TWI548631B - 光感測材料與光學裝置 - Google Patents

光感測材料與光學裝置 Download PDF

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TWI548631B
TWI548631B TW104141253A TW104141253A TWI548631B TW I548631 B TWI548631 B TW I548631B TW 104141253 A TW104141253 A TW 104141253A TW 104141253 A TW104141253 A TW 104141253A TW I548631 B TWI548631 B TW I548631B
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林建文
蔡易良
楊忠烈
劉仕賢
廖釗鋙
鄭功龍
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財團法人工業技術研究院
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Priority to CN201510995832.6A priority patent/CN106854194B/zh
Priority to US14/983,840 priority patent/US9771518B2/en
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Description

光感測材料與光學裝置
本技術領域關於光感測材料，更特別關於應用光感測材料之光學裝置。
感光變色性為習知的物理現象，其可見於某些化合物中。此現象的詳細討論可參考有機化學40中的研討專文“感光變色性：分子與系統”(由H.Durr及H.Bouas-Laurent主編，Elsevier,1990)。吡喃衍生物是習知具有感光變色效果的化合物，其於激發狀態下具有吸收波長。
上述感光變色材料可應用於變色鏡片、智慧窗、隔熱貼、或其他感光變色之樣用，其需具有快速與可逆的光變色特性。然而現有的感光變色材料之紫外光吸收係數較低，即對紫外光敏感性不足。現有的感光變色材料之恢復時間過長，即在不照射紫外光後亦無法快速轉變回透明態。此外，現有的感光變色材料熔點高且溶解性不佳，不易加工且需添加至其他材料(如液晶、溶劑、或高分子)中以改善其加工問題。綜上所述，目前亟需新的感光變色材料以克服上述缺點。
本揭露一實施例提供之光感測材料，其結構為： ，其中A1係、、、、、或，其 中A2與A3各自擇自、、、、、、或，其中X係鹵素；R係H、C1-12之烷基、或C1-12之烷氧基；以及R’係C1-12之烷基。
本揭露一實施例提供之光學裝置，包括：第一透明基板；第二透明基板；以及液晶材料夾設於第一透明基板與第二透明基板之間，且液晶材料包括光感測材料，其結構為：，其中A1係、、、、、或，其中A2與A3各自擇自、、、、、、或，其中X係鹵素；R係H、C1-12之烷基、或C1-12之烷氧基；以及R’係C1-12之烷基。
1‧‧‧液晶材料
3、5‧‧‧透明基板
10‧‧‧光學裝置
第1圖係本揭露一實施例中，光學裝置的示意圖。
本揭露一實施例提供之光感測材料，其結構如式1所示： 在式1中，A1係、、、、、或。A2與A3各自擇自、、、、、、或。上述X係鹵素，R係H、C1-12之烷基、或C1-12之烷氧基，且R’係C1-12之烷基。
在一實施例中，光感測材料之合成方式如下。值得注意的是，下述合成方式僅用以舉例，本技術領域中具有通常知識者自可依其設備與藥材選用其他合成路徑以形成光感測材料。
首先，取鹵化醛、二酸二酯、與鹼加熱反應，如式2所示。在式2中，X為鹵素，而R’為C1-12之烷基。
接著取式2之產物、醋酸鈉、與醋酸酐加熱迴流反應，如式3所示。
接著取式3之產物與碳酸鉀加熱迴流反應，如式4所示。
接著取式4之產物、炔類化合物、原甲酸三甲酯、與對甲苯磺酸吡啶鹽(PPTS)反應，如式5所示。在式5中，A2與A3之定義如前述。
