TWI775423B - 共聚物與複合材料 - Google Patents
共聚物與複合材料 Download PDFInfo
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Abstract
Description
本揭露關於導熱的共聚物,更特別關於共聚物的單體種類。
雲端、互聯、及物聯網的興起、4G、5G通訊技術與顯示技術提升,光電與半導體等產業所需之電路板與IC載板走向高速化、高密度化、密集化、與積層化,因此未來其特性需求除低介電、高絕緣性外,需兼具低介電損失、與高導熱性,以電路板為例,其結構中的銅箔基板之簡易結構為銅箔/介電層/銅箔,中間介電層之組成物多為導熱性差之樹脂、玻纖布、或絕緣紙,導致銅箔基板的導熱性差。
為解決上述問題,目前亟需新的導熱樹脂,以增加銅箔之間的介電層導熱性。
本揭露一實施例提供之共聚物,係由:(A)芳香性單體、其寡聚物、或其聚合物,以及(B)脂肪族單體、其寡聚物、或其聚合物共聚而成,其中芳香性單體的化學結構為
,其中每一R
1各自為H或CH
3,且n=1-4;R
2係單鍵、-O-、
、
、
、
、
、
、
、
、
、
、或
,R
4係C
2-10的烷撐基;每一R
5各自為單鍵、-O-、
、
、
、
、
、
、
、
、
、或
,且o係1-70;每一R
3各自為
或
,其中R
6係H或CH
3,且R
7係C
1-10的烷撐基。
在一些實施例中,脂肪族單體係1,3-丁二烯、異戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯、2-甲基-1,3-戊二烯、2,3-二甲基-1,3-戊二烯、4,5-二乙基-1,3-辛二烯、
、
、或
;其中R
8係C
1-12的烷撐基或環烷撐基;R
9係
或
,R
10係H或CH
3;R
11係C
2-5的烷撐基;R
12係H或CH
3;以及q=1-70。
在一些實施例中,(A)芳香性單體、其寡聚物、或其聚合物與(B)脂肪族單體、其寡聚物、或其聚合物的莫耳比例(A/B)為1:2至99:1。
本揭露一實施例提供之複合材料,包括:1重量分的共聚物;以及9至99重量分的無機粉體,其中共聚物係由:(A)芳香性單體、其寡聚物、或其聚合物,以及(B)脂肪族單體、其寡聚物、或其聚合物共聚而成,其中芳香性單體的化學結構為
,其中每一R
1各自為H或CH
3,且n=1-4;R
2係單鍵、-O-、
、
、
、
、
、
、
、
、
、
、或
,R
4係C
2-10的烷撐基;每一R
5各自為單鍵、-O-、
、
、
、
、
、
、
、
、
、或
,且o係1-70;每一R
3各自為
或
,其中R
6係H或CH
3,且R
7係C
1-10的烷撐基。
在一些實施例中,脂肪族單體係1,3-丁二烯、異戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯、2-甲基-1,3-戊二烯、2,3-二甲基-1,3-戊二烯、4,5-二乙基-1,3-辛二烯、
、
、或
;其中R
8係C
1-12的烷撐基或環烷撐基;R
9係
或
,R
10係H或CH
3;R
11係C
2-5的烷撐基;R
12係H或CH
3;以及q=1-70。
在一些實施例中,(A)芳香性單體、其寡聚物、或其聚合物與(B)脂肪族單體、其寡聚物、或其聚合物的莫耳比例(A/B)為1:2至99:1。
在一些實施例中,無機粉體包括氮化鋁、氮化硼、氧化鋁、氫氧化鎂、二氧化矽、或上述之組合。
本揭露一實施例提供之共聚物,係由(A)芳香性單體、其寡聚物、或其聚合物,以及(B)脂肪族單體、其寡聚物、或其聚合物共聚而成。芳香性單體的化學結構為
,其中每一R
1各自為H或CH
3,且n=1-4;R
2係單鍵、-O-、
、
、
、
、
、
、
、
、
、
、或
,R
4係C
2-10的烷撐基;每一R
5各自為單鍵、-O-、
、
、
、
、
、
、
、
、
、或
,且o係1-70;每一R
3各自為
或
,其中R
6係H或CH
3,且R
7係C
1-10的烷撐基。
在一些實施例中,脂肪族單體係1,3-丁二烯、異戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯、2-甲基-1,3-戊二烯、2,3-二甲基-1,3-戊二烯、4,5-二乙基-1,3-辛二烯、
、
、或
;其中R
8係C
1-12的烷撐基或環烷撐基;R
9係
或
,R
10係H或CH
3;R
11係C
2-5的烷撐基;R
12係H或CH
3;以及q=1-70。
在一些實施例中,(A)芳香性單體、其寡聚物、或其聚合物與(B)脂肪族單體、其寡聚物、或其聚合物的莫耳比例(A/B)為1:2至99:1。若(A)芳香性單體、其寡聚物、或其聚合物的比例過 低,則聚合物的傳熱性不足(比如傳熱係數(W/mK)低於0.3)。
