CN110330622B - 荧光水性聚氨酯及其制备方法 - Google Patents
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- CN110330622B CN110330622B CN201910640788.5A CN201910640788A CN110330622B CN 110330622 B CN110330622 B CN 110330622B CN 201910640788 A CN201910640788 A CN 201910640788A CN 110330622 B CN110330622 B CN 110330622B
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Abstract
本发明涉及一种荧光水性聚氨酯及其制备方法，属于功能型水性聚氨酯合成技术领域。本发明的荧光水性聚氨酯的制备方法包括如下步骤：在惰性气氛下将二异氰酸酯和荧光素混合，50～70℃反应后加入低聚物二元醇、亲水扩链剂、催化剂，再升温至70～90℃反应得到含端异氰酸根的荧光水性聚氨酯预聚体；再降温至40～60℃，调节固含量，加入小分子扩链剂反应后再加入中和剂反应，得到荧光聚氨酯。采用本发明的方法制备荧光水性聚氨酯，有利于将荧光素充分的引入到聚氨酯主链上，避免由于低聚物二元醇和预聚物的粘性和分子量较大导致聚氨酯分子大而影响荧光素小分子的引入，此外，可控制荧光素的添加量来调整聚氨酯分子的发色团含量。
Description
技术领域
本发明涉及一种荧光水性聚氨酯及其制备方法，属于功能型水性聚氨酯合成技术领域。
背景技术
随着环保法规和意识的建立，水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系，具有无污染、相容性能好、力学性能优异、易于改性等优点，可广泛用涂料、胶粘剂、织物涂层和整理剂、皮革涂饰剂等，具有功能性结构的水性聚氨酯也逐渐被广泛的研究和应用。
荧光水性聚氨酯也是近年来研究的热点，将具有共轭双键和发光效率的荧光分子通过化学结构的方式引入到水性聚氨酯主链上，解决了水性聚氨酯与荧光材料直接物理共混而引起的荧光稳定性差、荧光猝灭现象和热迁移率大问题。
申请号为2013102238683的中国专利申请公布了一种含荧光染料的水性聚氨酯的制备方法，利用分子上含有羟基或氨基的苯环共轭结构荧光染料与异氰酸根反应接入聚氨酯分子链上，形成荧光聚氨酯预聚体再进一步反应得到荧光水性聚氨酯。其选取的荧光染料为端羟基或端氨基的分子结构，与异氰酸根进行封端反应。申请号为2015107121406的中国专利申请公布了一种环境友好型荧光水性聚氨酯及其制备方法，选取了含端羟基的荧光剂进行扩链作用，利用荧光剂分子上的荧光基团使的水性聚氨酯激发跃迁发光，所采用的荧光剂为碳碳和碳氮双键平面共轭结构。然而这些现有技术制备得到的产品荧光分子的引入量少，荧光发光效应较低。
发明内容
本发明要解决的第一个问题是提供一种荧光水性聚氨酯的制备方法，采用该方法荧光素能充分反应，从而充分将荧光素引入到聚氨酯主链上。
为解决本发明的第一个技术问题，所述荧光水性聚氨酯的制备方法包括如下步骤：
a.在惰性气氛下将二异氰酸酯和荧光素混合，50～70℃反应2～3h；
所述荧光素为双羟基苯环共轭结构；优选为含硫的双羟基苯环共轭结构；
b.在a步骤反应后的溶液中加入低聚物二元醇、亲水扩链剂、催化剂，再升温至70～90℃反应得到含端异氰酸根的荧光水性聚氨酯预聚体；
c.将b步骤所述的荧光水性聚氨酯预聚体降温至40～60℃，调节固含量为40～70％，加入小分子扩链剂反应后再加入中和剂反应，得到荧光聚氨酯；
其中，所述二异氰酸酯中-NCO基团与低聚物二元醇和小分子扩链剂中总的-OH的摩尔比为1.2～2.0：1；
所述二异氰酸酯中-NCO基团:含硫荧光素:亲水扩链剂:催化剂:小分子扩链剂:中和剂:荧光水性聚氨酯预聚体的重量比为：2～48:0.01～1:3～9:0.01～0.1:0.03～0.9:1～7:100。
