個或多個環氧戊烷基團之環氧化物的環氧樹脂。
特別適宜的非縮水甘油基環氧化合物包括以下雙官能團非縮水甘油基環氧化合物,其中環氧基形成脂環或雜環體系之一部分:雙(2,3-環氧環戊基)醚、1,2-雙(2,3-環氧環戊氧基)乙烷、3,4-環氧環己烷甲酸3,4-環氧環己基-甲酯、3,4-環氧-6-甲基環己烷甲酸3,4-環氧-6-甲基-環己基甲酯、二(3,4-環氧環己基甲基)己二酸酯、二(3,4-環氧-6-甲基環己基甲基)己二酸酯、伸乙基雙(3,4-環氧環己烷甲酸酯)、乙二醇二(3,4-環氧環己基甲基)醚、二氧化乙烯基環己烯、二氧化二環戊二烯或2-(3,4-環氧環己基-5,5-螺-3,4-環氧)環己烷-1,3-二氧雜環己烷及2,2'-雙-(3,4-環氧環己基)-丙烷。
不含鹵素之可固化組合物亦相對每100重量份不含鹵素之可固化組合物包括約0.1-20重量份、較佳約0.5-15重量份之觸媒,以加速不含鹵素之可固化組合物之固化。
在一個實施例中,該觸媒為酚類化合物,較佳具有兩個或更多官能團。此等酚類化合物之實例包括:a)自苯酚或烷基化苯酚與甲醛之反應所獲得之樹脂,諸如酚醛清漆樹脂或可溶酚醛樹酯;及b)多羥基芳香族物質,諸如:參(羥基苯基)甲烷;參(羥基苯基)乙烷;1,3,5-三羥基苯;及四酚基乙烷。
本發明之不含鹵素之可固化組合物進一步在每100重量份之不含鹵素之可固化組合物中包括約0.1-40重量份、較佳約0.5-20重量份之增韌劑。
在一個實施例中,該增韌劑為如下通式之化合物
其中m為1或2,n為2至6,R0
為除去終端異氰酸根、胺基或羥基後之彈性預聚合物之n價自由基,該彈性預聚合物可溶於或分散於環氧樹脂中;X及Y彼此獨立,代表-O-或-NR3
-,至少一個X或Y為-NR3
-;R2
為除去酚系羥基及(視需要)胺基後之多酚或胺基酚之m+1價自由基;R3
為氫、C1
-C6
烷基或酚基。
美國專利第5,278,257號,第4欄第20行至第16欄第20行詳細敍述通式(II)之增韌劑,其揭示內容係以引用之方式併入文中。增韌劑之一實例為Flexibilizer DY 965(自美國亨斯邁先進材料有限公司(Hustsman Advanced Materials Americas Inc.)可購得,根據美國專利第5,278,257號之實例16製備)。
除組分(a)-(d)外,本發明之不含鹵素之可固化組合物亦相對每100重量份之不含鹵素之可固化組合物包括約1-50重量份、較佳約5-40重量份、更佳約20-30重量份之溶劑。
在一個實施例中,該溶劑係選自包括甲基乙基酮、丙酮、N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、戊醇、丁醇、二氧戊環、異丙醇、甲氧基丙醇、甲氧基丙醇醋酸酯、二甲基甲醯胺、乙二醇、乙二醇醋酸酯、甲苯、二甲苯及其混合物之群。
除以上確定之組分(a)-(e)外,該不含鹵素之可固化組合物亦可包括(如需要)可提高強度、釋放性、耐水解性、導電性及其他特性之添加劑。可以相對每100重量份不含鹵素之可固化組合物添加少於約50重量份、更佳少於約30重量份及最佳少於約20重量份之添加劑至不含鹵素之可固化組合物中。
此等視需要選用的添加劑可包括補強纖維,諸如:金屬纖維(例如鐵、銅、黃銅、青銅、鋁)、陶瓷纖維、玻璃纖維、碳纖維、石膏纖維、石棉、矽灰石、海泡石、矽鎂土、合成礦物纖維、芳族聚醯胺纖維、聚醯亞胺纖維、聚醯胺纖維、酚系纖維、纖維素纖維及丙烯酸纖維;填料;微球體或空心球體;可塑劑;碳黑或石墨;染料;及金屬粉末。
本發明之不含鹵素之可固化組合物可依己知方式製備,例如,可藉由預混合單獨組分,然後混合此等預混合物,或使用常規裝置,諸如攪拌容器、攪拌棒、球磨機、樣品混合器、靜態混合器或螺帶式摻混機,將所有組分一起混合。調配後,本發明之不含鹵素之可固化組合物可包裝於各種容器中,諸如不銹鋼、錫、鋁、塑膠、玻璃或紙板容器中。
根據一項實施例,相對每100重量份之不含鹵素之可固化組合物,取約10-90重量份之苯并單體、約2-60重量份之環氧樹脂、約0.1-20重量份之觸媒、約0.1-40重量份之增韌劑及約1-50重量份之溶劑一起混合,製備本發明之不含鹵素之可固化組合物。在另一項實施例中,相對每100重量份之不含鹵素之可固化組合物,取約30-50重量份之苯并單體、約20-40重量份之環氧樹脂、約0.5-15重量份之觸媒、約0.5-20重量份之增韌劑及約5-40重量份之溶劑一起混合,製備本發明之不含鹵素之可固化組合物。
混合後,然後可將該不含鹵素之可固化組合物施用於基材上,在大於150℃之溫度下固化,形成複合物物件。
在另一實施例中,混合及固化後,該不含鹵素之可固化組合物提供具有大於120℃、更佳大於160℃、最佳大於200℃及尤佳大於230℃之玻璃轉化溫度之固化的複合物物件。
因此,在另一實施例中,本發明提供一種不含鹵素之可固化組合物,相對每100重量份之不含鹵素之可固化組合物,其包含:(a)10-90重量份之結構式(I)之苯并單體
其中R各自獨立代表烯丙基、未經取代或經取代之苯基、未經取代或經取代之C1
-C8
烷基或未經取代或經取代之C3
-C8
環烷基;(b)2-60重量份之至少一種環氧樹脂;(c)0.1-20重量份之觸媒;(d)0.1-40重量份之增韌劑;及(e)1-50重量份之溶劑,其中該不含鹵素之可固化組合物經固化後,具有大於160℃、較佳大於200℃及更佳大於230℃之玻璃轉化溫度。
本發明之不含鹵素之可固化組合物可用於多種應用,諸如,澆鑄、層壓、浸滲、塗佈、黏結或膠合、塗漆、結合、絕緣,或包埋、壓製、射出成型、擠製、砂模結合、發泡和燒蝕材料。
