CN107141682B - 一种白光发射的纤维素基荧光膜及其制备方法 - Google Patents
一种白光发射的纤维素基荧光膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种白光发射的纤维素基荧光膜的制备方法,该方法包括如下步骤:(1)合成一种荧光单体吩噻嗪‑二苯胺基二苯酮;(2)合成纤维素/丙烯酸丁酯共聚物;(3)制备纤维素基荧光膜。本发明通过合成一种荧光单体和不同的纤维素/丙烯酸丁酯共聚物,然后掺杂得到一种白光发色的纤维素基荧光膜。本发明所得到的纤维素基荧光膜在光学材料、信息技术、包装防伪等领域具有广泛的应用前景。
Description
技术领域
本发明具体涉及一种白光发射的纤维素基荧光膜的制备方法
背景技术
纤维素是地球上含量最丰富的天然聚合物,由于具有生物兼容性、可降解、无毒等优点,纤维素得到了广泛研究和应用。纤维素薄膜具有良好的透光性和柔性,其和荧光化合物结合制备的纤维素基荧光膜可应用于光电材料、生物医药和包装防伪等领域。
发明内容
本发明的目的是提供一种纤维素基荧光膜的制备方法,通过该方法可得到白光发射的纤维素基荧光膜。
本发明的目的是通过以下技术方案实现的:一种白光发射的纤维素基荧光膜的制备方法,包括如下步骤:
(1)合成一种荧光单体吩噻嗪-二苯胺基二苯酮;
(2)合成纤维素/丙烯酸丁酯共聚物;
(3)制备纤维素基荧光膜。
在本发明的一个优选实施方案中,所述步骤(1)是将吩噻嗪和4-碘-4’-二苯胺基二苯酮溶解于N,N-二甲基甲酰胺DMF,通氩气,加入催化剂量碘化亚铜,升温至165~175℃,反应15~17h,反应结束后分离提纯,即可得到荧光单体吩噻嗪-二苯胺基二苯酮,其中吩噻嗪、4-碘-4’-二苯胺基二苯酮、碘化亚铜摩尔比为1:(0.5~2):(0.01~0.1)。
优选地,所述4-碘-4’-二苯胺基二苯酮的制备是通过以下步骤获得:将二苯胺溶解于N,N-二甲基甲酰胺DMF中,然后加入NaH,升温至70~80℃,再加入4-氟-4’-碘二苯酮,升温至105~115℃,反应11~13h,反应结束后分离提纯所得,其中二苯胺、DMF、NaH、4-氟-4’-碘二苯酮的摩尔比例依次为1:(5~10):14:(1~2)。
优选地,所述4-氟-4’-碘二苯酮的制备是通过以下步骤获得:将4-碘苯甲酰氯和氟苯加入到干燥三颈瓶中搅拌,再加入无水氯化铝,升温至40~50℃,反应5~6h,反应结束后,分离提纯所得,其中4-碘苯甲酰氯、氟苯、无水氯化铝的摩尔比依次为1:(3~4):2。
在本发明的一个优选实施例中,所述步骤(2)是将纤维素溶解在DMAc及LiCl中,得到2~5%浓度的纤维素溶液,缓慢加入丙烯酸丁酯,加入AIBN,搅拌升温至75~85℃,反应11~13h,冷却得到纤维素/丙烯酸丁酯共聚混合反应液,其中纤维素、DMAc、LiCl、丙烯酸丁酯、AIBN的质量比依次为1:(17~45):(2~8):(0.05~1):0.01。
进一步地,所述步骤(3)是将步骤(1)所获得的荧光单体吩噻嗪-二苯胺基二苯酮加入步骤(2)所获得的纤维素/丙烯酸丁酯共聚混合反应液中,搅拌均匀,用线棒涂膜,将膜泡在水中除去DMAc及LiCl得到湿膜,干燥后得到纤维素基荧光膜。
本发明的有益效果是:本发明合成一种荧光化合物和纤维素/丙烯酸丁酯共聚物,将荧光化合物掺杂于纤维素/丙烯酸丁酯共聚物中,得到纤维素基荧光膜,通过控制纤维素和丙烯酸丁酯的反应比例,可得到白光发射的纤维素基荧光膜。本发明制备的纤维素基荧光膜荧光聚合物在光电材料、生物医药和包装防伪等领域有着广泛的应用前景。
附图说明
图1是实施例1-6中得到的纤维素基荧光膜的荧光光谱图。
图2是实施例1-6中得到的纤维素基荧光膜的荧光CIE坐标图。随着纤维素/丙烯酸丁酯比例的增大,得到荧光膜的发光从围合区域内的位于左边蓝色区域转移到位于右边的黄色区域,并经过中间白光区。
具体实施方式