本发明所述的惰性气氛是指不与原料、中间体和产品反应的气体，例如氮气、可以是氩气、氦气等等。
优选的，所述荧光素为
优选的，所述二异氰酸酯为甲苯二异氰酸酯，1,5-萘二异氰酸酯，六亚甲基二异氰酸酯，对苯二异氰酸酯，异佛尔酮二异氰酸酯，二苯基甲烷二异氰酸酯，3,3’-二甲基-4,4’-联苯二异氰酸酯，4,4’-二环己基甲烷二异氰酸酯中的至少一种。
优选的，所述亲水扩链剂为二羟甲基丙酸，二羟甲基丁酸中的至少一种；所述催化剂优选为二月桂酸二丁基锡，辛酸亚锡中的至少一种；所述小分子扩链剂优选为1,2-丙二醇，1,4-丁二醇，1,6-己二醇，乙二醇，一缩二乙二醇，新戊二醇，1,4-环己二醇中的至少一种；所述中和剂优选为三甲胺，三乙胺，三丙胺，氢氧化钠，氨水中的至少一种。
优选的，b步骤所述反应的时间为3～6h；
c步骤所述加入小分子扩链剂反应的时间优选为2～5h；c步骤所述加入中和剂反应的时间优选为0.5～2h。
优选的，b步骤所述低聚物二元醇为4～60个单体聚合而成，优选4～20个单体聚合而成；优选的，所述低聚物二元醇为聚乙二醇，聚碳酸酯二醇，聚四氢呋喃二醇，聚己内酯二醇，聚己二酸丁二醇酯，聚己二酸己二醇酯，聚丙二醇，聚四亚甲基二醇中的一种或两种。
所述低聚物二元醇中不能有水份，为了确保没有水份可以采用常规的干燥方法先将低聚物二元醇进行干燥处理，例如将低聚物二元醇经过减压真空干燥处理。
优选的，c步骤采用甲酮或丙酮调节固含量。
进一步地，所述方法还包括步骤d.将荧光聚氨酯与水混合，乳化，制备荧光水性聚氨酯乳液；优选为将荧光聚氨酯与水混合，大于1000rpm搅拌乳化10～30min，得到含荧光的水性聚氨酯乳液。
进一步地，所述方法还包括将所述含荧光的水性聚氨酯乳液甲酮或丙酮蒸发回收，得到固含量为20～40％的荧光水性聚氨酯。
本发明要解决的第二个技术问题是提供一种荧光水性聚氨酯，该荧光水性聚氨酯采用上述的方法制备得到，荧光素小分子的引入量为荧光水性聚氨酯总质量的0.01～1％。
有益效果：
采用本发明的方法制备荧光水性聚氨酯，有利于将荧光素充分的引入到聚氨酯主链上，避免由于低聚物二元醇和预聚物的粘性和分子量较大导致聚氨酯分子大而影响荧光素小分子的引入，此外，可控制荧光素的添加量来调整聚氨酯分子的发色团含量。
采用本发明的方法过程工艺简单、重现性好、软硬段可供调节，由于荧光素充分反应，因此添加荧光素不用过量，成本低，少量即可获得具有荧光特性的水性聚氨酯。
附图说明
图1为本发明实施例1所述异硫氰酸荧光素和含硫荧光水性聚氨酯预聚体的红外光谱图。
图2为本发明实施例1所述异硫氰酸荧光素(λex＝490nm，狭缝8nm)和含硫荧光水性聚氨酯(λex＝470nm，狭缝10nm)的荧光光谱图。
图3本发明实施例3所制备的含硫荧光水性聚氨酯的扫描电镜图(左)和硫元素的面分析图(右)；
图4水性聚氨酯(拉伸强度＝25.6MPa)和本发明实施例3制备的含硫荧光水性聚氨酯(拉伸强度＝32.7MPa)的力学数据图；
WPU-水性聚氨酯；FWPU--荧光水性聚氨酯；FITC-异硫氰酸荧光素。
具体实施方式
为解决本发明的第一个技术问题，所述荧光水性聚氨酯的制备方法包括如下步骤：
a.在惰性气氛下将二异氰酸酯和荧光素混合，50～70℃反应2～3h；
所述荧光素为双羟基苯环共轭结构；优选为含硫的双羟基苯环共轭结构；
b.在a步骤反应后的溶液中加入低聚物二元醇、亲水扩链剂、催化剂，再升温至70～90℃反应得到含端异氰酸根的荧光水性聚氨酯预聚体；
c.将b步骤所述的荧光水性聚氨酯预聚体降温至40～60℃，调节粘度，加入小分子扩链剂反应后再加入中和剂反应，得到荧光聚氨酯；
其中，所述二异氰酸酯中-NCO基团与低聚物二元醇和小分子扩链剂中总的-OH的摩尔比为1.2～2.0：1；
所述二异氰酸酯中-NCO基团:含硫荧光素:亲水扩链剂:催化剂:小分子扩链剂:中和剂:荧光水性聚氨酯预聚体的重量比为：2～48:0.01～1:3～9:0.01～0.1:0.03～0.9:1～7:100。
优选的，所述荧光素为
优选的，所述二异氰酸酯为甲苯二异氰酸酯，1,5-萘二异氰酸酯，六亚甲基二异氰酸酯，对苯二异氰酸酯，异佛尔酮二异氰酸酯，二苯基甲烷二异氰酸酯，3,3’-二甲基-4,4’-联苯二异氰酸酯，4,4’-二环己基甲烷二异氰酸酯中的至少一种。
