TW201529611A - 合成聚３，４－伸乙二氧基噻吩（ｐｅｄｏｔ）－電解共聚物之方法 - Google Patents
合成聚３，４－伸乙二氧基噻吩（ｐｅｄｏｔ）－電解共聚物之方法 Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract 3
- 239000004816 latex Substances 0.000 claims description 17
- 229920000126 latex Polymers 0.000 claims description 17
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 230000005693 optoelectronics Effects 0.000 claims description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002109 single walled nanotube Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 9
- -1 poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 210000003739 neck Anatomy 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241001479434 Agfa Species 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QIFCIFLDTQJGHQ-UHFFFAOYSA-M potassium;2-phenylethenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 QIFCIFLDTQJGHQ-UHFFFAOYSA-M 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Abstract
本發明關於一種於單一步驟中合成聚(3,4-伸乙二氧基噻吩)-電解共聚物複合物之方法。
Description
本發明關於一種於單一步驟中合成聚(3,4-伸乙二氧基噻吩)-電解共聚物複合物之方法。
已知縮寫為PEDOT之聚(3,4-伸乙二氧基噻吩)為1980年代末期於德國Bayer AG之實驗室中與AGFA集團共同研究發現的聚合物。
該聚合物特別被用於有機電子應用中，尤其用於光伏打電池中，但是更普遍地用光電子應用中，因為其良好的導電性及特別因為其對氧化的穩定性和其透明性。
該聚合物係與合成之後添加的電解共聚物一起使用，使得所得複合物形成予體-受體系統且為水溶性。PEDOT的合成通常發生在界面活性劑的存在下，其偶爾難以移除。
申請者發現可相伴製備PEDOT-電解共聚物之複合乳膠，亦即在單一步驟中。除了簡化方法之外，還不用額外
的添加劑(諸如界面活性劑)直接獲得PEDOT-電解共聚物，電解共聚物充當為穩定劑。當與添加電解共聚物至預製備之PEDOT中比較時，在以此方式製備時所獲得的乳膠亦更穩定。
本發明的概述：
本發明關於一種相伴合成PEDOT及電解共聚物之方法，其包含以下的連續步驟：-在反應器中於介於15與25℃之間的溫度下以攪拌製備水與離子性單體之溶液，- 引入預溶解在溶劑中的EDOT之溶液，- 攪拌，直到溶解為止，- 引入溶劑-非離子單體分散液，- 攪拌，直到所得分散液轉變成白色為止，- 加熱至介於35與55℃之間的溫度，- 引入引發劑與剩餘EDOT之溶液，- 連續攪拌及加熱，同時連續或半連續引入剩餘EDOT與引發劑之溶液。
明確地理解此方法包含其他的初步或中間步驟或繼上述那些步驟之後的步驟。
詳細說明：
術語〝聚(3,4-伸乙二氧基噻吩)與電解共聚物之複合乳膠的相伴聚合反應〞意指其中單體3,4-伸乙二氧基噻
吩(EDOT)及電解共聚物之前驅物單體係使用相同的引發劑同時聚合的聚合反應。
術語〝電解共聚物〞意指包含至少一種離子性單體之任何聚合物。
該共聚物可為離子性與非離子性單體之任何組合。
離子性單體可為苯乙烯磺酸鹽、丙烯酸鹽、攜帶膦醯基醯亞胺官能和磺醯基醯亞胺官能之化合物。其較佳為苯乙烯磺酸鈉或鉀，及其更佳為苯乙烯磺酸鈉。
非離子性單體可為苯乙烯、經取代之苯乙烯或(甲基)丙烯酸烷酯。此單體較佳為苯乙烯。
EDOT與電解共聚物之前驅物單體的相伴聚合反應係於使用水溶性引發劑的乳液中進行。該引發劑優先為過硫酸鹽，及更特別為過硫酸銨，但是可使用任何其他的水溶性引發劑。過硫酸銨有可能經由自由基途徑而使EDOT氧化聚合成PEDOT及電解共聚物之前驅物單體氧化聚合成電解共聚物。聚合反應可以分批、連續或半連續模式進行，有或沒有接種之初步合成步驟。聚合反應較佳地以半連續進行。合成溫度係介於35與55℃之間，較佳為介於40與50℃之間，及更佳為介於44與46℃之間。
(3,4-伸乙二氧基噻吩)-聚電解質共聚物複合乳膠可被用於分散奈米填充劑，諸如碳奈米管(CNT)(無論其為單壁或多壁)、石墨烯、富勒烯或該等奈米填充劑之組合。
