TWI405801B - 具有電磁波干擾遮蔽效應之多壁碳奈米管/高分子奈米複合材之製備方法 - Google Patents
具有電磁波干擾遮蔽效應之多壁碳奈米管/高分子奈米複合材之製備方法 Download PDFInfo
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Description
本發明係關於一種具有電磁波干擾遮蔽效果之碳奈米管/高分子奈米複合材料,及其製備方法。
美國專利US2007012900-A1添加導電填充物製成導電高分子複合材料來提高材料對電磁波干擾遮蔽的效果,導電填充物是以碳為填充物的基本核心,如天然石墨、合成石墨、碳黑等,在核心外表面鍍上導電金屬,如鎳、銅、鋁、錫、鋅、金、銀、鉑等,選用橡膠烴做為材料之基材。由於該導電填充物的添加,提升了材料的導電性、電穩定性及機械性質,減少金屬的使用量,降低了材料的密度及材料成本。
WO 2007/010517 A1將合成好之聚合物添加到分散於乙醇或乙醚有機溶液的單、多壁奈米管(長度與半徑比大於100)或金屬、分金屬、氧化金屬等奈米粒子的懸浮液中,藉助於加熱迴流或超音波震盪使該聚合物於其中膨潤(swelling),再從該懸浮液中分離出該經過改質的聚合物。改質後的聚合物提升了原材料的強硬度、導電性、磁性,使該材料可以用為醫院之醫療設備達到電磁波干擾的遮蔽效應。
美國專利US2005/0127329 A1使用分散劑將將奈米材料分散在溶劑中,隨後混摻進熱固或熱塑性高分子中,移去溶劑後再添加硬化劑,製得奈米複合材料,奈米材料選用碳奈米管、奈米矽粒子、奈米石墨粒子等,高分子選用Epoxy、PC、壓克力樹酯等。製備出的材料具有高導電性及高導熱性,且提升了原基材的機械強度及尺寸穩定性,降低了表面摩擦力,因此在電磁波干擾的遮蔽效應上有優異的表現,可以應用在電子產品之塗料。
WO2004097853-A1將單壁或多壁碳奈米管及導電填充物(如碳黑或小碳球)添加到粒徑約0.5~5微米的水溶性高分子中,形成網狀結構的導電複合材料。該複合材料在奈米碳管含量0.04~3 wt%時,即達到展透值。可應用於電磁波干擾遮蔽之塗漆,塗料厚度約在25~500微米。
本發明的一主要目的在於提供一種具有電磁波干擾遮蔽效果之碳奈米管/高分子奈米複合材料之製備方法.本發明的較佳具體實施例包括(但不限於)下列項目:1.一種具有電磁波遮蔽效果之碳奈米管/高分子奈米複合材料的製備方法,包含下列步驟:a)製備一分散有碳奈米管的高分子溶液,該高分子溶液含有0.5-10重量%的碳奈米管;及b)將該分散有碳奈米管的高分子溶液塗佈於一基材,及乾燥所獲得的塗層。
2.如前述第1項的方法,其進一步包含c)堆疊多片步驟b)所得到的之具乾燥的塗層的基材。
3.如前述第2項的方法,其中步驟c)進一步包含於堆疊多片該具乾燥的塗層的基材之前先施予黏著劑於該基材上,而使堆疊的多片基材被黏結。
4.如前述第1項的方法,其中步驟b)所得到的之具乾燥的塗層的基材具有一厚度為0.05 mm至0.1 cm的乾燥的塗層。
5.如前述第4項的方法,其中步驟b)所得到的之具乾燥的塗層的基材具有一厚度為0.05 mm至0.1 cm的乾燥的塗層,及步驟c)堆疊2-100片之具乾燥的塗層的基材。
6.如前述第1項的方法,其中步驟a)包含將碳奈米管分散於溶劑中,將高分子單體及自由基起始劑溶解於該溶劑中,並於其中進行自由基聚合反應而形成該分散有碳奈米管的高分子溶液。
7.如前述第1項的方法,其中步驟a)包含將高分子溶於溶劑中或於一溶劑中聚合高分子單體而形成一高分子溶液,再將碳奈米管分散於該高分子溶液而形成該分散有碳奈米管的高分子溶液。
8.如前述第1項的方法,其中該碳奈米管為多壁碳奈米管。
9.如前述第1項的方法,其中該碳奈米管為單壁碳奈米管。
10.如前述第1項的方法,其中該碳奈米管為雙壁碳奈米管。