接著取式5之產物、1,3,2-二氧雜硼烷類化合物、碳酸鈉、與四(三苯基膦)鈀進行Suzuki coupling，即得光感測材料如式6所示。在式6中，A1與R之定義同前述。
在一實施例中，光感測材料之結構如式7或式8所示。在式7與式8中，R之定義同前述。
在一實施例中，可先將多種液晶材料混合形成液晶主體材料後，將上述光感測材料添加至液晶主體材料中以形成液晶材料1。接著將上述液晶材料1置於透明基板3與5之間，即得光學裝置10，如第1圖所示。在一實施例中，透明基板3與5可為相同或不同材料，其可為剛性基板如玻璃或石英，亦可 為可撓性基板如塑膠。此光學裝置10在未照射紫外線時呈透明，但在照射紫外線後將迅速轉變為深色而不透光。當顏色變深之光學裝置10不再照射紫外線後，會在一段時間後轉變回透明無色。上述變色過程為可逆現象，因此光學裝置10可用於變色鏡片、智慧窗、隔熱貼、或他感光變色裝置。
為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下：
實施例
實施例1
將0.33莫耳之第三丁醇鉀與500mL之第三丁醇加入1L雙頸瓶中攪拌至全溶。混合0.3莫耳之三溴苯甲醛、0.3莫耳之琥珀酸二乙酯、與100mL之第三丁醇後，慢慢滴入反應瓶中。將上述混合物加熱至100℃後於100℃下反應4小時。接著將反應結果冷卻至室溫，以乙酸乙酯與水萃取數次，收集乙酸乙酯層並以無水硫酸鎂除水。過濾後取濾液濃縮，即得淡黃色液體產物(106g，產率96%)。上述反應如式9所示：
接著取0.288莫耳式9之產物、0.316莫耳之醋酸鈉、與0.5莫耳之醋酸酐加入500mL之雙頸瓶中攪拌至全溶，再加熱至140℃並迴流反應6小時。接著將反應結果冷卻至室溫，抽乾醋酸酐後，以乙酸乙酯與水萃取數次。收集乙酸乙酯層並 以無水硫酸鎂除水、過濾後取濾液濃縮。即得棕色液體產物(77g，產率75%)。上述反應如式10所示：
接著取0.216莫耳式10之產物、0.324莫耳之碳酸鉀、與150mL之乙醇加入250mL之雙頸瓶中攪拌至全溶，加熱至80℃並迴流反應4小時。接著將反應結果冷卻至室溫，抽乾乙醇後，以乙酸乙酯與水萃取數次。收集乙酸乙酯層並以無水硫酸鎂除水、過濾後取濾液濃縮。即得淡黃色液體(106g，產率95%)。上述反應如式11所示：
接著取0.194莫耳式11之產物、0.194莫耳之1-苯基-1-[4-(1-哌啶基)苯基]-2-丙炔-1-醇、0.388莫耳之原甲酸三甲酯、與150mL之二氯甲烷加入250mL之雙頸瓶中攪拌至全溶後，加入0.097莫耳之對甲苯磺酸吡啶鹽(PPTS)並加熱至迴流反應隔夜。接著將反應結果冷卻至室溫，以二氯甲烷與水萃取數次。收集二氯甲烷層並以無水硫酸鎂除水、過濾後取濾液濃縮。即得棕色液體產物(5.76g，產率52.5%)。上述反應如式12所示：
將1莫耳之4-(4-己基苯基)-苯甲酸溶於100mL之甲苯與100mL之異辛烷中。接著將1.5莫耳之1,3-丙二硫醇滴入上述溶液，並加熱至50℃。接著將1.5莫耳之三氟甲磺酸滴入上述溶液後，加熱至110℃並反應約4-6小時。反應結束後降至室溫，靜置後析出黃色固體(9.7g，產率約86%)。上述反應如式13所示。
將1莫耳式13之產物溶於150mL之二氯甲烷中，再降溫至-68℃。將1.2莫耳之4-溴酚與1.2莫耳之三乙胺溶於二氯甲烷後，將其慢慢滴入式13之產物溶液，並於-68℃下反應1小時，且溶液顏色由黃轉變至透明。接著於-68℃下再反應1小時，其由白色懸浮液析出黃色固體。之後以1M NaOH調整反應後之液體的pH值至5-8。接著以300mL之二氯甲烷與300mL之食鹽水萃取，取二氯甲烷層並以無水硫酸鎂除水。過濾後取濾液濃縮，以二氯甲烷/己烷(1/20)再結晶後，於室溫下抽真空三小時以得白色固體(6.8g，產率78%)。上述反應如式14所示。
取1莫耳式14之產物、2莫耳之雙戊醯二硼、3.4莫耳之醋酸鉀溶於甲苯，持續攪拌反應30分鐘。之後將0.02莫耳之四(三苯基膦)鈀加入上述溶液後繼續攪拌30分鐘，之後加熱至120℃並反應隔夜。反應完成後冷卻至室溫，以300mL之乙酸乙酯與300mL之食鹽水萃取反應結果，取乙酸乙酯層並以無水硫酸鎂除水，過濾後取濾液濃縮。以二氯甲烷/甲醇(1/20)再結晶後，於室溫下抽真空三小時以得白色固體(6.8g，產率90.6%)。上述反應如式15所示。