(3,4-伸乙二氧基噻吩)-聚電解質共聚物複合乳膠可
被用於在奈米填充劑存在或不存在下製造導電性透明膜。導電性透明膜可被用於光伏打有機電池中或任何其他光電子應用中。
[圖1]聚(3,4-伸乙二氧基噻吩)-(共)-苯乙烯-苯乙烯磺酸酯複合乳膠之粒徑
[圖2]聚(3,4-伸乙二氧基噻吩)-(共)-苯乙烯-苯乙烯磺酸酯複合乳膠之Z-電位
[圖3]聚(3,4-伸乙二氧基噻吩)-(共)-苯乙烯-苯乙烯磺酸酯複合乳膠之兩種大小的TEM影像
[圖4]聚(3,4-伸乙二氧基噻吩)-(共)-苯乙烯-苯乙烯磺酸酯複合乳膠之AFM影像
PEDOT-聚苯乙烯-共-聚苯乙烯磺酸酯乳膠的合成：
聚合反應器裝配有循環用於加熱/冷卻系統之熱交換流體的夾套、引入用於測量介質溫度之探針的頸部、引入用於吹淨易於抑制聚合反應的氧氣之氮氣的頸部、連接至以不同的速度旋轉之馬達的攪拌器、兩個用於添加添加劑的頸部及連接至冷凝/回流系統的頸部。
將溶解在10毫升去礦質水中的390毫克苯乙烯磺酸酯(1莫耳/當量)(濃度0.04克/毫升)放入反應器中。
將攪拌設定在每分鐘450轉(rpm)。反應器進料係經由氮管線經至少15分鐘除氣，直到溶液均勻為止。接著將反應器維持在持久的氮氣流下。
在第二階段中，在適合的容器中製備以下三種混合物：a)自0.2毫升(亦即266毫克=1莫耳/當量)EDOT及6.6毫升異丙醇製成之溶液；b)藉助於超聲波浴，在3.4毫升異丙醇中的0.15毫升(亦即137.2毫克=0.6莫耳/當量)苯乙烯(St)之分散液；c)在26.4毫升去礦質水中的1.057克(亦即相對於EDOT的2.3莫耳/當量及相對於St+SS的0.1莫耳/當量)過硫酸銨之溶液(濃度0.04克/毫升)。
接著將反應器在600rpm下攪拌且引入第一個EDOT溶液(a)。將反應溫度維持在25℃±2℃。當反應器組份混合時，將苯乙烯單體之分散液(b)引入反應器中。在反應介質轉變成白色之後(形成乳膠晶種)，將標稱加熱上升，以便在反應器中到達45℃。當到達此溫度時，引入第一個四等分的引發劑溶液(c)且反應介質的顏色逐漸改變成綠/藍-綠色，其顯示EDOT開始聚合。在反應3小時之後，使用幫浦或針筒式壓力機開始連續計量剩餘的引發劑(c)，每3小時一個四等分(三次)，同時將反應器溫度維持在45℃±2℃。
在添加結束時，將溫度維持在45℃±2℃再經2小
時，然後冷卻且排出產物。最終產物的純化係以超過濾進行。所使用的過濾器為100千道爾頓(kilodalton)過濾器。此反應的產率持穩在80%。
最終產物藉由以下的各種技術特徵化。
DLS(動態光散射)技術顯示約0.16之粒子多分散性(PDI)及80奈米之體積直徑(圖1)。粒子係帶負電荷且Z-電位值等於-75.8mV(圖2)。
以透射顯微術(圖3)及AFM(圖4)觀察到球狀粒子。
將實施例1中所製備之PEDOT-聚苯乙烯-共-聚苯乙烯磺酸酯乳膠與市售乳膠(來自Clevios公司的PH1000)比較。
將該等產物分散在去離子水中(1質量%)且使用IKA T18 Ultra-Turrax機器在不同的速度下(15 500、20 000、24 000rpm)進行剪切，每一速度進行5分鐘。
接著以DLS測量粒子大小。粒子大小在任何試驗中皆未改變，證明市售產品及根據本發明所製備之產物有滿意的穩定性。
Claims (13)
- 一種相伴合成PEDOT及電解共聚物之方法，其包含以下的連續步驟：- 在反應器中於介於15與25℃之間的溫度下以攪拌製備水與離子性單體之溶液，- 引入預溶解在溶劑中的EDOT之溶液，- 攪拌，直到溶解為止，- 引入溶劑-非離子單體分散液，- 攪拌，直到所得分散液轉變成白色為止，- 加熱至介於35與55℃之間的溫度，- 引入引發劑與剩餘EDOT之溶液，- 連續攪拌及加熱，同時連續或半連續引入剩餘EDOT與引發劑之溶液。
- 根據申請專利範圍第1項之方法，其中該電解共聚物係由苯乙烯及苯乙烯磺酸酯所組成。
- 根據申請專利範圍第1項之方法，其中該電解共聚物係由丙烯酸之鹽及至少一種(甲基)丙烯酸烷酯所組成。
- 根據申請專利範圍第1項之方法，其中該引發劑為水溶性。
- 根據申請專利範圍第1項之方法，其中該引發劑為過硫酸鹽。
- 根據申請專利範圍第1項之方法，其中該引發劑為過硫酸銨。
- 一種乳膠，其係如申請專利範圍第1至6項中任一項之方法所獲得。
- 一種如申請專利範圍第7項之乳膠的用途，其係用於分散奈米填充劑。
- 根據申請專利範圍第8項之乳膠的用途，其中該奈米填充劑為碳奈米管。
- 根據申請專利範圍第8項之乳膠的用途，其中該奈米填充劑為單壁碳奈米管。
- 根據申請專利範圍第7至10項中任一項之乳膠的用途，其係用於製備導電性透明膜。
- 一種如申請專利範圍第11項所獲得之導電性透明膜。
- 一種如申請專利範圍第12項之透明膜的用途，其係用於光電子應用中，尤其用於光伏打有機電池中。
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| EP3063248A1 (fr) | 2016-09-07 |
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