优选的，所述亲水扩链剂为二羟甲基丙酸，二羟甲基丁酸中的至少一种；所述催化剂优选为二月桂酸二丁基锡，辛酸亚锡中的至少一种；所述小分子扩链剂优选为1,2-丙二醇，1,4-丁二醇，1,6-己二醇，乙二醇，一缩二乙二醇，新戊二醇，1,4-环己二醇中的至少一种；所述中和剂优选为三甲胺，三乙胺，三丙胺，氢氧化钠，氨水中的至少一种。
优选的，b步骤所述反应的时间优选为3～6h；
c步骤所述加入小分子扩链剂反应的时间优选为2～5h；c步骤所述加入中和剂反应的时间优选为0.5～2h。
优选的，b步骤所述低聚物二元醇为4～60个单体聚合而成，优选4～20个单体聚合而成；优选的，所述低聚物二元醇为聚乙二醇，聚碳酸酯二醇，聚四氢呋喃二醇，聚己内酯二醇，聚己二酸丁二醇酯，聚己二酸己二醇酯，聚丙二醇，聚四亚甲基二醇中的一种或两种。
优选的，c步骤采用甲酮或丙酮调节固含量。
进一步地，所述方法还包括步骤d.将荧光聚氨酯与水混合，乳化，制备荧光水性聚氨酯乳液；优选为将荧光聚氨酯与水混合，大于1000rpm搅拌乳化10～30min，得到含荧光的水性聚氨酯乳液。
进一步地，所述方法还包括将所述含荧光的水性聚氨酯乳液甲酮或丙酮蒸发回收，得到固含量为20～40％的荧光水性聚氨酯。
本发明要解决的第二个技术问题是提供一种荧光水性聚氨酯，该荧光水性聚氨酯采用上述的方法制备得到，荧光素小分子的引入量为荧光水性聚氨酯总质量的0.01～1％。
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。
实施例1
将聚碳酸酯二醇(数均分子量为1000)在120℃下进行减压脱水2h，在氮气保护下，将15.28ml异佛尔酮二异氰酸酯和10mg异硫氰酸荧光素(FITC)加入到100ml烧瓶中于60℃反应2h。
然后依次加入30.00g聚碳酸酯二醇，2.31g二羟甲基丙酸(少量二甲基甲酰胺溶解)，加入0.02g二月桂酸二丁基锡，升温至80℃下反应4h，接着降温至50℃后加入丙酮50ml搅拌溶解30min，再加入0.23ml的1,4-丁二醇继续反应2h，然后加入2.39ml三乙胺进行中和反应30min得到荧光聚氨酯。最后倒入烧杯中，加入75ml去离子水于1000rpm下进行高速乳化20min，最后通过旋转蒸发仪回收丙酮后得到黄绿色的含硫荧光素的水性聚氨酯乳液。
检测反应后的溶液中异硫氰酸荧光素(FITC)，异硫氰酸荧光素的反应率为98.5％。
实施例2
将聚四氢呋喃二醇(数均分子量为2000)在120℃下进行减压脱水2h，在氮气保护下，将5.80ml甲苯二异氰酸酯和8mg异硫氰酸荧光素(FITC)加入到100ml烧瓶中于60℃反应2h。
然后依次加入20.00g聚四氢呋喃二醇，1.90g二羟甲基丙酸(少量二甲基甲酰胺溶解)，加入0.01g二月桂酸二丁基锡，升温至80℃下反应4h，接着降温至50℃后加入丙酮50ml搅拌溶解30min，再加入0.12ml的一缩二乙二醇继续反应2h，然后加入1.97ml三乙胺进行中和反应30min得到荧光聚氨酯。最后倒入烧杯中，加入70ml去离子水于1000rpm下进行高速乳化20min，最后通过旋转蒸发仪回收丙酮后得到黄绿色的含硫荧光素的水性聚氨酯乳液。
检测反应后的溶液中异硫氰酸荧光素(FITC)，异硫氰酸荧光素的反应率为96.4％。
实施例3
将聚碳酸酯二醇(数均分子量为1000)在120℃下进行减压脱水2h，在氮气保护下，将8.17ml甲苯二异氰酸酯和15mg异硫氰酸荧光素(FITC)加入到100ml烧瓶中于60℃反应3h。
然后依次加入30.00g聚碳酸酯二醇，2.80g二羟甲基丁酸(少量二甲基甲酰胺溶解)，加入0.02g二月桂酸二丁基锡，升温至80℃下反应4h，接着降温至50℃后加入丙酮50ml搅拌溶解30min，再加入0.18ml的一缩二乙二醇继续反应3h，然后加入2.63ml三乙胺进行中和反应1h得到荧光聚氨酯。最后倒入烧杯中，加入65ml去离子水于1000rpm下进行高速乳化30min，最后通过旋转蒸发仪回收丙酮后得到黄绿色的含硫荧光素的水性聚氨酯乳液。
