新型萘酚吡喃光致变色聚合物材料的合成与光学性质的研究
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摘要
光致变色材料广泛应用于光信息存储、光转换器件和光开关等前沿领域。由于聚合物比小分子具有好的成膜性,有利于器件的制造,使得光致变色聚合物的研究成为光功能材料研究的一个前沿领域。
萘酚吡喃分子是一类性能优良的光致变色材料,而目前很少有关于萘酚吡喃聚合物的报道。本文主要设计和合成新型的含萘酚吡喃基团的光致变色单体并通过原子转移自由基聚合(ATRP)反应得到线性的和交联的聚合物光致变色材料,主要从光辐射后吸收光谱的变化、热消色速率、抗疲劳程度、漂白动力学等方面研究它们的光致变色性质。合成含有香豆素基团的单体,并和含萘酚吡喃的光致变色单体或者和具有其他性质的单体如丙烯酸丁酯通过原子转移自由基聚合(ATRP)反应得到不同结构和性质的光致变色聚合物,研究并讨论光致变色性能的变化。通过调节萘酚吡喃单体的含量,也可以调节聚合物的光学和成膜性质。在这样的聚合物体系中,光学活性基团是通过化学键连接到聚合物主链上,与通过掺杂方式得到的光致变色体系相比,光学活性基团不与材料的主体发生分离,使材料具有更长的使用寿命。
本文通过核磁共振波谱(1H NMR)、质谱(MS)、凝胶渗透色谱、紫外-可见吸收光谱等手段对单体化合物和聚合物进行了表征。光学性能是在CHF-XM35-500W氙灯-汞灯高亮度点光源平行光源系统的照射下进行测定的。
Photochromic materials are widely used in optical information storage, optical switching devices and optical switches and other frontier areas. Polymer is beneficial to the manufacture of the device due to that polymer has better advantage to form film that small molecule.
Naphthopyran is a kind of photochromic materials with good performance, whereas there are just several reports about naphthopyran polymers. In this work, a novel naphthopyran-containing monomer is designed and synthesized, and used to fabricate linear and cross-linked polymer photochromic materials via atom transfer radical polymerization (ATRP). Their photochromic properties were mainly evaluated using changes of absorption spectra after UV light irradiation, rate of heat achromatic, fatigue resistivity and bleaching kinetics. Meanwhile, the containing-coumarin monomer was also synthesized, which was reacted with naphthopyran-containing photochromic monomer or butyl acrylate via ATRP in order to prepare photochromic polymers with different structures and property. The experimental results indicated that the photocrosslink of coumarin in polymer decrease the rate of heat achromatic. Optical and film-forming properties of polymer can be also regulated by changing the content of naphthopyran monomer. Compared with photochromic system obtained by doping mode, optically active groups in synthesized polymers were bonded to the main chain of polymer by chemical bonds in this polymer system, so that the optical groups were not dissociate from the main body of the material.
In this paper, monomers and polymers were characterized by means of NMR (1H NMR), mass spectrometry (MS), gel permeation chromatography and UV- visible absorption spectra. Optical performance was measured under the irradiation of the CHF-XM35-500W xenon lamp with a parallel light source system.
萘酚吡喃分子是一类性能优良的光致变色材料,而目前很少有关于萘酚吡喃聚合物的报道。本文主要设计和合成新型的含萘酚吡喃基团的光致变色单体并通过原子转移自由基聚合(ATRP)反应得到线性的和交联的聚合物光致变色材料,主要从光辐射后吸收光谱的变化、热消色速率、抗疲劳程度、漂白动力学等方面研究它们的光致变色性质。合成含有香豆素基团的单体,并和含萘酚吡喃的光致变色单体或者和具有其他性质的单体如丙烯酸丁酯通过原子转移自由基聚合(ATRP)反应得到不同结构和性质的光致变色聚合物,研究并讨论光致变色性能的变化。通过调节萘酚吡喃单体的含量,也可以调节聚合物的光学和成膜性质。在这样的聚合物体系中,光学活性基团是通过化学键连接到聚合物主链上,与通过掺杂方式得到的光致变色体系相比,光学活性基团不与材料的主体发生分离,使材料具有更长的使用寿命。
本文通过核磁共振波谱(1H NMR)、质谱(MS)、凝胶渗透色谱、紫外-可见吸收光谱等手段对单体化合物和聚合物进行了表征。光学性能是在CHF-XM35-500W氙灯-汞灯高亮度点光源平行光源系统的照射下进行测定的。
Photochromic materials are widely used in optical information storage, optical switching devices and optical switches and other frontier areas. Polymer is beneficial to the manufacture of the device due to that polymer has better advantage to form film that small molecule.