因此,在本發明之另一項實施例中,該不含鹵素之可固化組合物可用作膠黏劑,以膠合或黏著由相同或不同基材製成之部件,形成物件。首先,將不含鹵素之可固化組合物與兩個或多個待結合之相同或不同基材中至少一個接觸。可依不同方式將不含鹵素之可固化組合物施用至基材,諸如經由擠出、噴霧、印刷或塗佈。在一項實施例中,不含鹵素之可固化組合物夾在第一與第二基材之間。然後在大於150℃之溫度下加熱該不含鹵素之可固化組合物及基材。藉由施加熱,形成黏結結合,以將基材膠黏在一起且形成物件。可施用不含鹵素之可固化組合物之基材包括塑膠、金屬、陶瓷、玻璃、石墨及纖維素材料。
本發明之不含鹵素之可固化組合物尤其適於需要高熱安定性之應用,例如形成複合物物件作為燃料電池,用於:提供一般汽車、混合動力汽車、小型船之能量;小規模局部發電;家庭發電;用於獨立場所(如露營地)的簡單供電;及用於衛星、空間開發及電腦的供電。
因此,在另一實施例中,將不含鹵素之可固化組合物施用至石墨且經鑄造以產製燃料電池。將石墨、不含鹵素之可固化組合物及(視需要)脫模劑(例如巴西棕櫚蠟、脂肪酸酯、硬脂酸或褐煤酸之金屬鹽)混合於混合器中,經揉捏及或射出成型、傳遞模塑或壓縮模塑,以產製燃料電池。
A)以苯并為主之不含鹵素之可固化組合物之製備將表1中以下組分加至玻璃容器中及充分地混合至均勻:
然後澆鑄實例1-6及在200℃至255℃下固化1-5小時,繼之在200℃至240℃下後固化1-4小時。根據ASTME1545-05、ASTME1641-07、ASTME831-05及AMTM-0046,分析性測試該固化產物且提供以下性質:
儘管上文己詳細敍述本發明之製造及應用之不同實施例,應理解本發明提供涵括可在許多不同明確內容中具體實現之可應用的發明觀念。文中討論之具體實施例僅說明製造及利用本發明之明確方式,而不限定本發明之範圍。
Claims (10)
- 一種不含鹵素之可固化組合物,其包含,相對每100重量份之該不含鹵素之可固化組合物,(a)30至50重量份之結構式(I)之苯并單體
- 如請求項1之不含鹵素之可固化組合物,其中R為苯基。
- 如請求項1之不含鹵素之可固化組合物,其中該酚系化合物具有兩個或更多官能團。
- 如請求項1之不含鹵素之可固化組合物,其中該環氧樹脂是非縮水甘油基化合物。
- 如請求項1之不含鹵素之可固化組合物,其中該溶劑係選自包括甲基乙基酮、丙酮、N-甲基-2-吡咯烷酮、N,N-二甲基甲醯胺、戊醇、丁醇、二氧戊環、異丙醇、甲氧基丙醇、甲氧基丙醇醋酸酯、二甲基甲醯胺、乙二醇、乙二醇醋酸酯、甲苯、二甲苯及其混合物之群。
- 一種不含鹵素之可固化組合物,其包含,相對每100重量份之該不含鹵素之可固化組合物:(a)30至50重量份之結構式(I)苯并單體
- 一種用於製造不含鹵素之可固化組合物之方法,其包含共同混合,相對每100重量份之該不含鹵素之可固化組合物,: (a)30至50重量份之結構式(I)苯并單體
- 一種根據如請求項7之方法所製造的不含鹵素之可固化組合物。
- 一種用於製造複合物物件之方法,其包括將如請求項1之不含鹵素之可固化組合物施用至至少一基材,且在大於150℃之固化溫度下加熱該基材與不含鹵素之可固化組合物以製造複合物物件。
- 如請求項9之方法,其中該基材為石墨。
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Publication number | Priority date | Publication date | Assignee | Title |
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TWI374137B (en) * | 2004-09-28 | 2012-10-11 | Huntsman Adv Mat Switzerland | Organic compounds |
WO2010031826A1 (en) * | 2008-09-19 | 2010-03-25 | Henkel Ag & Co. Kgaa | Benzoxazine-based compositions containing isocyanate-based tougheners |
CN102372903B (zh) * | 2010-08-18 | 2014-04-16 | 合正科技股份有限公司 | 无卤无磷热固型树脂组成物 |
TWI405787B (zh) * | 2010-10-08 | 2013-08-21 | Uniplus Electronics Co Ltd | 熱固型樹脂組成物 |
US20120095132A1 (en) * | 2010-10-19 | 2012-04-19 | Chung-Hao Chang | Halogen- and phosphorus-free thermosetting resin composition |
JP5948662B2 (ja) * | 2011-10-20 | 2016-07-06 | パナソニックIpマネジメント株式会社 | 樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板 |
GB201205574D0 (en) | 2012-03-29 | 2012-05-16 | Cytec Tech Corp | Benzoxazines and compositions containing the same |
US9902706B2 (en) | 2014-10-27 | 2018-02-27 | Cytec Industries Inc. | Process for making benzoxazines |