检测反应后的溶液中异硫氰酸荧光素(FITC)，异硫氰酸荧光素的反应率为97.3％。
实施例4
将聚丙二醇(数均分子量为3000)在120℃下进行减压脱水2h，在氮气保护下，将10.16ml异佛尔酮二异氰酸酯和20mg异硫氰酸荧光素(FITC)加入到100ml烧瓶中于60℃反应2h。
然后依次加入40.00g聚丙二醇，1.79g二羟甲基丙酸(少量二甲基甲酰胺溶解)，加入0.02g二月桂酸二丁基锡，升温至80℃下反应4h，接着降温至50℃后加入丙酮50ml搅拌溶解30min，再加入0.13ml的一缩二乙二醇继续反应2h，然后加入1.85ml三乙胺进行中和反应30min得到荧光聚氨酯。最后倒入烧杯中，加入100ml去离子水于1000rpm下进行高速乳化20min，最后通过旋转蒸发仪回收丙酮后得到黄绿色的含硫荧光素的水性聚氨酯乳液。
检测反应后的溶液中异硫氰酸荧光素(FITC)，异硫氰酸荧光素的反应率为95.3％。
对比例1
将聚碳酸酯二醇(数均分子量为1000)在120℃下进行减压脱水2h，在氮气保护下，将30.00g聚碳酸酯二醇，2.31g二羟甲基丙酸(少量二甲基甲酰胺溶解)，15.28ml异佛尔酮二异氰酸酯和10mg异硫氰酸荧光素(FITC)加入到100ml烧瓶中，升温至80℃后，继续加入0.02g二月桂酸二丁基锡反应6h。接着降温至50℃后加入丙酮50ml搅拌溶解30min，再加入0.23ml的1,4-丁二醇继续反应2h，然后加入2.39ml三乙胺进行中和反应30min得到荧光聚氨酯。最后倒入烧杯中，加入75ml去离子水于1000rpm下进行高速乳化20min，最后通过旋转蒸发仪回收丙酮后得到黄绿色的含硫荧光素的水性聚氨酯乳液。
检测反应后的溶液中异硫氰酸荧光素(FITC)，异硫氰酸荧光素的反应率为91.7％。
Claims (12)
1.荧光水性聚氨酯的制备方法，其特征在于，所述制备方法为：
a.在惰性气氛下将二异氰酸酯和荧光素混合，50～70℃反应2～3h；
b.在a步骤反应后的溶液中加入低聚物二元醇、亲水扩链剂、催化剂，再升温至70～90℃反应得到含端异氰酸根的荧光水性聚氨酯预聚体；
c.将b步骤所述的荧光水性聚氨酯预聚体降温至40～60℃，采用甲酮或丙酮调节固含量为40～70％，加入小分子扩链剂反应后再加入中和剂反应，得到荧光聚氨酯；
d.将荧光聚氨酯与水混合，乳化，得到含荧光水性聚氨酯乳液，将所述含荧光的水性聚氨酯乳液甲酮或丙酮蒸发回收，得到固含量为20～40％的荧光水性聚氨酯；所述乳化为大于1000rpm搅拌乳化10～30min；
其中，所述二异氰酸酯中-NCO基团与低聚物二元醇和小分子扩链剂中总的-OH的摩尔比为1.2～2.0：1；
所述二异氰酸酯中-NCO基团:含硫荧光素:亲水扩链剂:催化剂:小分子扩链剂:中和剂:荧光水性聚氨酯预聚体的重量比为：2～48:0.01～1:3～9:0.01～0.1:0.03～0.9:1～7:100；
所述荧光素为：
2.根据权利要求1所述的荧光水性聚氨酯的制备方法，其特征在于，所述二异氰酸酯为甲苯二异氰酸酯，1,5-萘二异氰酸酯，六亚甲基二异氰酸酯，对苯二异氰酸酯，异佛尔酮二异氰酸酯，二苯基甲烷二异氰酸酯，3,3’-二甲基-4,4’-联苯二异氰酸酯，4,4’-二环己基甲烷二异氰酸酯中的至少一种。
3.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，所述亲水扩链剂为二羟甲基丙酸，二羟甲基丁酸中的至少一种。
4.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，所述催化剂为二月桂酸二丁基锡，辛酸亚锡中的至少一种。
5.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，所述小分子扩链剂为1,2-丙二醇，1,4-丁二醇，1,6-己二醇，乙二醇，一缩二乙二醇，新戊二醇，1,4-环己二醇中的至少一种。
6.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，所述中和剂为三甲胺，三乙胺，三丙胺，氢氧化钠，氨水中的至少一种。