接著取0.102莫耳式12之產物、0.102莫耳之式15之產物、0.4莫耳之碳酸鈉、與300mL之甲苯加入500mL之雙頸瓶中攪拌至全溶後，加入0.01莫耳之四(三苯基膦)鈀並加熱至100℃並於100℃下反應6小時。接著將反應結果冷卻至室溫，以乙 酸乙酯與水萃取數次。收集乙酸乙酯層並以無水硫酸鎂除水、過濾後取濾液濃縮。即得棕色粗產物。接著以二氯甲烷/甲醇(v/v=1/2)再結晶上述粗產物即得淡紫色固體。上述固體於室溫下抽真空8小時以去除溶劑，得淡紫色固體產物(6.75g，產率85.8%)。上述反應如式16所示。
式16產物之光譜數據如下：1H NMR(400MHz,Acetone-d6)：δ 8.50(d,1H),8.23(d,1H),8.19(s,1H),8.00(t,1H),7.89(t,4H),7.83(d,2H),7.67(s,1H),7.64(d,2H),7.59(d,2H),7.57(s,2H),7.48(d,2H),7.40(s,2H),7.37(d,2H),7.33(t,1H),6.86(d,2H),6.43(d,1H),6.39(d,2H),3.10(t,4H),2.67(t,2H),1.63(d,3H),1.63(d,3H),1.59(s,2H),1.58(s,2H),1.40(t,2H),1.33(m,4H),1.28(m,4H),0.87(t,3H).ESI-Mass：分子式：C58H55F2N1O4，理論值：868.06，量測值：868.4715。
取0.00868g之式16產物溶於二氯甲烷，形成10mL之透明溶液，抽取1mL再以二氯甲烷稀釋成10mL，重複上述稀釋步驟3次後，配置成莫爾濃度1×10-6M之量測溶液，並將其置入槽內寬度為1cm之透明石英槽，並以UV/可見光光譜儀(SLM-468)量測其UV-Vis吸收光譜，求得最大吸收波長強度(absorption spectrum intensity)後以beer’s law(A=ε b c)換算，得知其吸收係數(ε)為1.02×106。
依第1表之組成與比例調配液晶的主體材料，添加式16產物後加熱至85℃使其完全溶解後冷卻至室溫。接著以虹吸方法將上述液晶材料灌入液晶測試盒(TN-Mode 22μm test cell)中，密封後測試樣品。接著將測試樣品放置於應答時間量測儀器(DMS-803c)上，先定義未曝照紫外光前之穿透率為基準線。之後以手持式UV燈(波長365nm)曝照液晶材料2分鐘，其外觀由透明色轉變成深紫色。接著迅速移除UV燈，並以DMS-803c評估測試樣品穿透率變化，計算測試樣品穿透率回復至100%所需時間(液晶材料之光應答時間)。式16產物之添加量、恢復時間、與最大添加量(超過則析出而不溶解)如第2表所示。
實施例2
將1莫耳之4-(4-戊基環己基)-苯甲酸溶於100mL之甲苯與100mL之異辛烷中。接著將1.5莫耳之1,3-丙二硫醇滴入上述溶液，並加熱至50℃。接著將1.5莫耳之三氟甲磺酸滴入上述溶液後，加熱至110℃並反應約4-6小時。反應結束後降至室溫，靜置後析出黃色固體(9.7g，產率約86%)。上述反應如式17所示。
將1莫耳式17之產物溶於150mL之二氯甲烷中，再降溫至-68℃。將1.2莫耳之4-溴酚與1.2莫耳之三乙胺溶於二氯甲烷後，將其慢慢滴入式17之產物溶液，並於-68℃下反應1小時，且溶液顏色由黃轉變至透明。接著於-68℃下再反應1小時，其由白色懸浮液析出黃色固體。之後以1M NaOH調整反應後之液體的pH值至5-8。接著以300mL之二氯甲烷與300mL之食鹽水萃取，取二氯甲烷層並以無水硫酸鎂除水。過濾後取濾液 濃縮，以二氯甲烷/己烷(1/20)再結晶後，於室溫下抽真空三小時以得白色固體(6.8g，產率78%)。上述反應如式18所示。
取1莫耳式18之產物、2莫耳之雙戊醯二硼、3.4莫耳之醋酸鉀溶於甲苯，持續攪拌反應30分鐘。之後將0.02莫耳之四(三苯基膦)鈀加入上述溶液後繼續攪拌30分鐘，之後加熱至120℃並反應隔夜。反應完成後冷卻至室溫，以300mL之乙酸乙酯與300mL之食鹽水萃取反應結果，取乙酸乙酯層並以無水硫酸鎂除水，過濾後取濾液濃縮。以二氯甲烷/甲醇(1/20)再結晶後，於室溫下抽真空三小時以得白色固體(6.8g，產率90.6%)。上述反應如式19所示。