Naphthopyran is a kind of photochromic materials with good performance, whereas there are just several reports about naphthopyran polymers. In this work, a novel naphthopyran-containing monomer is designed and synthesized, and used to fabricate linear and cross-linked polymer photochromic materials via atom transfer radical polymerization (ATRP). Their photochromic properties were mainly evaluated using changes of absorption spectra after UV light irradiation, rate of heat achromatic, fatigue resistivity and bleaching kinetics. Meanwhile, the containing-coumarin monomer was also synthesized, which was reacted with naphthopyran-containing photochromic monomer or butyl acrylate via ATRP in order to prepare photochromic polymers with different structures and property. The experimental results indicated that the photocrosslink of coumarin in polymer decrease the rate of heat achromatic. Optical and film-forming properties of polymer can be also regulated by changing the content of naphthopyran monomer. Compared with photochromic system obtained by doping mode, optically active groups in synthesized polymers were bonded to the main chain of polymer by chemical bonds in this polymer system, so that the optical groups were not dissociate from the main body of the material.
In this paper, monomers and polymers were characterized by means of NMR (1H NMR), mass spectrometry (MS), gel permeation chromatography and UV- visible absorption spectra. Optical performance was measured under the irradiation of the CHF-XM35-500W xenon lamp with a parallel light source system.
引文
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[44]Fang Zheng,wang Shu-zhi. Synthesis and photochromism in solution of Phenoxy naphthacenequinone derivatives.Journal of Photochemistry and Photobiology A: Chemistry,1995,88:23-30.
[45]李红霞,刘颖.苯氧基蒽醌的合成和光致变色性质.延边大学学报(自然科学版),2004,30(4):278-280.
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[49]Ryoka Matsushima,Masafumi Nishiyama,Masamichi Doi. Improvements in the fatigue resistances of photochromic compounds.Journal of Photochemistry and Photobiology A:Chemistry,2001,139:63-69.
[50]刘莹,姚祖光.俘精酸酐—光致变色化合物.感光材料,1996.1:5-12.
[51]Irie M,Uchida K.Bul1.Chem.Soc.Jpn,1998,71:985-996.
[52]黄震年(Huang Z N),赵伟利(Zhao W L),樊美公(Fan M G).化学通报(Chemistry),1996,12:l6-2l.
[53]Irie M. Chem.Rev,2000,l00:l685-l7l6.
[54]Cabrera I,Dittrich A,Ringsdorf H. Angew.Chem.Int.Ed.Eng1,1991,30:76-78.
[55]Fukaminato T,Kawai T,irie M. Jpn.J.App1.Phys,2000,39:L633-L634.
[56]于明昕(Yu M x),周啸(Zhou x).功能材料(Functional Materials),2001,32(2):203-205.
[57]Kanakkanatt S V,Patel V S,Pate1 R G,eta1. Mo1.Cryst.Liq.Cryst,1994,246:159- 168.
[58]Li J,Schuster G B,Green M. Mo1.Cryst.Liq.Cryst,2000,34:7-l3.
[59]Terazono Y,Kodis G,Dflrr H,et a1. J.Phys.Chem.B,2O04,108:1812-18l4.
[60]Bouas-Laurent H,Pozzo J,Defieux A,et a1. Mo1.Cryst.Liq.Cryst,1997,298:161-167.
[61]Gabbutt C.D,Heron B.M,Instone A.C. Heterocycles,2003,60(4):843-845.
[62]Zhao.Yue,Jiang.JinQiang,Qi.Bo,et al. Macromolecules,2007,40:790-792.
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[68]Francesca Ercole,Thomas P.Davis,Richard A.Evans. Macromolecules,2009,42:790-792.
[69]Nino Malic,Jonathan A.Campbell,Richard A.Evans. Macromolecules,2008,41:1206-1214.
[70]Such.G. K,Evans.R.A,Davis.T.P. Macromolecules 2006,39:1391-1396.
[2]Raymo F.M,Giordani S. Proc.Natl.Acad.Sci.USA,2002,99(8):4941-4944.
[3]樊美公(Fan M G).化学进展(Progress in Chemistry),1997,9:17O-178.
