含三苯胺結構熱敏性凝膠之製備與性質研究

Studies on Preparation and Properties of Thermosensitive Hydrogels Containing Triphenylamine Moiety

陳重諭(Chong-Yu Chen)

指導教授 ： 李文福

大同大學/工程學院/化學工程學系所/碩士(2011年)

摘要

本論文係先合成具光致發光特性之單體tris(4-acrylamidophenyl)amine與4, 4’-diacrylamidotriphenylamine，以此單體與N, N’-methylene-bis-acrylamide (NMBA)為交聯劑，與具熱敏性質的N-isopropyl acrylamide (NIPAAm)為單體，製備成一系列具光致發光與熱敏性質的膠體。
第一部分先以對氟硝基苯及硝基苯胺合成出tris(4-nitrophenyl)amine (TNPA)，再加入聯胺及碳鈀在乙醇的環境中將其還原成tris(4-aminophenyl)amine (TAPA)之後，再與acryloyl chloride反應成具有三雙鍵的tris(4-acrylamidophenyl)amine (TAAPA)。再以不同比例的單體(TAAPA)與NMBA當雙交聯劑與NIPAAm單體溶於DMSO共聚合，製備一系列具溫度敏感性與光致發光性凝膠。本文主要探討TNPA、TAPA及TAAPA單體的光學性質以及TAAPA交聯劑含量對膠體特性之膨潤度、機械性質、孔隙度和發光特性的影響。
結果顯示TNPA、TAPA與TAAPA單體在溶劑中的光學性質量測上，當TNPA濃度大於6 ppm (1.58x10-5M)與TAPA濃度高於6 ppm (2x10-5M)時，其螢光發射會有自消光（Self-Quenching）現象，使得濃度高於此濃度時會導致螢光強度減弱的現象。將各單體溶於DMSO中，其TNPA的螢光波長出現在535 nm黃光，單體TAPA的螢光波長出現在442 nm藍光，但是TAAPA則無螢光產生；且吾人亦發現吸收波長會隨溶劑極性越高越往紅位移方向移動。而在膨潤度方面，以NIPAAm與NMBA及不同含量之TAAPA雙交聯劑的膠體在25 ℃量測，當添加0.1 mol%的TAAPA後，其膠體的膨潤度與吸水速率都有提升，但隨著TAAPA含量增加會使得吸水速率與膨潤度下降，此可用孔隙度儀量測膠體孔洞大小說明。在膠體強度方面，隨著TAAPA含量越高其膠體強度越大。NN-TAAPA膠體在光學量測上，其螢光顏色為淡藍色，且對200 nm到375 nm波長的光擁有非常好的吸收。
第二部分先以對氟硝基苯及苯胺合成出4, 4’-dinitrotriphenylamine (DNTPA)，再將其還原成4, 4’-diaminotriphenylamine (DATPA)之後，再與acryloyl chloride反應成具有二雙鍵的4, 4’-diacrylamidotriphenylamine (DAATA)。再將單體(DAATPA) 以不同比例與NMBA)當雙交聯劑與N-isopropyl acrylamide (NIPAAm)單體溶於DMSO共聚合，製備一系列具溫度敏感性與光致發光性水膠。本文主要探討此系列三胺衍生物單體的光學性質及DAATPA交聯劑含量對膠體之膨潤度、機械性質、孔隙度和發光特性等之影響。
DNTPA與DATPA、DAATPA單體在溶劑中的光學性質量測上，當DNTPA濃度大於4x10-5M與DATPA濃度高於5x10-5M時會有自消光（Self-Quenching）現象，其螢光強度會隨著濃度成長而減弱。將單體溶於DMSO中，其DNTPA的螢光波長出現在570 nm黃光，DATPA的螢光波長則出現在436 nm藍光，而DAATPA單體則沒有螢光產生，且發現吸收波長會隨溶劑極性越高越往紅位移方向移動。
而在膨潤度方面，以NIPAAm為主體以不同比例DAATPA含量與NMBA為交聯劑，所製的膠體在25 ℃量測，當添加0.1 mol%到0.2 mol%的DAATPA後，其膠體之膨潤度與吸水速率都有提升，但隨著添加量超過0.2 mol%時會使得吸水速率與膨潤度下降，此可用孔隙度儀量測膠體孔洞大小說明。此系列膠體在10分鐘的膨潤度即可達到平衡膨潤度的90%以上，具有較佳的溫敏性質。而在膠體強度方面，隨著DAATPA含量越高其膠體強度越大。NN-DAATPA膠體在光致發光行為上，結果顯示膠體添加DAATPA 交聯劑時，其螢光顏色為淡藍光，且對200 nm到334 nm波長的光擁有非常好的吸收。
第三部分係利用第一部分與第二部分所合成的單體4, 4’-diacrylamido triphenylamine (DAATPA)與tris(4-acrylamidophenyl)amine (TAAPA)，以不同比例與NMBA當雙交聯劑與NIPAAm單體溶於DMSO共聚合，製備一系列具溫度敏感性與光致發光性水膠。並且引述蘇培元學長合成之單體 (4-Acrylamido triphenylamine) (AATPA) 以不同比例與交聯劑NMBA與NIPAAm單體溶於DMSO，製備一系列具溫度敏感性與光致發光性水膠。本文主要比較不同三苯胺衍生物單體的含量對膠體膨潤度、機械性質和發光特性的影響與三苯胺衍生物的光學性質量測。
在膨潤度方面，當三苯胺衍生物AATPA含量提升時會造成膨潤度下降，而以DAATPA或TAAPA當作交聯劑與NMBA以雙交聯劑的方式與單體NIPAAm所製成之膠體，當添加DAATPA 0.2 mol%或TAAPA 0.1 mol%時，在吸水速率與膨潤度上比不添加三苯胺衍生物的膠體來的好。NN-DAATPA系列膠體在熱可逆量測上，前10分鐘的膨潤度即可達到平衡膨潤的90%以上，具有相當良好的溫敏性。
而在膠體強度方面，隨著三苯胺衍生物含量越高其膠體強度越大。在光學性質量測上，吸收波長會隨溶劑極性越高越往紅位移方向移動，含AATPA的copolymer的螢光波長在不可見光(395 nm)，而NN-DAATPA與NN-TAAPA系列膠體的螢光顏色皆為淡藍色(NN-DAATPA膠體PL放射波長在424 nm, 461 nm 與 483 nm ; NN-TAAPA膠體PL放射波長在424 nm, 461 nm 與483 nm)，且在這系列三苯胺衍生物中，發現當每增加一個acrylamido官能基時，其UV吸收與PL放射會有紅位移的現象。