本揭露一實施例提供之複合材料,包括:1重量分的上述共聚物;以及9至99重量分的無機粉體。複合材料中的共聚物可與前述的共聚物類似,在此不贅述。若無機粉體的比例過高,則 粉體不易均勻分散在共聚物中。在一些實施例中,無機粉體包括氮化鋁、氮化硼、氧化鋁、氫氧化鎂、二氧化矽、或上述之組合。
在一實施例中,上述共聚物或複合材料可用於接著劑或封裝材料。在一實施例中,可將含共聚物或複合材料的塗料(含有機溶劑)塗佈至載體上,接著烘乾塗料以形成塗層。在一些實施例中,載體可為銅箔、聚合物膜(如聚醯亞胺膜、聚對苯二甲酸乙二酯膜、或其他聚合物膜)、或類似物。上述塗層具有熱傳導性高(傳熱係數(W/mK)≥0.3,甚至傳熱係數(W/mK)≥0.4)、高頻介電常數低(Dk @10 GHz ≤3.2甚至Dk @10 GHz ≤2.8)、以及高頻介電損失低(Df @10 GHz ≤ 0.003甚至Df @10 GHz ≤ 0.0027)等特性。
在一實施例中,可將含有塗層於其上的載體對向壓合,且塗層彼此接觸。當載體為銅箔時,壓合後的結構即所謂的銅箔基板。在一實施例中,上述壓合製程的壓力介於5Kg至50Kg之間,溫度介於150℃至250℃之間,且歷時1小時至10小時之間。
在一實施例中,可將補強材含浸於塗料中(A-stage),接著將含浸後的補強材置入50.0℃至500.0℃的烘箱,烘乾塗料以形成膠片(B-stage)。在一實施例中,補強材包括玻璃、陶瓷、碳材、樹脂、或上述之組合,且補強材之形狀為纖維、粉體、片狀物、編織物、或上述之組合。舉例來說,補強材可為玻纖布。上述膠片具有熱傳導性高(傳熱係數(W/mK)≥ 0.3,甚至傳熱係數(W/mK)≥0.4)、高頻介電常數低(Dk @10 GHz ≤ 3.2甚至Dk @10 GHz ≤2.8)、以及高頻介電損失低(Df @10 GHz ≤ 0.003甚至Df @10 GHz ≤ 0.0027)等特性。在一實施例中,可將一或多個膠片夾設於銅箔之間,再壓合成銅箔基板,在一實施例中,壓合製程的壓力介於5Kg至50Kg之間,溫度介於150℃至250℃之間,且歷時1小時至10小時之間。
為讓本揭露之上述內容和其他目的、特徵、和優點能更明顯易懂,下文特舉出較佳實施例,作詳細說明如下:
[實施例]
在下述實施例中,傳熱係數(W/mK)的量測標準為ASTMD5470,高頻介電常數(Dk@10 GHz)的量測標準為ASTM D150-11,高頻介電損耗(Df@10 GHz)的量測標準為ASTM D150-11。
合成例a-1
取4,4’-二羥基聯苯(186 g,1 mol)、甲基丙烯酸酐(370 g,2.4 mol)、碳酸氫鈉(17g,0.2 mol)於氮氣下加熱至80℃並反應2小時。反應完成後加入2M氫氧化鈉水溶液1公升,攪拌隔夜後過濾產物,水洗後烘乾。得產物312克,其氫譜如下:
1H NMR (400 MHz, CDCl
3): 7.58 (d, 4H, J=8.0 Hz), 7.19 (d, 4H, J=8.0 Hz), 6.37 (s, 2H),5.77 (s, 2H), 2.08(s, 6H)。上述產物之結構如下:
合成例a-2
取4,4’-二羥基苯乙酮(214 g,1 mol)、甲基丙烯酸酐(370 g,2.4 mol)、碳酸氫鈉(17g,0.2 mol),於氮氣下加熱至80°C並反應2小時。反應完成後加入2M氫氧化鈉水溶液1公升,攪拌隔夜後過濾產物,水洗後烘乾得產物(345 g),其氫譜如下:
1H NMR (400 MHz, d
6-DMSO): 7.83 (d, 4H, J=8.0 Hz), 7.39 (d, 4H, J=8.0 Hz), 6.30 (s, 2H), 5.95 (s, 2H), 2.02(s, 6H)。上述產物之結構如下:
合成例a-3
取4-羥基苯乙酮(136 g,1 mol)、甲基丙烯酸酐(185 g,1.2 mol)、碳酸氫鈉(8.4 g,0.1 mol),於氮氣下加熱至80°C反應2小時。反應完成後加入2M氫氧化鈉水溶液700毫升,攪拌隔夜後過濾產物,水洗後烘乾。得中間產物198克(收率97%)。將中間產物加入硫酸肼(64 g,0.49mol)、三乙胺(49 g,0.49mol)、與乙醇(200 g)後,迴流反應5小時。反應結束後降至室溫,待產物析出後以乙醇與去離子水清洗產物並烘乾得產物(120克),其氫譜如下:
1H NMR (400 MHz, d
6-DMSO): 7.97 (d, 4H, J=8.0 Hz), 7.26 (d, 4H, J=8.0 Hz), 6.30 (s, 2H), 5.91 (s, 2H), 2.29 (s, 6H), 2.01(s, 6H)。上述產物之化學結構如下:
合成例a-4