BR112017013941B1 (pt) * | 2014-12-29 | 2021-08-24 | Cytec Industries Inc | Composição curável, material compósito, e, métodos para formar um pré-impregnado e para fabricar uma peça compósita, pré-impregnado |
CA2987755A1 (en) | 2015-06-12 | 2016-12-15 | Leon Dyers, Jr. | Curable compositions containing benzoxazine epoxy blend and use thereof |
RU2748127C2 (ru) * | 2015-07-23 | 2021-05-19 | ХАНТСМАН ЭДВАНСТ МАТИРИАЛЗ АМЕРИКАС ЭлЭлСи | Отверждаемые бензоксазиновые композиции |
KR102324393B1 (ko) * | 2016-04-28 | 2021-11-10 | 에네오스 가부시키가이샤 | 경화 수지용 조성물 및 그 경화물 |
KR102338982B1 (ko) * | 2016-06-27 | 2021-12-14 | 코오롱인더스트리 주식회사 | 열경화성 수지 조성물, 이를 이용한 프리프레그 및 기판 |
WO2018051930A1 (ja) * | 2016-09-16 | 2018-03-22 | Jsr株式会社 | レジスト下層膜形成用組成物、レジスト下層膜及びその形成方法並びにパターニングされた基板の製造方法 |
US11555095B2 (en) | 2019-03-29 | 2023-01-17 | Carbon, Inc. | Dual cure resin for the production of moisture-resistant articles by additive manufacturing |
WO2022066565A1 (en) | 2020-09-25 | 2022-03-31 | Carbon, Inc. | Epoxy dual cure resin for the production of moisture-resistant articles by additive manufacturing |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU529162A1 (ru) * | 1975-07-11 | 1976-09-25 | Пермский государственный фармацевтический институт | Способ получени производных 1,4-бензоксазина |
ES2025260B3 (es) * | 1987-08-26 | 1992-03-16 | Ciba-Geigy Ag | Resinas epoxidicas modificadas |
EP0307666A1 (de) * | 1987-08-26 | 1989-03-22 | Ciba-Geigy Ag | Phenol-terminierte Polyurethane oder Polyharnstoffe und Epoxidharze enthaltend diese Verbindungen |
US5278257A (en) * | 1987-08-26 | 1994-01-11 | Ciba-Geigy Corporation | Phenol-terminated polyurethane or polyurea(urethane) with epoxy resin |
ES2088905T3 (es) | 1988-07-18 | 1996-10-01 | Gurit Essex Ag | Resinas endurecibles para formar plasticos dificilmente inflamables y resistentes a altas temperaturas y procedimientos para su fabricacion. |
ES2111522T3 (es) * | 1988-09-06 | 1998-03-16 | Ciba Geigy Ag | Resinas epoxi modificadas por polimeros en bloque y poliuretanos o poliureas. |
DE4016296C1 (en) | 1990-05-21 | 1991-09-05 | Gurit-Essex Ag, Freienbach, Ch | Flame retardant thermosetting adhesive for metals etc. - comprises oxa:aza:tetralin, halogenated epoxy] resins and opt. additives |
EP0493310A1 (de) | 1990-12-21 | 1992-07-01 | Gurit-Essex AG | Zu schwerentflammbaren Kunststoffen härtbare Harzmischungen und deren Verwendung |