關鍵字

凝膠 ； 溫度感應性 ； 三苯胺 ； 光致發光凝膠 ； 光致發光

並列摘要

In this thesis, the tris(4-acrylamidophenyl)amine and 4, 4’-diacrylamidotriphenylamine monomer with photoluminescence were synthesized at first, then the synthesized monomer and NMBA as crosslinkers and monomer, N-isopropyl acrylamide (NIPAAm), was polymerized to prepare a series of hydrogels having photoluminescence and thermosensitivity.
In the first part, tris(4-nitrophenyl)amine (TNPA) was prepared with 4-fluoronitrobenzene and nitrophenylamine, then reduced to tris(4-aminophenyl)amine (TAPA) by adding hydrazine and Pd/C in ethanol. Finally, the TAPA was acrylated with acryloyl chloride to form tris(4-acrylamidophenyl) amine (TAAPA). Then, a series of thermosensitive and photoluminescent hydrogels were prepared from NIPAAm and TAAPA and NMBA crosslinkers with different molar ratios. The effect of the content of crosslinker TAAPA in the hydrogels on their swelling ratio, mechanical property, and photoluminescent characteristic was investigated, and the optical property of three triphenylamine derivatives was also investigated.
The results showed that the self-quenching phenomenon was occurred in fluorescence emission when the concentration of TNPA is over 6 ppm (1.58x10-5M) and concentration of TAPA is over 6 ppm (2x10-5M) during measuring the optical property of TNPA and TAPA in solution, and the self-quenching phenomenon could diminish the intensity of fluorescence. But when the three monomers were dissolved in DMSO, the wavelength of fluorescence emission appears at 535 nm (yellow) for TNPA, at 442 nm (blue) for TAPA, but fluorescence emission does not appear for TAAPA. At the same time, we observed the red shift of the absorption wavelength when the polarity of solvent used is higher.
In the swelling ratio measurement, when adding 0.1 mol % of TAAPA, the swelling ratio and water absorption rate for the hydrogels increased, but decreased with an increase of TAAPA content. This result can be explained by capillary flow porometer measurement. In gel strength measurement, the gel strength became stronger with increasing amount of TAAPA. In photoluminescence measurement, the NN-TAAPA hydrogel showed the light blue fluorescence and absorbed UV well wavelength ranged from 200 nm to 375 nm when adding TAAPA into the hydrogels.
In the second part, 4, 4’-dinitrotriphenylamine (DNTPA) was prepared with 1-fluoro-4-nitrobenzene and aniline, then reduced to 4, 4’-diaminotriphenylamine (DATPA). The DATPA was acrylated by acryloyl chloride to form 4, 4’-diacrylamidotriphenylamine (DAATPA). Then, a series of thermosensitive and photoluminescent hydrogels were prepared from NIPAAm and DAATPA and NMBA crosslinkers with different molar ratios. The effect of the contents of DAATPA in the hydrogels on swelling ratio, mechanical property, pore size, and photoluminescent characteristic was investigated, and the optical property of the triphenylamine derivatives was also measured. The results showed that the self-quenching phenomenon was occurred in fluorescence emission when the concentration of DNTPA is over 4x10-5M and concentration of DATPA is over 5x10-5M during measuring the optical property of DNTPA, DATPA, and DAATPA in solution, and the self-quenching phenomenon could diminish the intensity of fluorescence. But when the three monomers were dissolved in DMSO, the wavelength of fluorescence for DNTPA and DATPA respectively appears at 