取4,4’-二羥基聯苯(47 g,0.25 mol)、碳酸鉀(53 g,0.5 mol)、與丙酮(100毫升)混合後加熱至迴流。另將1,3-二溴丙烷(20 g,0.1 mol)溶於丙酮(100 mL),慢慢滴入迴流的混合物中。滴加完成後迴流反應二小時。反應結束後過濾去除鹽類,並濃縮濾液以去除溶劑,水洗後烘乾得產物(40 g),其氫譜如下:
1H NMR (400 MHz, d
6-DMSO): 7.40 (d, 4H, J=8.0 Hz), 7.36 (d, 4H, J=8.0 Hz), 6.99 (d, 4H, J = 8.0 Hz), 6.78 (d, 4H, J = 8.0 Hz), 4.16 (t, 4H, J = 4.0 Hz), 2.20-2.16 (m, 2H)。上述產物之化學結構如下:
合成例a-5
取4-羥基苯甲醛(122 g,1 mol)、1-溴丙烯(145 g,1.2 mol)、碳酸鉀(207 g,1.5 mol)與四氫呋喃(500 mL),於氮氣下加熱迴流三小時。反應完成後過濾,迴旋濃縮去除溶劑,得產物4-丙烯基苯甲醛(154 g)。將4-丙烯基苯甲醛加入1,3-丙二醇雙(4-氨基苯甲酸酯)(31.4 g,0.1 mol)、氯化鋅催化劑(5 g)與乙醇(500 mL),加熱迴流反應4小時。反應結束後降至室溫,過濾產物並用乙醇清洗後烘乾以得產物(55 g),其氫譜如下:
1H NMR (400 MHz,d6-DMSO):8.50(s,2H),7.95(d,4H,J=8.0Hz),7.86(d,4H,J=8.0Hz),7.24(d,4H,J=8.0Hz),7.06(d,4H,J=8.0Hz),6.10-6.02(m,2H),5.43(dd,2H,J=8.0,1.2Hz),5.29(dd,2H,J=8.0,1.2Hz),4.66(d,4H,J=8.0Hz),4.45(t,4H,J=4.0Hz),2.23-2.18(m,2H)。上述產物之結構如下:
實施例1
取322g之合成例a-1的產物、318g之雙馬來醯亞胺(購自大和化成工業株式會社之BMI-TMH)、與5g之自由基起始劑101(2,5-Bis(tert-butyl peroxy)-2,5-dimethylhexane,購自Aldrich)溶於1000mL的環己酮中,迴流反應2小時以得共聚物。合成例a-1的產物與BMI-TMH的莫耳比為50:50。將上述共聚物塗佈成厚100μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.3,高頻介電常數(Dk@10GHz)為2.36,高頻介電損耗(Df@10GHz)為0.0021。此外,上述共聚物於THF的溶解度為67wt%。BMI-TMH之結構如下:
實施例2
取635 g之合成例a-3的產物、304 g之聚乙二醇二甲基丙烯酸酯(購自Sigma-aldrich之PEGDMA,Mw=700)、與7 g之自由基起始劑101溶於1000 mL的N-甲基吡咯烷酮(NMP)中,迴流反應2小時以得共聚物。合成例a-3的產物與PEGDMA的莫耳比為55:35。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.34,高頻介電常數(Dk@10 GHz)為2.42,高頻介電損耗(Df@10 GHz)為0.0023。此外,上述共聚物於THF的溶解度為65 wt%。PEGDMA之結構如下:
實施例3
取602 g之合成例a-5的產物、159 g之BMI-TMH、與7.6 g之自由基起始劑101溶於1000 mL的二甲基乙醯胺(DMAc)中,迴流反應2小時以得共聚物。合成例a-5的產物與BMI-TMH的莫耳比為50:25。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.39,高頻介電常數(Dk@10 GHz)為2.43,高頻介電損耗(Df@10 GHz)為0.0026。此外,上述共聚物於THF的溶解度為62 wt%。
實施例4
取492 g之合成例a-4的產物、53 g之環烷基二丙烯酸酯(購自日本化藥之R-684)、與5.5 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。合成例a-4的產物與R-684的莫耳比為75:13。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.43,高頻介電常數(Dk@10 GHz)為2.4,高頻介電損耗(Df@10 GHz)為0.0028。此外,上述共聚物於THF的溶解度為60 wt%。R-684的結構如下:
實施例5
取347 g之合成例a-2的產物、2 g之PEGDMA、與3.5 g之自由基起始劑101溶於1000 mL的環己酮中,迴流反應2小時以得共聚物。合成例a-2的產物與PEGDMA的莫耳比為99:1。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.45,高頻介電常數(Dk@10 GHz)為2.38,高頻介電損耗(Df@10 GHz)為0.0029。此外,上述共聚物於THF的溶解度為60 wt%。
