CN107353383B - 一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法 - Google Patents

一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法 Download PDF

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CN107353383B
CN107353383B CN201710558711.4A CN201710558711A CN107353383B CN 107353383 B CN107353383 B CN 107353383B CN 201710558711 A CN201710558711 A CN 201710558711A CN 107353383 B CN107353383 B CN 107353383B
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范浩军
田赛琦
陈意
颜俊
章培昆
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Sichuan University
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Abstract

本发明公开了一种无溶剂型光致变色蓄能发光合成革用聚氨酯的制备方法，将长余辉发光材料和光转换剂同时引入聚氨酯，赋予了聚氨酯良好的变色发光特性。该聚氨酯可以同时吸收紫外光和可见光，白天时为红色，夜晚则发出黄色的光，克服了现有发光材料颜色集中在较窄的波长范围内且较为单一的问题，可赋予合成革制品新的花色品种。所选用的光转换剂本身含有羟基和亚氨基，可通过化学键嵌入到聚氨酯结构单元中，解决了现有共混复配型光转换剂与聚氨酯配伍性差、易迁移析出等问题，使其具有更稳定持久变色效果。另外，该聚氨酯不含任何有机溶剂，具有突出的绿色、环保、健康等特性，可用于高性能、高品质、高环保的合成革制造及皮革等涂层材料。