[4] Kim.E,Cho.S.Y. Mol.Cryst.Liq.Cryst,2002,377:385-390.
[5]Ichimura K. Organic Photochromic and Thermochromic Compounds(eds.Crano J C,Gugllemetti R J).New York:Plenum Press,1999.2、9-63.
[6]Mylcs A J,Branda N R. Macmmohcules,2003,36:298-303.
[7]Hattori.H,Uryu.T,J.Polym.Sci.Part A:Polym.Chem,1999,37:3513-3522.
[8] Ranter.J,Noda.F,Horii.T,et al. Poly.Adv.Tech,2002,13(2):81-86.
[9]Fu.Y,Chen.H,Qiu.D,et al. Langmuir,2002,18:4989-4995.
[10]Nagata.T,Matsui.T,Ozaki.M,et al. Synthetic Metals,2001,19:607-608.
[11]Delaire.J.A,Nakatani.K. Chem.Rev,2000,100:1817-1845.
[12]Malkin.J,Zelichenok.A,Krongauz.V,et al. J.Am.Chem.Soc,1994,116:1101-1105.
[13]Kim.J.M,Shin.H.Y,Park K.H. Macromolecules,2001,34(13):4291-4293.
[14]Nakatani.K,Yu.P. Adv.Mater,2001,13(18):1411-1413.
[15]Maurel.F,Delbaere.S,Truong.S.L,et al. J.Phys.Org.Chem,2007,20:944-952.
[16]Zhao.W,Carreira.E.M. Organic Letters,2003,5(22):4153-4154.
[17]Tan.T.F,Han.J,Pang.M.L,et al. etrahedron,2006,62:4900-4906.
[18]Ahmed.S.A,Tanaka.M,Ando.H,et al. Eur.J.Org.Chem,2003,2437-2442.
[19]Allcock.H.R,Kim.C. Macromolecules,1991,24:2846-2851.
[20]Yassar.A,Moustrou.C,Youssoufi.H.K,et al. Chem.Commun,1995,471-472.
[21]Wigglesworth.T.J,Branda.N.R. Adv.Mater,2004,1692:123-125.
[22]Ho.M.S,Natansohn.A,Rochon.P. Macromolecules,1995,28:6124-6127.
[23]Coelho.P.J,Salvador. M.A,Heron .B.M,et al. Tetrahedron,2005,61:11730-11743.
[24]Zhao W,Carreira E.M. J.Am.Chem.Soc,2002,124(8):1582-1583.
[25]Berthet. J,Micheau .J.C,Metelitsa.A,et al. J.Phys.Chem.A,2004,108:10934-10940.
[26]Delbaere.S,Micheau.J.C,Frigoli.M,et al. J.Org.Chem,2005,70:5302-5304.
[27]Delbaere.S,Vermeersch .G,Frigoli .M,et al. Organic Letters,2006,8(21):4931-4934.
[28]Sallenave.X,Delbaere.S,Vermeersch.G,et al. J.Phys.Org.Chem,2007,20:872-877.
[29]Jiang.J.Q,Tong.X,Zhao.Y. J.Am.Chem.Soc,2005,127:8290-8291.
[30]Dürr H,Bouas-Laurent H. Photochromism:Molecules and Systems,Am sterdam:Elsevier,1990.
[31]McArdle C B. Applied Photochromism Polymer Systems,London: Blakie & Son Lim ited,1991.
[32]黄维垣,闻建勋.高技术有机高分子材料进展.北京:化学工业出版社,1994,250.
[33]Friedrich J,Haarer D. Angrew Chem,1984,96:96.
[34]Kaempf G. Polym J,1987,19(2):257.
[35]樊美公等.光化学基本原理与光子学材料[M].科学出版社,2001.226.
[36]Li Xiaoliu,Li Jinliang,Wang Yongmei,et al.Synthesis of functionalized spiropyran and spirooxazine derivatives and their photochromic propenies.Journal of Photochemis try and Photobiology A:Chemistry,2004,161:201-213.
[37]谈廷风,韩杰,庞美丽,高用彬,孟继本.6-氯-8-溴螺(吲哚啉-2,2’[2H]苯并[b]吡喃)的合成及光致变色性能研究.高等学校化学学报,2007.28(3):472-475.
[38]Sung-Hoon Kima,Hee-Jung Suha,Jian-Zhong Cuia,et al. Crystalline-state photo chromism and thermochromism of new spiroxazine.Dyes and Pigments,2002,53:25l-256.