11.如前述第1項的方法,其中該碳奈米管為竹節形壁碳奈米管。
12.如前述第1項的方法,其中該碳奈米管為螺絲形壁碳奈米管。
13.如前述第1項的方法,其中該碳奈米管為具有二氧化鈦塗層的奈米碳管。
14.如前述第1項的方法,其中該碳奈米管為金屬包覆的奈米碳管。
15.如前述第6項的方法,其中該高分子單體選自丙烯酸,甲基丙烯酸,丙烯酸甲酯,甲基丙烯酸甲酯,及苯乙烯所組成的群組,或者該高分子單體同時為丙烯腈、丁二烯及苯乙烯。
16.如前述第15項的方法,其中該高分子單體為甲基丙烯酸甲酯。
17.如前述第16項的方法,其中將溶劑為N,N-二甲基乙醯胺(DMAc),該自由基起始劑為2,2-偶氮雙異丁腈(AIBN),及該自由基聚合反應係於120℃進行。
18.如前述第7項的方法,其中該高分子選自聚丙烯酸,聚甲基丙烯酸,聚丙烯酸甲酯,聚甲基丙烯酸甲酯,可溶性聚醯亞胺,可溶性聚醯胺醯亞胺,聚醯胺,聚苯乙烯,可溶性聚胺基甲酸酯,不飽和聚酯,丙烯腈-丁二烯-苯乙烯共聚物,聚醚碸(Poly-ether-sulfone,PES),可溶性聚醚醯亞胺(Poly-ether-imide,PEI)及環氧樹脂所組成的群組。
19.如前述第18項的方法,其中該高分子為聚甲基丙烯酸甲酯。
20.如前述第19項的方法,其中甲基丙烯酸甲酯單體被溶解於N,N-二甲基乙醯胺(DMAc)溶劑,加入2,2-偶氮雙異丁腈(AIBN)的自由基起始劑,及於120℃進行自由基聚合反應而形成聚甲基丙烯酸甲酯的溶液。
21.如前述第1項的方法,其中該基材為聚對苯二甲酸伸乙酯(PET)薄膜,聚醯亞胺(PI)薄膜,聚乙烯薄膜,聚丙烯薄膜,或聚氯乙烯薄膜。
22.如前述第21項的的方法,其中該基材為聚對苯二甲酸伸乙酯(PET)薄膜。
23.如前述第1項的方法,其中該基材為包覆電線的絕緣層。
24.如前述第4項的具有電磁波遮蔽效果之碳奈米管/高分子奈米複合材料可塗佈於PP薄膜上.
25.如前述第3項的具有電磁波遮蔽效果之碳奈米管/高分子奈米複合材料可塗佈於PVC薄膜上。
依本發明的一較佳具體實施例所完成的一種具有電磁波干擾遮蔽效果之奈米碳管/高分子複合材料之製備方法,包含以下步驟:(a)多壁碳奈米管(MWCNT)分散於N,N-二甲基乙醯胺(DMAc)溶劑中;(b)加入高分子單體甲基丙烯酸甲酯(MMA)及起始劑2,2-偶氮雙異丁腈(AIBN);(c)於120℃下聚合MMA而形成含有MWCNT/PMMA奈米複合材料的溶液;(d)將該溶液塗佈於PET薄膜上,乾燥所塗佈的塗層;及(e)堆疊多片所得到的之具乾燥的塗層的PET薄膜並作為電磁波遮蔽材料使用。
依本發明的另一較佳具體實施例所完成的一種具有電磁波干擾遮蔽效果之奈米碳管/高分子複合材料之製備方法,包含以下步驟:(A)將高分子單體甲基丙烯酸甲酯(MMA)及起始劑2,2-偶氮雙異丁腈(AIBN)溶解於N,N-二甲基乙醯胺(DMAc)溶劑中;(B)於120℃下聚合MMA而形成含有PMMA的溶液;(C)加入多壁碳奈米管(MWCNT)並藉助超音波將MWCNT分散於PMMA的溶液;(D)將分散有MWCNT的PMMA溶液塗佈於PET薄膜上,乾燥所塗佈的塗層;及(E)堆疊多片所得到的之具乾燥的塗層的PET薄膜並作為電磁波遮蔽材料使用。
本發明將藉由下列實施例被進一步了解,該等實施例僅作為說明之用,而非用於限制本發明範圍。
於下列的實施例及對照例中使用以下材料:多壁奈米碳管(MWCNT):The CNT Company製造,仁川,韓國。此奈米碳管以CVD方法製造。奈米碳管純度為93%,直徑為10-50 nm,長度為1-25 μm,比表面積為150-250 m2
g-1
。
甲基丙烯酸甲酯(MMA):Acros Organics Co.製造,New Jersey,USA。
2,2-偶氮雙異丁腈(AIBN):Tokyo Chemical Industry Co.,Ltd.製造,Tokyo,Japan.