7.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，b步骤所述反应的时间为3～6h。
8.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，c步骤所述加入小分子扩链剂反应的时间为2～5h。
9.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，c步骤所述加入中和剂反应的时间为0.5～2h。
10.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，b步骤所述低聚物二元醇为4～60个单体聚合而成。
11.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，b步骤所述低聚物二元醇为4～20个单体聚合而成。
12.根据权利要求1或2所述的荧光水性聚氨酯的制备方法，其特征在于，所述低聚物二元醇为聚乙二醇，聚碳酸酯二醇，聚四氢呋喃二醇，聚己内酯二醇，聚己二酸丁二醇酯，聚己二酸己二醇酯，聚丙二醇中的一种或两种。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006007209A2 (en) * | 2004-06-25 | 2006-01-19 | Leatech, Llc | Pressure and temperature sensitive material |
| CN103172829A (zh) * | 2013-03-21 | 2013-06-26 | 中国科学技术大学 | 基于二异氰酸酯中发色团的荧光型水性聚氨酯乳液的制法 |
| CN104164079A (zh) * | 2013-08-14 | 2014-11-26 | 长春工业大学 | 磁性荧光发光pH敏感聚氨酯材料的制备方法 |
| CN106349449A (zh) * | 2016-09-14 | 2017-01-25 | 潍坊昊海新材料有限公司 | 环保型荧光水性聚氨酯及其制备方法 |
Family Cites Families (1)
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006007209A2 (en) * | 2004-06-25 | 2006-01-19 | Leatech, Llc | Pressure and temperature sensitive material |
| CN103172829A (zh) * | 2013-03-21 | 2013-06-26 | 中国科学技术大学 | 基于二异氰酸酯中发色团的荧光型水性聚氨酯乳液的制法 |
| CN104164079A (zh) * | 2013-08-14 | 2014-11-26 | 长春工业大学 | 磁性荧光发光pH敏感聚氨酯材料的制备方法 |
| CN106349449A (zh) * | 2016-09-14 | 2017-01-25 | 潍坊昊海新材料有限公司 | 环保型荧光水性聚氨酯及其制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| A pH-triggered charge reversal and self-fluorescent micelle as a smart nanocarrier for doxorubicin controlled release;Shan Xia等;《J Polym Res》;20170523;第24卷(第6期);全文 * |
| 环境pH响应性聚氨酯材料的合成及荧光性质的研究;蔡桂媂;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140115(第01期);全文 * |
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