[39]Kluter U,Ltub w,Schneider S.Springer Proc.Phys,1985,4,152.
[40]Fan M G. Basic fundamentals of photochemistry and materials science of photoni cs[M].Science Press,Beijing,2001,226(in Chinese).
[41]龚涛,冯嘉春,韦玮.二芳基乙烯类化合物用作光开关的最新研究.化学进展,2006.18(6):698-706.
[42]樊贵宝,明阳福,樊美公.二芳杂环基乙烯的合成及其光致变色反应研究.有机化学, 1994.14:599-603.
[43]Bobrovsky .A.Yu,Boiko .N.I,Shibaev V.P.Dual photochromism of copolymers Containing two different types of photoisomerizable side groups.Journa1 ofPhotochemistry and Photobiology A:Chemistry,2001,138:261-267.
[44]Fang Zheng,wang Shu-zhi. Synthesis and photochromism in solution of Phenoxy naphthacenequinone derivatives.Journal of Photochemistry and Photobiology A: Chemistry,1995,88:23-30.
[45]李红霞,刘颖.苯氧基蒽醌的合成和光致变色性质.延边大学学报(自然科学版),2004,30(4):278-280.
[46]Eich M,Werdoff J H,Reck B.Ringsdorfh makromol[J].Chem.rapid Commun,1987,8,59.
[47]于联合,明阳福,樊美公等.光致变色俘精酸酐的制备及其在光信息存储的应用[J].中国科学B辑),1995,25,799.
[48]Heller H G,New Fatigue-resistant organic photochromic materials,in:fine chemicals for the electronics industry (p.bamfielded.)[J].Royal.Soc.Chem, London P.120 1986.
[49]Ryoka Matsushima,Masafumi Nishiyama,Masamichi Doi. Improvements in the fatigue resistances of photochromic compounds.Journal of Photochemistry and Photobiology A:Chemistry,2001,139:63-69.
[50]刘莹,姚祖光.俘精酸酐—光致变色化合物.感光材料,1996.1:5-12.
[51]Irie M,Uchida K.Bul1.Chem.Soc.Jpn,1998,71:985-996.
[52]黄震年(Huang Z N),赵伟利(Zhao W L),樊美公(Fan M G).化学通报(Chemistry),1996,12:l6-2l.
[53]Irie M. Chem.Rev,2000,l00:l685-l7l6.
[54]Cabrera I,Dittrich A,Ringsdorf H. Angew.Chem.Int.Ed.Eng1,1991,30:76-78.
[55]Fukaminato T,Kawai T,irie M. Jpn.J.App1.Phys,2000,39:L633-L634.
[56]于明昕(Yu M x),周啸(Zhou x).功能材料(Functional Materials),2001,32(2):203-205.
[57]Kanakkanatt S V,Patel V S,Pate1 R G,eta1. Mo1.Cryst.Liq.Cryst,1994,246:159- 168.
[58]Li J,Schuster G B,Green M. Mo1.Cryst.Liq.Cryst,2000,34:7-l3.
[59]Terazono Y,Kodis G,Dflrr H,et a1. J.Phys.Chem.B,2O04,108:1812-18l4.
[60]Bouas-Laurent H,Pozzo J,Defieux A,et a1. Mo1.Cryst.Liq.Cryst,1997,298:161-167.
[61]Gabbutt C.D,Heron B.M,Instone A.C. Heterocycles,2003,60(4):843-845.
[62]Zhao.Yue,Jiang.JinQiang,Qi.Bo,et al. Macromolecules,2007,40:790-792.
[63]Trenor,S. R,Shultz,A. R,Love, B. J,et al. Chem. ReV.2004,104,3059.
[64]M.Irie. Chem.Rew,2000,100:1685-1716.
[65]Berkovic G,Krongauz.V. Chem.Rew,2000,100:1741-1754.
[66]Kawata.S,Kawata.Y. Chem.Rew,2000,100:1777-1788.
[67]V.Mol.Cryst.Liq.Cryst,1994,246:339-346.
[68]Francesca Ercole,Thomas P.Davis,Richard A.Evans. Macromolecules,2009,42:790-792.
[69]Nino Malic,Jonathan A.Campbell,Richard A.Evans. Macromolecules,2008,41:1206-1214.
[70]Such.G. K,Evans.R.A,Davis.T.P. Macromolecules 2006,39:1391-1396.