2.62 g多壁碳奈米管分散於97.5g DMAc溶劑中,加入52.5 g高分子單MMA及0.11 g起始劑AIBN,於120℃下反應而成多壁碳奈米管/PMMA奈米複合材料。將上述之多壁碳奈米管/PMMA奈米複合材料模製成20 cm x 20 cm x 0.1 cm之板材.
重覆對照例1的步驟,但奈米碳管含量不同,其中:對照例2加入奈米碳奈量為0.13g;對照例3加入奈米碳奈量為0.26g;對照例4加入奈米碳奈量為0.39g;對照例5加入奈米碳奈量為0.53 g;及對照例6加入奈米碳奈量為1.31 g。
於97.5 g的DMAc中加入52.5 g高分子單體MMA及0.11 g起始劑AIBN,於120℃下反應而形成PMMA,加入2.62 g多壁碳奈米管並以超音波加予分散。將多壁碳奈米管/PMMA奈米複合材料模製成20 cm x 20 cm x 0.1 cm之板材。
重覆對照例2的步驟,但奈米碳管含量不同,其中:對照例8加入奈米碳奈量為0.13 g;對照例9加入奈米碳奈量為0.26 g;對照例10加入奈米碳奈量為0.39 g;對照例11加入奈米碳奈量為0.53 g;及對照例12加入奈米碳奈量為1.31 g。
2.62 g多壁碳奈米管分散於97.5 g DMAc溶劑中,加入52.5 g高分子單體MMA及0.11 g起始劑AIBN,於120℃下反應而成多壁碳奈米管/PMMA奈米複合材料。將上述之多壁碳奈米管/PMMA奈米複合材料塗佈於厚度為0.1 mm的PET薄膜上,並加熱揮發塗層中的溶劑,得到厚度為0.1 mm的多壁碳奈米管/PMMA奈米複合材料之塗層。塗佈面積為20 cm x 20 cm。依上述方法製備10片塗佈有多壁碳奈米管/PMMA奈米複合材料塗層的PET薄膜。將單片被塗佈的PET薄膜或多片被塗佈的PET薄膜堆疊在一起並作為電磁波遮蔽材料使用。
於97.5 g的DMAc中加入52.5 g高分子單體MMA及0.11 g起始劑AIBN,於120℃下反應而形成PMMA,加入2.62 g多壁碳奈米管並以超音波加予分散。將上述之多壁碳奈米管/PMMA奈米複合材料塗佈於厚度為0.1 mm的PET薄膜上,並加熱揮發塗層中的溶劑,得到厚度為0.1 mm的多壁碳奈米管/PMMA奈米複合材料之塗層。塗佈面積為20 cm x 20 cm。依上述方法製備10片塗佈有多壁碳奈米管/PMMA奈米複合材料塗層的PET薄膜。將單片被塗佈的PET薄膜或多片被塗佈的PET薄膜堆疊在一起並作為電磁波遮蔽材料使用。
測試方法:電磁波遮蔽效果(2~18GHz)以HP 8722ES測試,製造商Damaskos,Inc.Concordville,PA,USA.
結果:表1列出對照例1~6的奈米碳管/PMMA複合材料板材於15GHz之電磁波干擾遮蔽效果。表2列出對照例7~12的奈米碳管/PMMA複合材料板材於15GHz之電磁波干擾遮蔽效果。表3列出實施例1之單片被塗佈的PET薄膜或多片被塗佈的PET薄膜堆疊在一起作為電磁波干擾遮蔽材料於15GHz之電磁波遮蔽效果。表4列出實施例2之單片被塗佈的PET薄膜或多片被塗佈的PET薄膜堆疊在一起作為電磁波干擾遮蔽材料於15GHz之電磁波遮蔽效果。表1至表4的結果分別被示於圖1至圖4。從表1至表4及圖1至圖4所顯示的結果可以看出,本發明實施例1及2所製備之單片被塗佈的PET薄膜或多片被塗佈的PET薄膜堆疊在一起作為電磁波干擾遮蔽材料相較於同樣MWCNT用量的奈米碳管/PMMA複合材料板材具有顯著較佳的電磁波干擾遮蔽效果,例如表3中實施例10的41.98 dB(塗層厚度0.1 mm,10片堆疊)對照於表1中對照例1的18.56 dB(厚度0.1 cm板材,MWCNT含量4.76重量%);實施例5的17.03 dB(塗層厚度0.1 mm,5片堆疊)對照於對照例6的10.70 dB(厚度0.1 cm板材,MWCNT含量2.44重量%)。
圖1為對照例1~6之電磁波干擾遮蔽效果(2~18GHz)。
圖2為對照例7~12之電磁波干擾遮蔽效果(2~18GHz)b。