US5152939A (en) | 1991-03-12 | 1992-10-06 | Edison Polymer Innovation Corp. | Composite densification with benzoxazines |
US5639413A (en) | 1995-03-30 | 1997-06-17 | Crivello; James Vincent | Methods and compositions related to stereolithography |
US7495060B2 (en) * | 1996-12-27 | 2009-02-24 | Nippon Soda Co., Ltd. | Tetrakisphenol and non-clathrated curing agent for epoxy resin |
SG63803A1 (en) * | 1997-01-23 | 1999-03-30 | Toray Industries | Epoxy-resin composition to seal semiconductors and resin-sealed semiconductor device |
US6207786B1 (en) * | 1998-11-10 | 2001-03-27 | Edison Polymer Innovation Corporation | Ternary systems of benzoxazine, epoxy, and phenolic resins |
EP1268665B1 (en) * | 1999-12-13 | 2005-11-02 | Dow Global Technologies Inc. | Flame retardant phosphorus element-containing epoxy resin compositions |
JP4258936B2 (ja) | 2000-02-07 | 2009-04-30 | 豊和工業株式会社 | 改装窓 |
JP2001220455A (ja) | 2000-02-10 | 2001-08-14 | Mitsubishi Gas Chem Co Inc | プリプレグ及び積層板 |
EP1366053B1 (en) | 2001-01-22 | 2005-01-05 | Huntsman Advanced Materials (Switzerland) GmbH | Flame-proofing agents |
US6743852B2 (en) * | 2001-11-13 | 2004-06-01 | Henkel Corporation | Benzoxazines, thermosetting resins comprised thereof, and methods for use thereof |
US6620905B1 (en) * | 2002-02-23 | 2003-09-16 | National Starch And Chemical Investment Holding Corporation | Curable compositions containing benzoxazine |
JP2004043653A (ja) | 2002-07-12 | 2004-02-12 | Toray Ind Inc | スリットテーププリプレグ、およびその成形品 |
JP4245377B2 (ja) | 2003-03-07 | 2009-03-25 | 株式会社Adeka | 高弾性エポキシ樹脂組成物 |
US20070221690A1 (en) * | 2004-05-18 | 2007-09-27 | Kuperus Johan B | Positioning of a Container in a Beverage Dispensing Apparatus |
CN103554184A (zh) * | 2004-05-28 | 2014-02-05 | 陶氏环球技术有限责任公司 | 可用于制造无卤素抗引燃聚合物的含磷化合物 |
TWI374137B (en) * | 2004-09-28 | 2012-10-11 | Huntsman Adv Mat Switzerland | Organic compounds |
US7649060B2 (en) | 2005-12-02 | 2010-01-19 | Henkel Corporation | Curable compositions |
EP1647576A1 (en) * | 2005-04-01 | 2006-04-19 | Huntsman Advanced Materials (Switzerland) GmbH | Composition comprising benzoxazine and epoxy resin |
WO2007075769A1 (en) * | 2005-12-22 | 2007-07-05 | Dow Global Technologies Inc. | A curable epoxy resin composition and laminates made therefrom |
JP2008214561A (ja) * | 2007-03-07 | 2008-09-18 | Toray Ind Inc | 繊維強化複合材料用樹脂組成物、プリプレグおよび繊維強化複合材料。 |
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