CN114907765B - 含硫醇-烯烃-异氰酸酯基质的量子点材料 - Google Patents
含硫醇-烯烃-异氰酸酯基质的量子点材料 Download PDFInfo
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- CN114907765B CN114907765B CN202210501893.2A CN202210501893A CN114907765B CN 114907765 B CN114907765 B CN 114907765B CN 202210501893 A CN202210501893 A CN 202210501893A CN 114907765 B CN114907765 B CN 114907765B
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Classifications
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及一种具有硫醇‑烯烃‑异氰酸酯基质的量子点材料,具体包括通过使用多硫醇和同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体来制备量子点的基质;含有本发明量子点材料的制品具有优异的阻隔水氧的能力、颜色稳定、使用寿命长。
Description
技术领域
本发明涉及一种具有聚合物基质的量子点材料,具体涉及一种具有硫醇-烯烃-异氰酸酯基质的量子点材料。
背景技术
随着电子技术的发展,LED显示屏已全面普及,LED显示屏在亮度、色彩等方面已取得巨大的进步,但传统荧光粉的半峰宽通常大于80nm,饱和性较差, 通常仅能覆盖NTSC(国家电视***委员会)标准色域的80%左右,与真实色彩之间仍存在较大的差别。为解决这一技术问题,量子点显示屏应运而生。量子点显示技术的核心有赖于直径范围在1~20nm的半导体纳米晶体,半峰宽通常为 30-40nm,色纯度高,当其受到光或电的刺激时,便会发出不同颜色的单色光,从而得到色域更加饱满的图像。
量子点材料虽然性能优异,但是由于其比表面积远大于体材料,具有极高的活性,易与空气中水汽和氧气发生反应而造成性能显著衰退。因此,量子点材料必须使用高阻隔薄膜材料进行封装才能满足其应用需求。目前,量子点膜产品的通用结构为,阻隔层对量子点发光层,即红绿量子点涂层,进行包夹式封装,最外侧为具备光扩散功能的扩散层。虽然阻隔层可使内部区域中的量子点免于因为暴露于氧气或水而遭到损坏,但制品的切割边缘会使基体材料暴露于大气环境中。在这些边缘区域中,保护分散于基质中的量子点主要依赖于基质本身的阻挡特性。因此,需要具有更好的阻挡特性的基体,以用于保护量子点免受劣化,从而延长寿命稳定性。
发明内容
本发明涉及在量子点材料中使用的基质,基质能抵抗水和/或氧气的侵入,提供较长时间的可接受的颜色稳定性。
本发明的一个方面,提供了一种量子点复合物,所述复合物包含分散于一种聚合物基质中的量子点,所述聚合物基质由至少一种具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体制备得到。
本发明的另一个方面,提供了一种量子点复合物的制备方法。
本发明再一个方面,提供了一种包含量子点复合物的量子点制品。
本发明的量子点复合物具有优异的阻隔水氧的能力,颜色稳定,可延长显示器应用中量子点制品的使用寿命。
如本发明所用:
“烯基”是指直链或支链的不饱和烃。
“(杂)烃基”,包括烃基烷基和烃基芳基基团,以及杂烃基杂烷基和杂烃基杂芳基基团,杂烃基杂烷基和杂烃基杂芳基基团包含一个或多个悬链(链中)杂原子,诸如醚基或氨基。杂烃基可以任选地包含一个或多个悬链(链中)官能团,所述悬链官能团包括酯、酰胺、脲、氨基甲酸酯和碳酸酯官能团。除非另外指明,否则 (杂)烃基通常包含1个至60个碳原子。
具体实施方式
本发明提供一种量子点复合物,所述复合物包含分散于一种聚合物基质中的量子点,所述聚合物基质由至少一种具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体制备得到。
所述聚合物基质的反应单体中,其中一种单体同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基,优选具有如下结构:
n为1-10;
或者,
n为1-10;
或者,
n为1-10;
或者,
m为1-10;
或者,
p为1-10;
例如所述m、n、p具体可为1、2、3、4、5、6、7、8、9或10。
同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体更优选为
所述聚合物基质的反应单体中,所述多硫醇单体具有下式:Rx(SH)y,其中 Rx为具有y价的烃基基团或杂烃基基团,并且y≥2。多硫醇的硫醇基团可以为伯硫醇或仲硫醇。上述化学式的化合物可包括具有二或更大的平均官能度的化合物的混合物。Rx包含任何(杂)烃基基团,其包括脂族和芳族多硫醇。Rx可任选地还包含一种或多种官能团,所述官能团包括悬垂的羟基、酸、酯或氰基基团或者悬链(链中)醚、脲、氨基甲酸酯和酯基团。
