光致变色化合物的制备及其在纺织品上的应用
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摘要
本论文制备了非反应性螺噁嗪光致变色化合物并制得了含有二氯均三嗪基的反应性螺噁嗪,对其结构进行了简单表征,检测了其光致变色性。研究了溶液浓度及温度、溶剂极性、聚合物介质、pH值等外部环境因素对螺噁嗪化合物光致变色性能的影响。结果表明:浓度越高、温度越低,光照后的溶液颜色越深;螺噁嗪表现出正的溶剂化显色效应;低温度和聚合物的强极性、强刚性都会降低螺噁嗪呈色体的消色速度;在一定的pH范围内,N-甲基螺噁嗪和N-甲基-9'-二氯均三嗪基螺噁嗪具有酸致变色性,N-甲基-9'-羟基螺噁嗪既有酸致变色性又有碱致变色性,螺噁嗪在碱性环境中仍有较好的光致变色性能。
通过研究粘合剂种类和用量、织物面料种类、焙烘条件等因素对螺噁嗪光致变色性能和织物性能的影响,确定了非反应性螺噁嗪光致变色色浆印花的最佳工艺条件,制得了具有较好光致变色功能的织物,获得了较好的抗疲劳性。
采用二浴法轧染、全料法直接印花和二步法直接印花的方法将反应性螺噁嗪应用到纯棉织物上,虽都可获得光致变色效果,但螺噁嗪利用率极低,均不具有可行性;若考虑选用具有反应性基团的逆光色性光致变色化合物,三种方法则具有可行性。采用无水印花方法虽可制得具有很好光致变色效果的纯棉织物,但易堵塞印花网网孔,也不具有可行性;若考虑选用不能与反应性螺噁嗪反应的粘合剂,无水印花方法则具有可行性。
The non-reactive photochromic spirooxazines were synthesized successfully and the reactive spirooxazine having a dichloro-s-triazinyl was also synthesized in this thesis,and their structures were characterized simply and photochromism was detected.The influence of solution concentration and external environmental factors such as temperature,polarity of solvents,polymer medium,and pH value etc.on the photochromism of spirooxazines was studied.The result showed that:the color of solution became deeper with the increase of solution concentration and reduction of temperature;sprirooxazines exhibited positive solvatochromism effect;the achromatic speed of colored form of spirooxazine could be decreased by low temperature,strong polarity and stiffness of polymer medium;in certain pH range,N-methyl sprirooxazine and N-methyl-9'-dichloro-s-triazinylsprirooxazine exhibited acidichromism,while N-methyl-9'-hydroxysprirooxazine exhibited both acidichromism and alkalichromism, besides,spirooxazines still exhibited photochromism in alkaline environment.
The optimum process conditions of printing with spirooxazine color paste were determined by studying the influence of kinds and dosage of adhesive,kinds of fabrics and curing conditions etc.on photochromism of spirooxazine and properties of fabrics. Eventually,fabrics of good photochromism were prepared,and good fatigue resistance was obtained.
The reactive spirooxzine was applied onto cotton fabric by adopting the two-bath padding-dyeing,one-step direct printing and two-step direct printing methods;though photochromic effect was obtained by all the three methods,the spirooxaxzine utilization ratio was extremely low,as a result,all the three methods were not feasible;the three methods might be all feasible if reverse optical photochromic compound of reactive anchor was considered to be apllied.The method of anhydrous printing could be adopted to prepare photochromic cotton fabric,however,the printing screen was blocked very easily,as a result,the method was not feasible as well;the method of anhydrous printing might be feasible if the adhesive that could not react with reactive spirooxazine was considered to be applied.