實施例6
取161 g之合成例a-1的產物、175 g之合成例a-2的產物、318 g之BMI-TMH、與4 g之自由基起始劑101溶於1000 mL的環己酮中,迴流反應2小時以得共聚物。「合成例a-1的產物及合成例a-2的產物」與BMI-TMH的莫耳比為50:50。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.3,高頻介電常數(Dk@10 GHz)為2.39,高頻介電損耗(Df@10 GHz)為0.0022。此外,上述共聚物於THF的溶解度為67 wt%。
實施例7
取100 g之合成例a-2的產物、140 g之合成例a-4的產物、57 g之PEGDMA、與3 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。「合成例a-2的產物及合成例a-4的產物」與PEGDMA的莫耳比為50:25。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.38,高頻介電常數(Dk@10 GHz)為2.36,高頻介電損耗(Df@10 GHz)為0.0024。此外,上述共聚物於THF的溶解度為63 wt%。
實施例8
取100 g之合成例a-3的產物、149 g之合成例a-5的產物、2 g之R-684、與2.5 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。「合成例a-3的產物及合成例a-5的產物」與R-684的莫耳比為99:1。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.42,高頻介電常數(Dk@10 GHz)為2.39,高頻介電損耗(Df@10 GHz)為0.0028。此外,上述共聚物於THF的溶解度為60 wt%。
實施例9
取100 g之合成例a-2的產物、140 g之合成例a-4的產物、57 g之PEGDMA、與3 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。「合成例a-2的產物及合成例a-4的產物」與PEGDMA的莫耳比為50:25。將300g的氮化硼與上述共聚物混合後塗佈成厚100 μm的膜,烘乾形成的塗層之傳熱係數(W/mK)為2.41,高頻介電常數(Dk@10 GHz)為3.08,高頻介電損耗(Df@10 GHz)為0.0025。上述塗層中的氮化硼含量約為50 wt%。
實施例10
取100 g之合成例a-2的產物、140 g之合成例a-4的產物、57 g之PEGDMA、與3 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。「合成例a-2的產物及合成例a-4的產物」與PEGDMA的莫耳比為50:25。將700g的氮化硼與上述共聚物混合後塗佈成厚100 μm的膜,烘乾形成的塗層之傳熱係數(W/mK)為3.24,高頻介電常數(Dk@10 GHz)為3.36,高頻介電損耗(Df@10 GHz)為0.0026。上述塗層中的氮化硼含量約為70 wt%。
實施例11
取100 g之合成例a-2的產物、140 g之合成例a-4的產物、57 g之PEGDMA、與3 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。「合成例a-2的產物及合成例a-4的產物」與PEGDMA的莫耳比為50:25。將1700g的氮化硼與上述共聚物混合後塗佈成厚100 μm的膜,烘乾形成的塗層之傳熱係數(W/mK)為4.85,高頻介電常數(Dk@10 GHz)為3.49,高頻介電損耗(Df@10 GHz)為0.0028。上述塗層中的氮化硼含量約為85 wt%。
實施例12
取20 g之合成例a-1的產物、4 g之聚(1,3-丁二烯) (購自日本曹達之NiSSO-PB B1000)、與0.24 g之自由基起始劑101溶於10 mL的NMP中,迴流反應2小時以得共聚物。合成例a-1的產物與B1000的莫耳比為19:1。將上述共聚物塗佈成厚150μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.32,高頻介電常數(Dk@10 GHz)為2.24,高頻介電損耗(Df@10 GHz)為0.0026。此外,上述共聚物於THF的溶解度為65 wt%。
比較例1