取0.102莫耳式12之產物、0.102莫耳式19之產物、0.4莫耳之碳酸鈉、與300mL之甲苯加入500mL之雙頸瓶中攪拌 至全溶後，加入0.01莫耳之四(三苯基膦)鈀並加熱至100℃並於100℃下反應6小時。接著將反應結果冷卻至室溫，以乙酸乙酯與水萃取數次。收集乙酸乙酯層並以無水硫酸鎂除水、過濾後取濾液濃縮。即得棕色粗產物。上述反應如式20所示。接著以二氯甲烷/甲醇(v/v=1/2)再結晶上述粗產物即得淡紫色固體。上述固體於室溫下抽真空8小時以去除溶劑，得淡紫色固體產物(6.52g，產率84.5%)。
式20之產物光譜數據如下：1H NMR(400MHz,Acetone-d6)：δ 8.50(d,1H),8.23(d,1H),8.19(s,1H),8.00(t,1H),7.89(dd,2H),7.69(dd,2H),7.59(d,1H),7.57(d,2H),7.43(dd,4H),7.35(q,4H),7.25(t,1H),6.87(d,2H),6.44(d,2H),6.39(dd,2H),3.11(t,4H),2.78(t,1H),1.88(d,4H),1.59(t,4H),1.53(dd,4H),1.40(t,3H),1.31(m,9H),1.28(dd,2H),0.89(t,3H).ESI-Mass：分子式：C57H59F2N1O4，理論值： 860.08，量測值：860.4502。
以實施例1之方法量測式20產物之吸收係數(ε)為1.06×106。
此外，以實施例1之方法量測式20產物於液晶材料中的添加量、恢復時間、與最大添加量，如第2表所示。
比較例1
依美國專利US 8697890揭露之方式合成式21之化合物。
以實施例1之方法量測式21之化合物，其吸收係數(ε)為8.21×105。
此外，以實施例1之方法量測式21之化合物於液晶材料中的添加量、恢復時間、與最大添加量，如第2表所示。
比較例2
依美國專利US 8697890揭露之方式合成式22之化合物。
以實施例1之方法量測式22之化合物，其吸收係數(ε)為8.23×105。
此外，以實施例1之方法量測式22之化合物於液晶材料中的添加量、恢復時間、與最大添加量，如第2表所示。
由第2表之比較可知，含有-CF2O-之光感測材料具有較高的吸收係數、較快的恢復時間、與較高的添加量(即較好溶解度)，可有效提升應用其之光學裝置的效能，讓感光變色之光學裝置更為敏感、變色機制更為快速，並且與主體液晶材料結合應用更為容易。
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，任何本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申請專利範圍所界定者為準。
1‧‧‧液晶材料
3、5‧‧‧透明基板
10‧‧‧光學裝置

Claims (6)

  1. 一種光感測材料，其結構為： 其中A1係、、、、、或， 其中A2與A3各自擇自、、、、 、或，其中X係鹵素；R係H、C1-12之烷基、或C1-12之烷氧基；以及R’係C1-12之烷基。
  2. 如申請專利範圍第1項所述之光感測材料，其結構為： 其中R係C1-12之烷基。
  3. 如申請專利範圍第1項所述之光感測材料，其結構為： 其中R係C1-12之烷基。
  4. 一種光學裝置，包括：一第一透明基板；一第二透明基板；以及一液晶材料，夾設於該第一透明基板與該第二透明基板之間，該液晶材料包括光感測材料，其結構為： 其中A1係、、、、、或， 其中A2與A3各自擇自、、、、 、或，其中X係鹵素；R係H、C1-12之烷基、或C1-12之烷氧基；以及R’係C1-12之烷基。
  5. 如申請專利範圍第4項所述之光學裝置，其中該光感測 材料之結構為： 其中R係C1-12之烷基。
  6. 如申請專利範圍第4項所述之光學裝置，其中該光感測材料之結構為： 其中R係C1-12之烷基。
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