本方法的原理是合成一种荧光化合物和一类纤维素/丙烯酸丁酯共聚物,然后将荧光化合物掺杂到纤维素/丙烯酸丁酯共聚物中,制备出纤维素基荧光膜,通过控制纤维素和丙烯酸丁酯的反应比例,可合成出具有不同比例刚性链段和柔性链段的纤维素/聚丙烯酸丁酯共聚物,从而使得荧光化合物在共聚物中具有不同的分布形态,可得到白光发射的纤维素基荧光膜。以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1:
本例是白光发射的纤维素基荧光膜的制造例。
(1)荧光化合物吩噻嗪-二苯胺基二苯酮ODP的合成:将4-碘苯甲酰氯(5.00g,18.8mmol)加入250mL干燥三颈瓶中,再加入氟苯(5.41g,56.3mmol),搅拌,加入无水氯化铝(3.88g,28.2mmol),升温至40~50℃,反应5~6h。反应结束后,在三颈瓶中加入二氯甲烷50ml溶解,缓慢滴加稀盐酸,搅拌至无气泡产生。然后将反应液倒入分液漏斗,用稀盐酸洗2~3次至水层变为无色。将有机层用无水硫酸钠干燥,过滤,滤液在旋转蒸发仪中旋干,得到5.06g黄白色固体4-氟-4’-碘二苯酮,产率83%。
将二苯胺(0.86g,5.06mmol)加入250mL三口瓶中,加入适量DMF,通气15min,于惰性气体氛围中加入NaH(0.33g,13.80mmol)。搅拌至无气泡产生后,升温至75℃,后加入4-氟-4’-碘二苯酮(1.50g,4.60mmol),升温至110℃,反应12h。反应结束后,冷却至室温,将反应液缓慢倒入冰水中,沉淀析出,抽滤,取滤饼用二氯甲烷溶解,无水硫酸钠干燥,在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯,淋洗液为体积比1:2的二氯甲烷和正己烷的混合溶液。得1.10g白色固体4-碘-4’-二苯胺基二苯酮,产率50.3%。
将吩噻嗪(0.50g,2.52mmol)和4-碘-4’-二苯胺基二苯酮(1.00g,2.10mmol)加入250mL三口瓶中,加入适量DMF溶解,通氩气15min,于惰性气体氛围中加入一小药勺的碘化亚酮,搅拌溶解后加入碳酸钾(0.87g,6.31mmol),升温至170℃,加热回流反应16h。反应结束后,冷却至室温,将反应液缓慢倒入冰水中,沉淀析出,抽滤,取滤饼用二氯甲烷溶解,无水硫酸钠干燥,在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯,淋洗液为体积比1:1的二氯甲烷和正己烷的混合溶液。得到黄白色固体吩噻嗪-二苯胺基二苯酮ODP0.55g,产率47.8%。
(2)纤维素/丙烯酸丁酯共聚物的合成:向配有冷凝管、磁力搅拌子的三口烧瓶中,加入微晶纤维素(1g)和DMAc(29g),升温至160℃,保温30min,降温至100℃,加入LiCl(3g),保温30min,降至室温静置过夜,得到浓度为3%的纤维素溶液;向纤维素溶液中缓慢加入丙烯酸丁酯(1g),加入AIBN(0.01g),升温至80℃,反应12h,降温得到纤维素/丙烯酸丁酯共聚物。
(3)制备纤维素基荧光膜:将荧光化合物吩噻嗪-二苯胺基二苯酮(0.1g)加入纤维素/丙烯酸丁酯(1g/1g)共聚混合液中,搅拌溶解,用线棒涂膜,将膜浸入水中除去DMAc/LiCl,得到湿膜,干燥得到透明的纤维素基荧光膜ODP/PC1BM。
实施例2:
本例是白光发射的纤维素基荧光膜的制造例。
步骤(1)和步骤(3)与实施例1操作相同。不同之处在于步骤(2)采用以下步骤:向配有冷凝管、磁力搅拌子的三口烧瓶中,加入微晶纤维素(1g)和DMAc(29g),升温至160℃,保温30min,降温至100℃,加入LiCl(3g),保温30min,降至室温静置过夜,得到浓度为3%的纤维素溶液;向纤维素溶液中缓慢加入丙烯酸丁酯(0.2g),加入AIBN(0.01g),升温至80℃,反应12h,降温得到纤维素/丙烯酸丁酯共聚物。
实施例3:
本例是白光发射的纤维素基荧光膜的制造例。