圖3為本發明實施例1~10之電磁波干擾遮蔽效果(2~18GHz)。
圖4本發明實施例11~20之電磁波干擾遮蔽效果(2~18GHz)。
Claims (16)
- 一種具有電磁波干擾遮蔽效果之碳奈米管/高分子奈米複合材料的製備方法,包含下列步驟:a)製備一分散有碳奈米管的高分子溶液,該高分子溶液含有0.5-10重量%的碳奈米管;b)將該分散有碳奈米管的高分子溶液塗佈於一基材,及乾燥所獲得的塗層;及c)堆疊多片步驟b)所得到的之具乾燥的塗層的基材,其中該高分子選自聚丙烯酸,聚甲基丙烯酸,聚丙烯酸甲酯,聚甲基丙烯酸甲酯,可溶性聚醯亞胺,可溶性聚醯胺醯亞胺,聚醯胺,聚苯乙烯,可溶性聚胺基甲酸酯,不飽和聚酯,丙烯腈-丁二烯-苯乙烯共聚物,聚醚碸(Poly-ether-sulfone,PES),可溶性聚醚醯亞胺(Poly-ether-imide,PEI)及環氧樹脂所組成的群組;該碳奈米管為多壁碳奈米管、單壁碳奈米管、雙壁碳奈米管、竹節形壁碳奈米管、螺絲形壁碳奈米管、二氧化鈦塗層的奈米碳管或金屬包覆的奈米碳管。
- 如申請專利範圍第1項的方法,其中步驟c)進一步包含於堆疊多片該具乾燥的塗層的基材之前先施予黏著劑於該基材上,而使堆疊的多片基材被黏結。
- 如申請專利範圍第1項的方法,其中步驟b)所得到的之 具乾燥的塗層的基材具有一厚度為0.05mm至0.1cm的乾燥的塗層。
- 如申請專利範圍第3項的方法,其中步驟b)所得到的之具乾燥的塗層的基材具有一厚度為0.05mm至0.1cm的乾燥的塗層,及步驟c)堆疊2-100片之具乾燥的塗層的基材。
- 如申請專利範圍第1項的方法,其中步驟a)包含將碳奈米管分散於溶劑中,將高分子單體及自由基起始劑溶解於該溶劑中,並於其中進行自由基聚合反應而形成該分散有碳奈米管的高分子溶液。
- 如申請專利範圍第1項的方法,其中步驟a)包含將高分子溶於溶劑中或於一溶劑中聚合高分子單體而形成一高分子溶液,再將碳奈米管分散於該高分子溶液而形成該分散有碳奈米管的高分子溶液。
- 如申請專利範圍第5項的方法,其中該高分子單體選自丙烯酸,甲基丙烯酸,丙烯酸甲酯,甲基丙烯酸甲酯,及苯乙烯所組成的群組,或者該高分子單體同時為丙烯腈、丁二烯及苯乙烯。
- 如申請專利範圍第7項的方法,其中該高分子單體為甲 基丙烯酸甲酯。
- 如申請專利範圍第8項的方法,其中將溶劑為N,N-二甲基乙醯胺(DMAc),該自由基起始劑為2,2-偶氮雙異丁腈(AIBN),及該自由基聚合反應係於120℃進行。
- 如申請專利範圍第6項的方法,其中該高分子為聚甲基丙烯酸甲酯。
- 如申請專利範圍第10項的方法,其中甲基丙烯酸甲酯單體被溶解於N,N-二甲基乙醯胺(DMAc)溶劑,加入2,2-偶氮雙異丁腈(AIBN)的自由基起始劑,及於120℃進行自由基聚合反應而形成聚甲基丙烯酸甲酯的溶液。
- 如申請專利範圍第1項的方法,其中該基材為聚對苯二甲酸伸乙酯(PET)薄膜,聚醯亞胺(PI)薄膜,聚乙烯薄膜,聚丙烯薄膜,或聚氯乙烯薄膜。
- 如申請專利範圍第12項的的方法,其中該基材為聚對苯二甲酸伸乙酯(PET)薄膜。
- 如申請專利範圍第1項的方法,其中該基材為包覆電線的絕緣層。
- 如申請專利範圍第12項的方法,其中該基材為聚丙烯薄膜。
- 如申請專利範圍第12項的方法,其中該基材為聚氯乙烯薄膜。
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| US12/081,517 US7955654B2 (en) | 2007-10-19 | 2008-04-17 | Method of preparation of a MWCNT/polymer composite having electromagnetic interference shielding effectiveness |
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