通过研究粘合剂种类和用量、织物面料种类、焙烘条件等因素对螺噁嗪光致变色性能和织物性能的影响,确定了非反应性螺噁嗪光致变色色浆印花的最佳工艺条件,制得了具有较好光致变色功能的织物,获得了较好的抗疲劳性。
采用二浴法轧染、全料法直接印花和二步法直接印花的方法将反应性螺噁嗪应用到纯棉织物上,虽都可获得光致变色效果,但螺噁嗪利用率极低,均不具有可行性;若考虑选用具有反应性基团的逆光色性光致变色化合物,三种方法则具有可行性。采用无水印花方法虽可制得具有很好光致变色效果的纯棉织物,但易堵塞印花网网孔,也不具有可行性;若考虑选用不能与反应性螺噁嗪反应的粘合剂,无水印花方法则具有可行性。
The non-reactive photochromic spirooxazines were synthesized successfully and the reactive spirooxazine having a dichloro-s-triazinyl was also synthesized in this thesis,and their structures were characterized simply and photochromism was detected.The influence of solution concentration and external environmental factors such as temperature,polarity of solvents,polymer medium,and pH value etc.on the photochromism of spirooxazines was studied.The result showed that:the color of solution became deeper with the increase of solution concentration and reduction of temperature;sprirooxazines exhibited positive solvatochromism effect;the achromatic speed of colored form of spirooxazine could be decreased by low temperature,strong polarity and stiffness of polymer medium;in certain pH range,N-methyl sprirooxazine and N-methyl-9'-dichloro-s-triazinylsprirooxazine exhibited acidichromism,while N-methyl-9'-hydroxysprirooxazine exhibited both acidichromism and alkalichromism, besides,spirooxazines still exhibited photochromism in alkaline environment.
The optimum process conditions of printing with spirooxazine color paste were determined by studying the influence of kinds and dosage of adhesive,kinds of fabrics and curing conditions etc.on photochromism of spirooxazine and properties of fabrics. Eventually,fabrics of good photochromism were prepared,and good fatigue resistance was obtained.
The reactive spirooxzine was applied onto cotton fabric by adopting the two-bath padding-dyeing,one-step direct printing and two-step direct printing methods;though photochromic effect was obtained by all the three methods,the spirooxaxzine utilization ratio was extremely low,as a result,all the three methods were not feasible;the three methods might be all feasible if reverse optical photochromic compound of reactive anchor was considered to be apllied.The method of anhydrous printing could be adopted to prepare photochromic cotton fabric,however,the printing screen was blocked very easily,as a result,the method was not feasible as well;the method of anhydrous printing might be feasible if the adhesive that could not react with reactive spirooxazine was considered to be applied.
引文
[1]王文志.变色纺织品及其应用[J].山东纺织科技,2007(2):54.
[2]黄慧华,刘及时.几种变色染料的变色机理以及在纺织品上的应用[J].化纤与纺织技术,2006(1):24.
[3]Durr H,Bouas-Laurent H.Photochromism:Molecules and Systems[J].Amsterdam:Elsevier,1990.
[4]樊美公.光致变色与光子器件[J].化学进展,1994,6(3):209-213.
[5]赵利华.3-吲哚俘精酰亚胺的合成与光致变色性能研[D].北京:中国科学院电子学研究所,2001.
[6]樊美公.光子存储原理与光致变色材料[J].化学进展,1997,9(2):170-178.
[7]A.Deffieux.,W.C.Hsieh,D.R.Squire,et al.Radiation-induced cationic polymerization of vinyl ethyl ethers in solution:2.Polymerization of ethyl vinyl ethyl ether in methylene dichloride solution[J].Polymer,1982,23(1 ):68.
[8]冯社永,顾利霞.光敏变色纤维材料[J].合成纤维工业,1997,20(3):36.
[9]杨武利,胡建华,府寿宽.光致变色高分子体系[J].高分子通报,1998(4):65.
[lO]艾克热木·克尤木.功能性染料-光致变色化合物的开发[J].新疆教育学院学报,2000,16(2):76.
[11]C.J.T.Landry,B.K.Coltrain,J.A.Wesson,et al.In situ polymerization of tetraethoxysilane in polymers:chemical nature of the interactions[J].Polymer,1992,33(7):1496.
[12]Hirshberg Y.,and Fischer E..Photochromism and reversible multiple internal transilation in some spiropyrans at low temperature[J].Part 2.,J.Chem.Soc.1954:3129.
[13]魏景强.吡喃化合物的合成与光致变色机理研究[D].北京:中国科学院感光化学研究所,2000.
[14]Pang M.L.Nie Y.C,Wang Y.M.Synthesis of New Spiropyrans with a Polyaromatic or Heteroaromatic Pendant and Their Photoch Romie Behaviors[J].Chin.J.Chem.2002,1(20):1102-1108.