Description

一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法
技术领域
本发明属于高分子材料合成技术领域，具体涉及一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法。
背景技术
聚氨酯行业将用PU树脂与基布生产的人造革称为PU合成革，简称合成革。PU合成革同时具有色彩丰富、花纹繁多等优点，价格又比皮质面料便宜，所以深受消费者的欢迎，并且作为一种常见的日用材料进入人们生活的各个方面，在家居装饰、服装、汽车内饰等各方面发挥着不可替代的作用。
随着全球聚氨酯合成革行业以及消费者对合成革产品的VOC含量环保要求越来越高，基于传统溶剂型树脂制造的合成革已无法满足国内外市场的要求，因而，环保型聚氨酯合成革产品在近年来备受关注并逐渐发展。其中，无溶剂型聚氨酯合成革因其突出的物理性能及加工成型上的节能减排优势，成为环保型聚氨酯合成革产品中被人们尤为看好的一类。此外，随着人们对于高性能、高品质、高环保的生态合成革的需求持续上升，单一性能的合成革产品已经不能满足的需求，近年来，如发光、变色、吸波、电磁屏蔽等功能性合成革制品备受消费者青睐。
长余辉发光材料，能够储存外界光辐照能量，在光线充足时吸收光并储存起来，在黑暗条件下，缓慢地以可见光的形式释放储存的能量。其中，稀土金属激发的碱土铝酸盐系列发光材料具有发光效率高、余辉时间长、化学性质稳定、无放射性危害等优点，一直受到人们的重视。将长余辉发光材料与合成革涂层用聚氨酯结合，可以赋予合成革制品新的花色品种。将其用于环卫工人服、消防员服、野外工作者、登山运动员服装等的制造，可减少特殊工作环境中潜在的危险；用于儿童服装，可提高儿童在夜间行走的安全性，同时可增加儿童服装的趣味性；用于夜间作业的工作服装，比如矿井工人的工作服，为夜间工作人员的工作提供便利条件，且在危险事故发生时，其自发光功能也便于搜救工作的展开，为救援工作提供帮助。蓄能发光型合成革可用于各类日常生活、休闲娱乐及交通运输等方面，为人类提供更加便利、丰富的生活条件。
中国专利201410784579.5公开了一种稀土铝酸盐蓝色长余辉聚氨酯弹性纤维的制备方法，将稀土铝酸盐发光材料均匀分散在聚氨酯原液中，通过干法纺丝系统，制备具有优异发光性能的聚氨酯纤维同时不影响其力学性能。中国专利201310589008.1公开了一种蓝绿光发光膜制备方法，提供了一种环保、韧性好，使用寿命长，且制作工艺简单的蓝绿光发光膜制备工艺。
然而目前应用最广的长余辉发光材料主要为绿色的铝酸盐或者蓝色的硅酸盐，发光颜色集中在较窄的波长范围内，较为单一，显得过于单调和呆板，无法给人们尤其是喜欢追求时尚元素的年轻人带来更多的美感与乐趣，单一颜色的面料满足不了市场的需求，也束缚了服装设计师对个性服装面料的选择，限制了其更为广阔的应用。
发明内容
本发明的目的是针对上述现有技术的不足而提供一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，采用长余辉发光材料和光转换剂结合的方式，赋予了聚氨酯良好的变色发光特性，该聚氨酯可以吸收紫外光和可见光，白天时呈红色，夜晚时则发出黄色的光，且在生产过程中不含任何有机溶剂，符合消费者的绿色消费、环保健康的需求。
本发明提供的合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，其特征在于包括如下步骤：(1)羟基封端的聚氨酯预聚体的制备：将聚醚或聚酯二元醇在120℃、-0.08MPa～-0.1MPa的真空条件下进行脱水4-5h，备用；将脱水后的聚醚或聚酯二元醇38-60份加入到反应釜中，再依次投入扩链剂1-3份和异氰酸酯12-18份，催化剂0.05-0.1份，升温至65-85℃，搅拌2-3h后降温至55℃，加入封端剂N-甲基单乙醇胺3.5-5份，搅拌0.5h，密封包装待用；
(2)合成革用无溶剂型光致变色蓄能发光聚氨酯的制备：将异氰酸酯8-30份、稀土金属激发的铝酸盐长余辉发光材料3-12份、光转换剂1-[(2-羟乙基)氨基]蒽醌0.3-1.2份加入到所制得的上述羟基封端的聚氨酯预聚体中，控制体系R值在1.0-1.5，进行充分混合，然后浇注涂覆于离型纸上，在90℃烘箱中烘干即可得到合成革用无溶剂型光致变色蓄能发光聚氨酯。
所述的聚醚或聚酯二元醇为数均分子量为1000-4000的聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚丙二醇、聚己内酯二醇、聚碳酸酯二醇、聚乙二醇、聚四氢呋喃中任意两种的组合。
所述的扩链剂优选使用小分子二元醇，小分子二元醇为1,4-丁二醇、1,6-己二醇、乙二醇、1,3-丙二醇、一缩二乙二醇或二乙烯基乙二醇中的任一种或其组合。
所述的催化剂为月桂酸二丁基锡、辛酸亚锡、二甲基环己胺或N-乙基吗啡啉中的任一种或其组合。
所述的异氰酸酯为2,4-甲苯二异氰酸酯、4,4'-二苯甲烷二异氰酸酯，异佛二酮二异氰酸酯，六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯或对苯二异氰酸酯中的任一种或其组合。
所述的稀土金属激发的铝酸盐长余辉发光材料的结构式为SrAl2O4:Eu2+,Dy3+。
所述的光转换剂1-[(2-羟乙基)氨基]蒽醌的结构式如下：
所述的聚氨酯树脂体系不包含有机溶剂。
所述的聚氨酯可用于聚氨酯合成革的面层或中层。
与现有技术相比，本发明具有以下明显优点：
(1)本发明在合成过程中不使用任何有机溶剂，所制得的合成革用无溶剂型光致变色蓄能发光聚氨酯为环保产品，符合合成革行业发展趋势，并且符合消费者的绿色消费、环保健康的需求；
(2)本发明采用一种红色荧光剂作为光转换剂引入至聚氨酯内，将长余辉发光材料发出的蓝绿光转换成黄光，所制得的聚氨酯可以吸收紫外光和可见光，白天时为红色，夜晚时发出黄色的光，呈现出良好的光致变色蓄能发光效果；
(3)本发明所选用的光转换剂本身含有羟基和亚氨基，可通过化学键嵌入到聚氨酯结构单元中，解决了现有共混复配型材料与聚氨酯配伍性差、易迁移析出等问题，具有稳定持久变色效果。
具体实施方式
下面通过实施例对本发明进行具体描述，有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1
(1)羟基封端的聚氨酯预聚体的制备：将数均分子量为2000的聚丙二醇(PPG2000)30份和数均分子量为1000的聚四氢呋喃二元醇(PTMG1000)8份在120℃、-0.08MPa～-0.1MPa的真空条件下进行脱水5h，以降低副反应的发生，备用；将脱水后的PTMG2000和PTMG1000加入到反应釜中，再依次投入扩链剂1,4-丁二醇1.35份和异佛尔酮二异氰酸酯15份，催化剂月桂酸二丁基锡0.1份，升温至75℃，搅拌3h后降温至55℃，加入封端剂N-甲基单乙醇胺4.5份，搅拌0.5h，密封包装待用；
(2)合成革用无溶剂型光致变色蓄能发光聚氨酯的制备：将4,4'-二环己基甲烷二异氰酸酯(H12MDI)30份、长余辉发光材料SrAl2O4:Eu2+,Dy3+12份、光转换剂1-[(2-羟乙基)氨基]蒽醌1.2份加入到所制得的上述羟基封端的聚氨酯预聚体中，控制体系R值在1.0，进行充分混合，然后浇注涂覆于离型纸上，在90℃烘箱中烘干即可得到合成革用无溶剂型光致变色蓄能发光聚氨酯。
该光致变色蓄能发光聚氨酯在制备和使用过程中不使用任何有机溶剂，可以吸收紫外光和可见光，白天时为红色，夜晚时发出黄色的光，适用于聚氨酯合成革的中层。
实施例2
(1)羟基封端的聚氨酯预聚体的制备：将数均分子量为4000的聚丙二醇(PPG4000)40份和数均分子量为1000的聚己二酸-1,4-丁二醇酯二醇(PBA1000)10份在120℃、-0.08MPa～-0.1MPa的真空条件下进行脱水4h，以降低副反应的发生，备用；将脱水后的PPG4000和PBA1000加入到反应釜中，再依次投入扩链剂二甘醇1份和异佛尔酮二异氰酸酯10份，六亚甲基二异氰酸酯2份，催化剂辛酸亚锡0.07份，升温至85℃，搅拌2h后降温至55℃，加入封端剂N-甲基单乙醇胺3.5份，搅拌0.5h，密封包装待用；
(2)合成革用无溶剂型光致变色蓄能发光聚氨酯的制备：将六亚甲基二异氰酸酯7.8份、长余辉发光材料SrAl2O4:Eu2+,Dy3+3份、光转换剂1-[(2-羟乙基)氨基]蒽醌0.3份加入到所制得的上述羟基封端的聚氨酯预聚体中，控制体系R值在1.5，进行充分混合，然后浇注涂覆于离型纸上，在90℃烘箱中烘干即可得到合成革用无溶剂型光致变色蓄能发光聚氨酯。
该光致变色蓄能发光聚氨酯在制备和使用过程中不使用任何有机溶剂，可以吸收紫外光和可见光，白天时为红色，夜晚时发出黄色的光，适用于聚氨酯合成革的面层。
实施例3
(1)羟基封端的聚氨酯预聚体的制备：将数均分子量为2000的聚乙二醇(PEG2000)40份和数均分子量为1000的聚乙二醇(PEG1000)20份在120℃、-0.08MPa～-0.1MPa的真空条件下进行脱水4.5h，以降低副反应的发生，备用；将脱水后的PEG2000和PEG1000加入到反应釜中，再依次投入扩链剂三甘醇3份和二苯基甲烷二异氰酸酯18份，催化剂二甲基环己胺0.05份，升温至65℃，搅拌2.5h后降温至55℃，加入封端剂N-甲基单乙醇胺5份，搅拌0.5h，密封包装待用；
(2)合成革用无溶剂型光致变色蓄能发光聚氨酯的制备：将4,4'-二环己基甲烷二异氰酸酯21份、长余辉发光材料SrAl2O4:Eu2+,Dy3+8份、光转换剂1-[(2-羟乙基)氨基]蒽醌0.8份加入到所制得的上述羟基封端的聚氨酯预聚体中，控制体系R值在1.2，进行充分混合，然后浇注涂覆于离型纸上，在90℃烘箱中烘干即可得到合成革用无溶剂型光致变色蓄能发光聚氨酯。
该光致变色蓄能发光聚氨酯在制备和使用过程中不使用任何有机溶剂，可以吸收紫外光和可见光，白天时为红色，夜晚时发出黄色的光，适用于聚氨酯合成革的中层。