570nm (yellow), at 436nm (blue), fluorescence of DAATPA does not appear. At the same time, the red shift of the absorption wavelength was occurred when the polarity of solvent used is higher. In the swelling ratio measurement, when adding 0.1 mol % to 0.2 mol % of DAATPA, the swelling ratio and water absorption rate for the hydrogels are increased, but decreased when adding more than 0.2 mol % of DAATPA into the hydrogels. The result can be explained by capillary flow porometer measurement. The swelling ratio of these series gels can reach 90% of equilibrium swelling ratio in 10 minutes with better thermosensitive. In gel strength measurement, the gel strength became stronger with increasing amount of DAATPA. In photoluminescence measurement, the NN-DAATPA gel showed the light blue fluorescence and absorbed UV well wavelength ranged from 200nm to 334nm when adding DAATPA into the hydrogels.
In final part, the study compares two series properties, one is a series of thermosensitive and photoluminescent hydrogels prepared from NIPAAm and DAATPA and TAAPA crosslinkers with different molar ratio. The other is from Pei-Yuan Su thesis, our previous study, that is a series of thermosensitive and photoluminescent hydrogels were prepared from NIPAAm and 4-acrylamido triphenylamine, (AATPA) and NMBA crosslinkers with different molar ratio. The effect of the contents of triphenylamine derivative in the hydrogels on swelling ratio, mechanical property, and photoluminescent characteristic was investigated, and the optical property of triphenylamine derivatives was also measured.
For swelling ratio measurement, the swelling ratio decreased when the amounts of triphenylamine derivative increased. And the hydrogels were prepared from NIPAAm and DAATPA or TAAPA and NMBA crosslinkers. When adding 0.1 mol % of DAATPA or 0.2 mol % TAAPA, the swelling ratio and water absorption rate for the hydrogels is better than pure poly(NIPAAm) gel. In thermoreversibity measurement for NN-DAATPA series hydrogels, the swelling ratio of these series gels can reach 90% of equilibrium swelling ratio in first 10 min with better thermosensitivity.
In gel strength measurement, the gel strength became stronger with increasing amount of triphenylamine derivative. In photoluminescent measurement, the red shift of the absorption wavelength was occurred when the higher polarity of solvent was used. And the wavelength of PL emission for the copolymeric hydrogels with AATPA appeared at invisible region (395 nm); but the NN-DAATPA and NN-TAAPA hydrogel showed a light blue fluorescence (PL emission spectrum for NN-DAATPA hydrogels appeared at 424 nm, 461 nm and 483 nm; PL emission spectrum for NN-TAAPA hydrogels appeared at 424 nm, 461 nm and 483 nm). Moreover, the red shift of the UV absorption and PL emission was arisen from adding one acrylamido functional group in these series of triphenylamine derivatives.

並列關鍵字

thermosensitive ； triphenylamine ； photoluminescence ； photoluminescence of hydrogel ； hydrogel

參考文獻

9. N. Satoh, T. Nakashima, K. Yamamoto, J. Am. Chem. Soc., 127, 13030, (2005).

12. C. Wang, C. Zhang, P. Wang, P. Zhu, W.Wu, C. Ye, L.R. Dalton, Polymer, 41, 2583 (2000).

14. S. H. Cheng, S. H. Hsiao, T. H. Su, G. S. Liou, Macromolecules, 38, 307, (2005).

15. J. H. Gorvin, J. Chem. Soc. Perkin Trans., 1331 (1988).

16. N. M. Patil, A. A. Kelkar, Z. N., R. V. Chaudhari, Chem. Commun., 2460, (2003).