[15]王哲.螺噁嗪的合成及其光致变色性能的研究[D].天津:天津大学,1999.
[16]赵秋月.茚满二酮类光致变色化合物的制备与表征[D].吉林:长春理工大学,2005.
[17]樊贵宝,明阳福,樊美公.顺式(2)1,2-双吡咯类乙烯衍生物的光致变色研究[J].中国科学(B).1995,6(25):1257-1260.
[18]王聪敏,潘桂兰,赵利华,等.有机光致变色材料的最新成就与机遇[J].有机化学,2001,21(11):954-961.
[19]潘桂兰,魏景强,朱爱平,等.萘并吡喃类化合物的光致变色性质和反应机理[J].中国科 学(B),2001,31(3):246-252.
[20]R.S.Becker,J.Michi.J.Chem.Soc.1966,88:5929.
[21]A.Senier,F.G.ShePheard.J.Chem.Soc.1912,101:195.
[22]Durr H.Perspectives in Photochromism:A Novel System Based on the 1,5-Electrocyclization of Heteroanalogous Pentadienyl Anions[J].Angew.Chem.,Int.Ed.Eng.,1989,28:413.
[23]Andes R.Y.and Manakoviski D.M..Photochromism of Salicylideneaniline[J].Appl.Opt.,1968,7:1179.
[24]Fischer E.,and Hirshberg Y..Formation of colored forms of spirans by low temperature irradiation[J].J.Chem.Soc.,1952:4522.
[25]冯社永,顾利霞.光敏变色纤维材料[J].合成纤维工业,1997,20(3):36-40.
[26]樊美公,周亚琳,刘小云.靛兰衍生物的光异构化[J].感光科学与光化学,1983(1):45.
[27]赵建章,赵冰,徐蔚青等.水杨醛缩胺类Schiff碱光致变色性质[J].高等学校化学学报,2003,24(2):324-328.
[28]P.F.Barbara,P.M.Rentzepis,L.E.Brus.Photochemical kinetics of salicylidenaniline[J].J.Am.Chem.Soc.,1980,102(8):2786-2791.
[29]李顺来,李宗和,冯文林.俘精酸酐分子光致变色反应机理的理论计算研究[J].北京化工大学学报,2003,30(5):62-65.
[30]王聪敏,潘桂兰,赵利华,等.有机光致变色材料的最新成就与机遇[J].有机化学,2001,21(11):954-961.
[31]梁永超,明阳福,樊美公,等.吲哚啉萘并噫嗪在异丙醇中的酸致变色研究[J].中国科学(B),1997,27(5):419-423.
[32]韩勇.新型二芳基乙烯化合物的合成、性质及光致变色化合物应用研究[D].北京:中国科学院理化技术研究所,2004.
[33]潘桂兰.新型二芳基乙烯的合成与光致变色性能研究[D].北京:中国科学院理化技术研究所,2001.
[34]Hirshberg Y.Reversible formation and eradication of colors by irradiation at low temperature:A photochemical memory model[J].J.Am.Chem.Soc.,1956,68:2304.
[35]Heller H G.The development of photochromic compounds for use in optical information stores [J].Chemistry and lndustry,1978,18.- 193.
[36]Chu N Y C,Phochromic of spiroindolinonaphthoxazine[J].Can.J.Chem.,1983,61:300.
[37]Chu N.Y.C..Photochromic performance of spiroindolino-napthxazines in plastics[J].Solar Energy Materials,1986,14(4):215.
[38]Melzig M.and Martinuzzi G..Photochromic substances[P].Europaisches Patent:WO 8502619(A1),1985-06-20.
[39]Yamamoto S.and Taniguchi T..Spiro-oxazine compounds and preparation thereof and photochromic shaped article[P].Japanese Patent:EP 0171909(A1),1986-02-19.
[40]Harris L.,Kaminsky J.,and Simard R.G..The absorption spectrum of malachite green leucocyanide and mechanism of the dark reaction after photolysis[J].J.Am.Chem.Soc.,1935,57:1151.
[41]Calvert J.G.,and Rechen H.J.L..Precision actinometry at low light intensities with malachite green leucocyanide[J].J.Am.Chem.Soc.,1952,74:2101.