Claims (6)

1.一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，包括如下步骤：
(1)羟基封端的聚氨酯预聚体的制备：将聚醚或聚酯二元醇在120℃、-0.08MPa～-0.1MPa的真空条件下进行脱水4-5h，备用；将脱水后的聚醚或聚酯二元醇38-60份加入到反应釜中，再依次投入扩链剂1-3份和异氰酸酯12-18份，催化剂0.05-0.1份，升温至65-85℃，搅拌2-3h后降温至55℃，加入封端剂N-甲基单乙醇胺3.5-5份，搅拌0.5h，密封包装待用；
(2)合成革用无溶剂型光致变色蓄能发光聚氨酯的制备：将异氰酸酯8-30份、稀土金属激发的铝酸盐长余辉发光材料3-12份、光转换剂1-[(2-羟乙基)氨基]蒽醌0.3-1.2份加入到所制得的上述羟基封端的聚氨酯预聚体中，控制体系R值在1.0-1.5，进行充分混合，然后浇注涂覆于离型纸上，在90℃烘箱中烘干即可得到合成革用无溶剂型光致变色蓄能发光聚氨酯，其中长余辉发光材料结构式为SrAl2O4:Eu2+，Dy3+。
2.根据权利要求1所述的合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，其特征在于该方法中所用的聚醚或聚酯二元醇为数均分子量为1000-4000的聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚丙二醇，聚己内酯二醇、聚碳酸酯二醇、聚乙二醇、聚四氢呋喃中任意两种的组合。
3.根据权利1所述的一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，其特征在于，所述的扩链剂使用小分子二元醇为1,4-丁二醇、1,6-己二醇、乙二醇、1,3-丙二醇、一缩二乙二醇或二乙烯基乙二醇中的任一种或其组合。
4.根据权利1所述的一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，其特征在于所述的催化剂为月桂酸二丁基锡、辛酸亚锡、二甲基环己胺或N-乙基吗啡啉中的任一种或其组合。
5.根据权利1所述的一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，其特征在于所述的芳香族族或脂肪族二异氰酸酯为2,4-甲苯二异氰酸酯、4,4’-二苯甲烷二异氰酸酯，异佛尔酮二异氰酸酯，六亚甲基二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯或对苯二异氰酸酯中的任一种或其组合。
6.根据权利1所述的一种合成革用无溶剂型光致变色蓄能发光聚氨酯的制备方法，其特征在于，所述的聚氨酯用于聚氨酯合成革的面层。
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