取20 g之合成例a-1的產物、174 g之PEGDMA、與1.8 g之自由基起始劑101溶於1000 mL的環己烷中,迴流反應2小時以得共聚物。合成例a-1的產物與PEGDMA的莫耳比為20:80。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.221,高頻介電常數(Dk@10 GHz)為2.44,高頻介電損耗(Df@10 GHz)為0.0031。此外,上述共聚物於THF的溶解度為66 wt%。
比較例2
取17 g之合成例a-4的產物、40 g之BMI-TMH、與0.5 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。合成例a-4的產物與BMI-TMH的莫耳比為20:80。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.227,高頻介電常數(Dk@10 GHz)為2.46,高頻介電損耗(Df@10 GHz)為0.0034。此外,上述共聚物於THF的溶解度為62 wt%。
比較例3
取10 g之合成例a-3的產物、7 g之合成例a-5的產物、與120 g之R-864、與1.3 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。「合成例a-3的產物及合成例a-5的產物」與R-864的莫耳比為20:80。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.223,高頻介電常數(Dk@10 GHz)為2.48,高頻介電損耗(Df@10 GHz)為0.0036。此外,上述共聚物於THF的溶解度為61 wt%。
比較例4
取207 g之市售PPE-acrylate (購自六和化工之Sabic SA9000)、12 g之聚(1,3-丁二烯) (購自日本曹達之NiSSO-PB B1000)、與2 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。PPE-acrylate與聚(1,3-丁二烯)的莫耳比為90:10。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.221,高頻介電常數(Dk@10 GHz)為2.44,高頻介電損耗(Df@10 GHz)為0.0042。此外,上述共聚物於THF的溶解度為65 wt%。
比較例5
取184 g之市售PPE-acrylate (購自六和化工之Sabic SA9000、24 g之聚(1,3-丁二烯) (購自日本曹達之NiSSO-PB B1000)、與2 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。PPE-acrylate與B1000的莫耳比為80:20。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.217,高頻介電常數(Dk@10 GHz)為2.46,高頻介電損耗(Df@10 GHz)為0.0037。此外,上述共聚物於THF的溶解度為65 wt%。
比較例6
取161 g之市售PPE-acrylate (購自六和化工之Sabic SA9000)、36 g之B1000、與2 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。PPE-acrylate與B1000的莫耳比為70:30。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.203,高頻介電常數(Dk@10 GHz)為2.48,高頻介電損耗(Df@10 GHz)為0.0034。此外,上述共聚物於THF的溶解度為65 wt%。
比較例7
取200 g之市售之液晶高分子E5204L (購自Sumitomo)、24 g之B1000、與2 g之自由基起始劑101溶於1000 mL的NMP中,迴流反應2小時以得共聚物。E5204L與B1000的莫耳比為70:30。將上述共聚物塗佈成厚100 μm的膜後,烘乾形成的塗層之傳熱係數(W/mK)為0.23,高頻介電常數(Dk@10 GHz)為2.8,高頻介電損耗(Df@10 GHz)為0.0045。此外,上述共聚物於THF的溶解度為5 wt%。
雖然本揭露已以數個實施例揭露如上,然其並非用以限定本揭露,任何所屬技術領域中具有通常知識者,在不脫離本揭露之精神和範圍內,當可作任意之更動與潤飾,因此本揭露之保護範圍當視後附之請求項所界定者為準。
無。
無。
無。
Claims (9)
- 如請求項5所述之複合材料,其中該無機粉體包括氮化鋁、氮化硼、氧化鋁、氫氧化鎂、二氧化矽、或上述之組合。
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