[42]Gheorghiu C.V.,and Mate V..Phototropy of ethylenic keton semicarbazones and phenylhydrazones[J].Bull.Soc.Chim.Fr.,1939,6..1324.
[43]Gheorghiu C.V.,and Arwentiew B..Condensation of methyl isobutyl ketone with anisalidehyde Ⅱ:Phototropy of semicarbazones of ethylenic ketons[J].Bull.Soc.Chim.Fr.,1930,47:195.
[44]Gheorghiu C.V..The phototropy of semicarbazones of ethylenic ketons:Thiosemicarbazones and δ-phenylsemicarbazones[J].Bull.Soc.Chim.Fr.,1934,1:97.
[45]Fischer E.,and Hirshberg Y..Formation of Colored forms of spirans by low temperature irradiation[J].J.Chem.Sot.,1952:4522.
[46]Porter G.,Die Blitzlicht photolyse and einige ihner Anwendungen(Nobel-Vortrag)[J].Angew.Chem.,1968,80:882.
[47]Norrish R.G.W.,and Porter G..Chemical Reactions Produced by very high light intensiries[J].Nature(London),1949,164:658.
[48]Heller,H.G..The development of photochromic compounds for use in optical information storage[J].Chemistry and lndustry,1978,18:193.
[49]H.G.Heller..The development of photochromic compounds for use in optical information storage[J].Chemistry andlndustry,1978,18:195.
[50]樊美公.光致变色与光子器件[J].化学进展,1994,6(3):211.
[51]王哲.螺噁嗪的合成及其光致变色性能的研究[D].天津:天津大学,1999.
[52]王建营,冯长根.螺噁嗪类光致变色化合物的合成研究进展[J].应用化学,2007,24(7):729-736.
[53]张文官,江和金.光致变色化合物的合成及应用研究[J].北京印刷学院学报,2000,8(2):33-39.
[54]徐晓明.含不对称双变色基光致变色化合物的合成及性能研究[D].河北:河北大学,2006.
[55]冯光华.含螺吡喃、螺噁嗪类基团高分子聚合物的制备和光致变色性质研究[D].兰州:西北师范大学,2007.
[56]Young-A Son,Young-Min Park,So-Yeon Park,et al.Exhaustion studies ofspiroxazine dye having reactive anchor on polyamide fibers and its photochromic properties[J].Dyes and Pigments,2007,73:76-88.
[57]葛婧嫒,杨文芳.变色材料在纺织品上的应用[J].染整技术,2007,29(10):5-9.
[58]唐克光.光致变色化合物的用途和性能[J].丝网印刷,2001(4):32-37.
[59]毛振鹏.各种功能材料在织物上的应用[J].印染译丛,1994(4):64.
[60]李春暖.变色纤维的开发和应用[J].染整技术,2006,28(9):9.
[61]习智华,赵振河.热敏液晶变色机理及应用[J].陕西纺织,1997(3):51-52.
[62]涂赞润,任宏图.光敏变色微胶囊的合成及其在纺织品中的应用[J].印染,1999(10):5-8.
[63]姜惠娣,金建平.光敏变色真丝印花绸的研制与生产[J].江苏丝绸,2001,(5):6-8.
[64]孟继本,戈金元,何善平.光致变色染料[P].中国专利:03120754.5,2004-03.17.
[65]郑今欢,邵建中,刘今强.光致变色印花涂层织物的制备工艺[P].中国专利:200710068399.7,2007-10-24.
[66]宋心远,沈煜如编著.新型染整技术[M].北京:中国纺织出版社,1999:167-171.
[67]万震,王炜,谢均.光敏变色材料及其在纺织品上的应用[J].针织工业,2003(6):87-89.
[68]李仲杰,谭永生,董绮功.N,N'-1,4-亚丁基双[螺吲哚啉萘并噁嗪]的合成[J].应用化学,1994.11(2):93-95.
[69]Zelichenok A,Brchholtz F,Yilzchaitetal S.Steric effects in photochromic polysiloxanes with spirooxazine side groups[J].Macromolecules,1992,25:3179-3183.
[70]刘伯军,杨志范,王淑芝等.N-甲基螺噁嗪光致变色化合物的合成[J].吉林工学院学报,2000,21(2):2.