步骤(1)和步骤(3)与实施例1操作相同。不同之处在于步骤(2)采用以下步骤:向配有冷凝管、磁力搅拌子的三口烧瓶中,加入微晶纤维素(1g)和DMAc(29g),升温至160℃,保温30min,降温至100℃,加入LiCl(3g),保温30min,降至室温静置过夜,得到浓度为3%的纤维素溶液;向纤维素溶液中缓慢加入丙烯酸丁酯(0.1g),加入AIBN(0.01g),升温至80℃,反应12h,降温得到纤维素/丙烯酸丁酯共聚物。
实施例4:
本例是白光发射的纤维素基荧光膜的制造例。
步骤(1)和步骤(3)与实施例1操作相同。不同之处在于步骤(2)采用以下步骤:纤维素/丙烯酸丁酯共聚物的合成:向配有冷凝管、磁力搅拌子的三口烧瓶中,加入微晶纤维素(1g)和DMAc(29g),升温至160℃,保温30min,降温至100℃,加入LiCl(3g),保温30min,降至室温静置过夜,得到浓度为3%的纤维素溶液;向纤维素溶液中缓慢加入丙烯酸丁酯(0.08g),加入AIBN(0.01g),升温至80℃,反应12h,降温得到纤维素/丙烯酸丁酯共聚物。
实施例5:
本例是白光发射的纤维素基荧光膜的制造例。
步骤(1)和步骤(3)与实施例1操作相同。不同之处在于步骤(2)采用以下步骤:向配有冷凝管、磁力搅拌子的三口烧瓶中,加入微晶纤维素(1g)和DMAc(29g),升温至160℃,保温30min,降温至100℃,加入LiCl(3g),保温30min,降至室温静置过夜,得到浓度为3%的纤维素溶液;向纤维素溶液中缓慢加入丙烯酸丁酯(0.06g),加入AIBN(0.01g),升温至80℃,反应12h,降温得到纤维素/丙烯酸丁酯共聚物。
实施例6:
本例是白光发射的纤维素基荧光膜的制造例。
步骤(1)和步骤(3)与实施例1操作相同。不同之处在于步骤(2)采用以下步骤:向配有冷凝管、磁力搅拌子的三口烧瓶中,加入微晶纤维素(1g)和DMAc(29g),升温至160℃,保温30min,降温至100℃,加入LiCl(3g),保温30min,降至室温静置过夜,得到浓度为3%的纤维素溶液;向纤维素溶液中缓慢加入丙烯酸丁酯(0.05g),加入AIBN(0.01g),升温至80℃,反应12h,降温得到纤维素/丙烯酸丁酯共聚物。
Claims (4)
1.一种白光发射的纤维素基荧光膜的制备方法,包括如下步骤:
(1)将吩噻嗪和4-碘-4’-二苯胺基二苯酮溶解于N,N-二甲基甲酰胺,通氩气,加入碘化亚铜,升温至165~175℃,反应15~17h,反应结束后分离提纯,合成荧光单体吩噻嗪-二苯胺基二苯酮,其中吩噻嗪、4-碘-4’-二苯胺基二苯酮、碘化亚铜摩尔比为1:(0.5~2):(0.01~0.1);
(2)将纤维素溶解在DMAc及LiCl中,得到2~5%质量浓度的纤维素溶液,缓慢加入丙烯酸丁酯,加入AIBN,搅拌升温至75~85℃,反应11~13h,冷却得到纤维素/丙烯酸丁酯共聚混合反应液从而合成纤维素/丙烯酸丁酯共聚物,其中纤维素、DMAc、LiCl、丙烯酸丁酯、AIBN的质量比依次为1:(17~45):(2~8):(0.05~1):(0.01~0.05);
(3)将步骤(1)所获得的荧光单体吩噻嗪-二苯胺基二苯酮加入步骤(2)所获得的纤维素/丙烯酸丁酯共聚混合反应液中,搅拌均匀,用线棒涂膜,将膜泡在水中除去DMAc及LiCl得到湿膜,干燥后制得纤维素基荧光膜。
2.如权利要求1所述的一种白光发射的纤维素基荧光膜的制备方法,其特征在于:所述4-碘-4’-二苯胺基二苯酮的制备是通过以下步骤获得:将二苯胺溶解于N,N-二甲基甲酰胺中,然后加入NaH,升温至70~80℃,再加入4-氟-4’-碘二苯酮,升温至105~115℃,反应11~13h,反应结束后分离提纯所得。
3.如权利要求2所述的一种白光发射的纤维素基荧光膜的制备方法,其特征在于:所述4-氟-4’-碘二苯酮的制备是通过以下步骤获得:将4-碘苯甲酰氯和氟苯加入到干燥三颈瓶中搅拌,再加入无水氯化铝,升温至40~50℃,反应5~6h,反应结束后,分离提纯所得,其中4-碘苯甲酰氯、氟苯、无水氯化铝的摩尔比依次为1:(3~4):(2~5)。
4.由权利要求1~3任一所述的方法所制得的纤维素基荧光膜。
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