[71]Deligeorgiev T.,Minkovska S.,Jejiazkova B..Synthesis of photochromic chelating spironaphthoxazines [J].Dye and pigrnents,2002,53:101-108.
[72]T.Kakishita,K.Matsumoto,T.Kiyotsukuri.Synthesis and NMR Study of 9'-Substituted Spiroindolinonaphoxazaine Derivatives[J].Heterocyclic Chem.,1992,29:1714.
[73]Young-A Son,Young-Min Park,So-Yeon Park,et al.Exhaustion studies of spiroxazine dye having reactive anchor on polyamide fibers and its photochromic properties[J].Dyes and Pigments,2007,73:77.
[74]R.E.Fox.Research Reports and Test Items Pertaining to Eye Protection of Air Crew Parsonal[C].Final Report on Coutract AF 41(657)-215,April 1961,AD440:226.
[75]樊美公.光化学基本原理与光子学材料科学[M].北京:科学出版社,2001:229.
[76]M.Nakamura,and T.Taniguchi.Yuki Gosei Kagaku Kyokaishi,1991,49:392.
[77]叶楚平,任家强,葛汉青等.苯并噻唑螺萘并噁嗪类化合物的微波合成与性质[J].有机化 学,2004,24(9):1058.
[78]Knauer B.R.,Napier J.J..The nitrogen hyperfine splitting constant of the nitroxide functional group as a solvent polarity parameter.The relative importance for a solvent polarity parameter of its being a cybotactic probe vs.its being a model process[J].J.Am.Chem.Soc.,1976,98(15):4397.
[79]Kosower E.M..The Effect of Solvent on Spectra.I.A New Empirical Measure of Solvent Polarity:Z-Values[J].J.Am.Chem.Soc.,1958,80(13):3257.
[80]张智斌.新型吲哚啉螺菲哕啉并噁嗪类化合物的合成及其光致变色性质研究[D].北京:中国科学院理化技术研究所,2004.
[81]Fan M.G.Basic fundamentals of photochemistry and materials science of photonics[M].Science Press,Beijing,2001:226.
[82]S.Schneider,A.Mindl,and G.Elfinger,et al.Photochromism of spirooxazines:Investigation of the primary processes in the ring-opening reaction by picosecond Time-resolved absorption and emission spectroscopy[J].Ber.Bunsenges Phys.Chem.,1987,91:1222.
[83]S.Schneider,F.Baumann,and U.Kluter,et al.Photochromism of spirooxazines Ⅱ:CARS-investigation of solvent effect on the isomeric ditribution[J].Ber.Bunsenges Phys.Chem.,1987,91:1225.
[84]刘茂栋.壳聚糖接枝/掺杂螺吡喃、螺噁嗪及光致变色性能的研究[D].甘肃:西北师范大学,2005.
[85]Hovey R.J.,Chu N.Y.C.,Piusz P.G.,et al.Photochromic compounds[P].US Patent:4215010,1980-7-29.
[86]Levitus M.,Aramendia P..Photochromism and Thermochromism of Phenanthrospirooxazine in Poly(Alkyl Methacrylates)[J].J.Phys.Chem.,1999,103:1864-1870.
[87]涂赞润,任宏图.光敏变色微胶囊的合成及其在纺织品中的应用[J].印染,1999(10):8.
[2]黄慧华,刘及时.几种变色染料的变色机理以及在纺织品上的应用[J].化纤与纺织技术,2006(1):24.
[3]Durr H,Bouas-Laurent H.Photochromism:Molecules and Systems[J].Amsterdam:Elsevier,1990.
[4]樊美公.光致变色与光子器件[J].化学进展,1994,6(3):209-213.
[5]赵利华.3-吲哚俘精酰亚胺的合成与光致变色性能研[D].北京:中国科学院电子学研究所,2001.
[6]樊美公.光子存储原理与光致变色材料[J].化学进展,1997,9(2):170-178.
[7]A.Deffieux.,W.C.Hsieh,D.R.Squire,et al.Radiation-induced cationic polymerization of vinyl ethyl ethers in solution:2.Polymerization of ethyl vinyl ethyl ether in methylene dichloride solution[J].Polymer,1982,23(1 ):68.
[8]冯社永,顾利霞.光敏变色纤维材料[J].合成纤维工业,1997,20(3):36.
[9]杨武利,胡建华,府寿宽.光致变色高分子体系[J].高分子通报,1998(4):65.
[lO]艾克热木·克尤木.功能性染料-光致变色化合物的开发[J].新疆教育学院学报,2000,16(2):76.
[11]C.J.T.Landry,B.K.Coltrain,J.A.Wesson,et al.In situ polymerization of tetraethoxysilane in polymers:chemical nature of the interactions[J].Polymer,1992,33(7):1496.
[12]Hirshberg Y.,and Fischer E..Photochromism and reversible multiple internal transilation in some spiropyrans at low temperature[J].Part 2.,J.Chem.Soc.1954:3129.
[13]魏景强.吡喃化合物的合成与光致变色机理研究[D].北京:中国科学院感光化学研究所,2000.
[14]Pang M.L.Nie Y.C,Wang Y.M.Synthesis of New Spiropyrans with a Polyaromatic or Heteroaromatic Pendant and Their Photoch Romie Behaviors[J].Chin.J.Chem.2002,1(20):1102-1108.
[15]王哲.螺噁嗪的合成及其光致变色性能的研究[D].天津:天津大学,1999.
[16]赵秋月.茚满二酮类光致变色化合物的制备与表征[D].吉林:长春理工大学,2005.
[17]樊贵宝,明阳福,樊美公.顺式(2)1,2-双吡咯类乙烯衍生物的光致变色研究[J].中国科学(B).1995,6(25):1257-1260.
[18]王聪敏,潘桂兰,赵利华,等.有机光致变色材料的最新成就与机遇[J].有机化学,2001,21(11):954-961.
[19]潘桂兰,魏景强,朱爱平,等.萘并吡喃类化合物的光致变色性质和反应机理[J].中国科 学(B),2001,31(3):246-252.
[20]R.S.Becker,J.Michi.J.Chem.Soc.1966,88:5929.
[21]A.Senier,F.G.ShePheard.J.Chem.Soc.1912,101:195.
[22]Durr H.Perspectives in Photochromism:A Novel System Based on the 1,5-Electrocyclization of Heteroanalogous Pentadienyl Anions[J].Angew.Chem.,Int.Ed.Eng.,1989,28:413.
[23]Andes R.Y.and Manakoviski D.M..Photochromism of Salicylideneaniline[J].Appl.Opt.,1968,7:1179.
[24]Fischer E.,and Hirshberg Y..Formation of colored forms of spirans by low temperature irradiation[J].J.Chem.Soc.,1952:4522.
[25]冯社永,顾利霞.光敏变色纤维材料[J].合成纤维工业,1997,20(3):36-40.
[26]樊美公,周亚琳,刘小云.靛兰衍生物的光异构化[J].感光科学与光化学,1983(1):45.
[27]赵建章,赵冰,徐蔚青等.水杨醛缩胺类Schiff碱光致变色性质[J].高等学校化学学报,2003,24(2):324-328.
[28]P.F.Barbara,P.M.Rentzepis,L.E.Brus.Photochemical kinetics of salicylidenaniline[J].J.Am.Chem.Soc.,1980,102(8):2786-2791.
[29]李顺来,李宗和,冯文林.俘精酸酐分子光致变色反应机理的理论计算研究[J].北京化工大学学报,2003,30(5):62-65.
[30]王聪敏,潘桂兰,赵利华,等.有机光致变色材料的最新成就与机遇[J].有机化学,2001,21(11):954-961.
[31]梁永超,明阳福,樊美公,等.吲哚啉萘并噫嗪在异丙醇中的酸致变色研究[J].中国科学(B),1997,27(5):419-423.
[32]韩勇.新型二芳基乙烯化合物的合成、性质及光致变色化合物应用研究[D].北京:中国科学院理化技术研究所,2004.
[33]潘桂兰.新型二芳基乙烯的合成与光致变色性能研究[D].北京:中国科学院理化技术研究所,2001.
[34]Hirshberg Y.Reversible formation and eradication of colors by irradiation at low temperature:A photochemical memory model[J].J.Am.Chem.Soc.,1956,68:2304.
[35]Heller H G.The development of photochromic compounds for use in optical information stores [J].Chemistry and lndustry,1978,18.- 193.
[36]Chu N Y C,Phochromic of spiroindolinonaphthoxazine[J].Can.J.Chem.,1983,61:300.
[37]Chu N.Y.C..Photochromic performance of spiroindolino-napthxazines in plastics[J].Solar Energy Materials,1986,14(4):215.
[38]Melzig M.and Martinuzzi G..Photochromic substances[P].Europaisches Patent:WO 8502619(A1),1985-06-20.
[39]Yamamoto S.and Taniguchi T..Spiro-oxazine compounds and preparation thereof and photochromic shaped article[P].Japanese Patent:EP 0171909(A1),1986-02-19.
[40]Harris L.,Kaminsky J.,and Simard R.G..The absorption spectrum of malachite green leucocyanide and mechanism of the dark reaction after photolysis[J].J.Am.Chem.Soc.,1935,57:1151.
[41]Calvert J.G.,and Rechen H.J.L..Precision actinometry at low light intensities with malachite green leucocyanide[J].J.Am.Chem.Soc.,1952,74:2101.
[42]Gheorghiu C.V.,and Mate V..Phototropy of ethylenic keton semicarbazones and phenylhydrazones[J].Bull.Soc.Chim.Fr.,1939,6..1324.
[43]Gheorghiu C.V.,and Arwentiew B..Condensation of methyl isobutyl ketone with anisalidehyde Ⅱ:Phototropy of semicarbazones of ethylenic ketons[J].Bull.Soc.Chim.Fr.,1930,47:195.
[44]Gheorghiu C.V..The phototropy of semicarbazones of ethylenic ketons:Thiosemicarbazones and δ-phenylsemicarbazones[J].Bull.Soc.Chim.Fr.,1934,1:97.
[45]Fischer E.,and Hirshberg Y..Formation of Colored forms of spirans by low temperature irradiation[J].J.Chem.Sot.,1952:4522.
[46]Porter G.,Die Blitzlicht photolyse and einige ihner Anwendungen(Nobel-Vortrag)[J].Angew.Chem.,1968,80:882.
[47]Norrish R.G.W.,and Porter G..Chemical Reactions Produced by very high light intensiries[J].Nature(London),1949,164:658.
[48]Heller,H.G..The development of photochromic compounds for use in optical information storage[J].Chemistry and lndustry,1978,18:193.
[49]H.G.Heller..The development of photochromic compounds for use in optical information storage[J].Chemistry andlndustry,1978,18:195.
[50]樊美公.光致变色与光子器件[J].化学进展,1994,6(3):211.
[51]王哲.螺噁嗪的合成及其光致变色性能的研究[D].天津:天津大学,1999.
[52]王建营,冯长根.螺噁嗪类光致变色化合物的合成研究进展[J].应用化学,2007,24(7):729-736.
[53]张文官,江和金.光致变色化合物的合成及应用研究[J].北京印刷学院学报,2000,8(2):33-39.
[54]徐晓明.含不对称双变色基光致变色化合物的合成及性能研究[D].河北:河北大学,2006.
[55]冯光华.含螺吡喃、螺噁嗪类基团高分子聚合物的制备和光致变色性质研究[D].兰州:西北师范大学,2007.
[56]Young-A Son,Young-Min Park,So-Yeon Park,et al.Exhaustion studies ofspiroxazine dye having reactive anchor on polyamide fibers and its photochromic properties[J].Dyes and Pigments,2007,73:76-88.
[57]葛婧嫒,杨文芳.变色材料在纺织品上的应用[J].染整技术,2007,29(10):5-9.
[58]唐克光.光致变色化合物的用途和性能[J].丝网印刷,2001(4):32-37.
[59]毛振鹏.各种功能材料在织物上的应用[J].印染译丛,1994(4):64.
[60]李春暖.变色纤维的开发和应用[J].染整技术,2006,28(9):9.
[61]习智华,赵振河.热敏液晶变色机理及应用[J].陕西纺织,1997(3):51-52.
[62]涂赞润,任宏图.光敏变色微胶囊的合成及其在纺织品中的应用[J].印染,1999(10):5-8.
[63]姜惠娣,金建平.光敏变色真丝印花绸的研制与生产[J].江苏丝绸,2001,(5):6-8.
[64]孟继本,戈金元,何善平.光致变色染料[P].中国专利:03120754.5,2004-03.17.
[65]郑今欢,邵建中,刘今强.光致变色印花涂层织物的制备工艺[P].中国专利:200710068399.7,2007-10-24.
[66]宋心远,沈煜如编著.新型染整技术[M].北京:中国纺织出版社,1999:167-171.
[67]万震,王炜,谢均.光敏变色材料及其在纺织品上的应用[J].针织工业,2003(6):87-89.
[68]李仲杰,谭永生,董绮功.N,N'-1,4-亚丁基双[螺吲哚啉萘并噁嗪]的合成[J].应用化学,1994.11(2):93-95.
[69]Zelichenok A,Brchholtz F,Yilzchaitetal S.Steric effects in photochromic polysiloxanes with spirooxazine side groups[J].Macromolecules,1992,25:3179-3183.
[70]刘伯军,杨志范,王淑芝等.N-甲基螺噁嗪光致变色化合物的合成[J].吉林工学院学报,2000,21(2):2.
[71]Deligeorgiev T.,Minkovska S.,Jejiazkova B..Synthesis of photochromic chelating spironaphthoxazines [J].Dye and pigrnents,2002,53:101-108.
[72]T.Kakishita,K.Matsumoto,T.Kiyotsukuri.Synthesis and NMR Study of 9'-Substituted Spiroindolinonaphoxazaine Derivatives[J].Heterocyclic Chem.,1992,29:1714.
[73]Young-A Son,Young-Min Park,So-Yeon Park,et al.Exhaustion studies of spiroxazine dye having reactive anchor on polyamide fibers and its photochromic properties[J].Dyes and Pigments,2007,73:77.
[74]R.E.Fox.Research Reports and Test Items Pertaining to Eye Protection of Air Crew Parsonal[C].Final Report on Coutract AF 41(657)-215,April 1961,AD440:226.
[75]樊美公.光化学基本原理与光子学材料科学[M].北京:科学出版社,2001:229.
[76]M.Nakamura,and T.Taniguchi.Yuki Gosei Kagaku Kyokaishi,1991,49:392.
[77]叶楚平,任家强,葛汉青等.苯并噻唑螺萘并噁嗪类化合物的微波合成与性质[J].有机化 学,2004,24(9):1058.
[78]Knauer B.R.,Napier J.J..The nitrogen hyperfine splitting constant of the nitroxide functional group as a solvent polarity parameter.The relative importance for a solvent polarity parameter of its being a cybotactic probe vs.its being a model process[J].J.Am.Chem.Soc.,1976,98(15):4397.
[79]Kosower E.M..The Effect of Solvent on Spectra.I.A New Empirical Measure of Solvent Polarity:Z-Values[J].J.Am.Chem.Soc.,1958,80(13):3257.
[80]张智斌.新型吲哚啉螺菲哕啉并噁嗪类化合物的合成及其光致变色性质研究[D].北京:中国科学院理化技术研究所,2004.
[81]Fan M.G.Basic fundamentals of photochemistry and materials science of photonics[M].Science Press,Beijing,2001:226.
[82]S.Schneider,A.Mindl,and G.Elfinger,et al.Photochromism of spirooxazines:Investigation of the primary processes in the ring-opening reaction by picosecond Time-resolved absorption and emission spectroscopy[J].Ber.Bunsenges Phys.Chem.,1987,91:1222.
[83]S.Schneider,F.Baumann,and U.Kluter,et al.Photochromism of spirooxazines Ⅱ:CARS-investigation of solvent effect on the isomeric ditribution[J].Ber.Bunsenges Phys.Chem.,1987,91:1225.
[84]刘茂栋.壳聚糖接枝/掺杂螺吡喃、螺噁嗪及光致变色性能的研究[D].甘肃:西北师范大学,2005.
[85]Hovey R.J.,Chu N.Y.C.,Piusz P.G.,et al.Photochromic compounds[P].US Patent:4215010,1980-7-29.
[86]Levitus M.,Aramendia P..Photochromism and Thermochromism of Phenanthrospirooxazine in Poly(Alkyl Methacrylates)[J].J.Phys.Chem.,1999,103:1864-1870.
[87]涂赞润,任宏图.光敏变色微胶囊的合成及其在纺织品中的应用[J].印染,1999(10):8.