具体地,多硫醇单体选自下式化合物中的一种或多种:
其中n为2~10,R1和R2相同或不同且独立地选自–CH2-CH(SH)CH3和–CH2-CH2-SH;
或者,
其中R3、R4、R5和R6相同或不同且独立地选自–C(O)-CH2-CH2-SH、 -(O)-CH2-CH(SH)CH3、-CH2-C(-CH2-O-C(O)-CH2-CH2-SH)3、-C(O)-CH2-SH和-C(O)-CH(SH)-CH3;
其中R7、R8和R9相同或不同且独立地选自–C(O)-CH2-CH2-SH、-C(O) -CH2-CH(SH)CH3、-C(O)-CH2-SH和-C(O)-CH(SH)-CH3。
优选的多硫醇单体选自下式化合物中的一种或多种:乙二醇双(巯基乙酸酯)、季戊四醇四(3-巯基丙酸酯)、二季戊四醇六(3-巯基丙酸酯)、乙二醇双(3-巯基丙酸酯)、三羟甲基丙烷三(巯基乙酸酯)、三羟甲基丙烷三(3-巯基丙酸酯)、季戊四醇四(巯基乙酸酯)、季戊四醇四(3-巯基丙酸酯)、季戊四醇四(3-巯基丁酸酯)和 1,4-双3-巯基丁酰氧基丁烷、三[2-(3-巯基丙酰氧基]乙基]异氰脲酸酯、三羟甲基丙烷三(巯基乙酸酯)、2,4-双(巯基甲基)-1,3,5,-三嗪-2,4-二硫醇、2,3-二(2-巯基乙基)硫基)-1-丙硫醇、二巯基二乙基硫化物和乙氧基化的三甲基丙-三(3-巯基丙酸酯)。更优选为乙二醇双(巯基乙酸酯)、乙二醇双(3-巯基丙酸酯)、三羟甲基丙烷三(巯基乙酸酯)、三羟甲基丙烷三(3-巯基丙酸酯)、三羟甲基丙烷三(巯基乙酸酯)。
所述聚合物基质的反应单体中,所述多硫醇单体的硫醇基团、所述多烯基的双键基团、以及所述异氰酸酯基团的化学计量摩尔比为(1.2-1.6):(1-1.2):(1-1.2)。在硫醇-异氰酸酯和硫醇-烯烃的不同固化条件下,分步固化有利于高质量量子点制品的固化热控制,尤其是对于同时固化可产生显著量的热的较厚制品。各类官能团的不同比例提供了固化热控制的可能性。
本发明的量子点复合物可以通过将具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体以适合的比率组合,进而固化制备得到。一般来说,在含磷化合物和丙烯酸酯化合物共同催化下,多硫醇基团和多异氰酸酯基团先进行反应,然后在含磷化合物和丙烯酸酯化合物共同催化下多硫醇基团和多烯基团发生迈克尔加成反应,最后多烯基团在光照下发生聚合反应。需要说明的是,此处所述的反应顺序并不是绝对地每一步反应中只有一种反应发生,而是所述反应为主反应,不排除在多硫醇基团和多异氰酸酯基反应时伴随少量的多硫醇基团和多烯基团的反应,在多硫醇基团和多烯基团反应时伴随少量的多硫醇基团和多异氰酸酯基反应。
所述含磷化合物选自如下化合物中的一种或多种:
所述丙烯酸酯化合物选自由丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丁酯、丙烯酸丁酯构成的组中的一种或多种。
所述丙烯酸酯化合物使用量占所有单体总量的0.005-0.05wt%,含磷化合物使用量占所有单体总量的0.005-0.05wt%,丙烯酸酯化合物与含磷化合物的摩尔比为4:1-1:1。
在反应过程中,含磷化合物与丙烯酸酯发生亲核加成反应形成,形成烯醇化磷(其中R独立地不同),该烯醇盐作为强碱催化剂脱去硫醇的质子形成硫醇阴离子,然后硫醇阴离子作为强亲核试剂与异氰酸酯基和/或多烯基团发生反应。
本发明还提供了一种量子点复合物的制备方法,包含以下步骤:
i)提供量子点材料、一种具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体;
ii)将量子点材料和具有≥2官能度的多硫醇单体、同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体以及含磷化合物、丙烯酸酯化合物和光引发剂进行混合,在低于60℃下反应一定时间;
iii)然后升温反应一段时间;
iv)保持步骤iii)的温度,向步骤iii)得到的中间体加入光引发剂光照一定的时间,最后再升温反应一定时间。
为了控制反应顺序以实现对反应产物物理化学性能的控制,每一步的反应需在合适的条件下进行,具体地:所述步骤ii)的反应条件为在10-60℃下反应10-30 分钟,在该步骤,硫醇基团和异氰酸酯基团先作为主要反应进行。
在一个实施方案中,所述步骤iii)的反应条件为在65-100℃下反应0.5-2小时,以使得硫醇基团和多烯基团作为主反应进行。
在一个实施方案中,所述步骤iv)的光照条件为紫外光下光照10-20分钟,以使得残留的烯基发生自聚反应。
所述步骤iv)还加入光引发剂来引发烯基的自聚反应。
优选地光引发能源可发出紫外线辐射,即,具有约180至460纳米之间波长的辐射,其包括诸如汞弧灯、碳弧灯、低、中或高压汞蒸气灯、湍流等离子体弧灯、氙闪光灯、紫外发光二极管和紫外发光激光器的光引发能源。
在一个实施方案中,引发剂是光引发剂并且能够通过紫外线辐射激活。可用的光引发剂包括(例如)苯偶姻醚(诸如,苯偶姻甲醚和苯偶姻异丙醚)、取代的苯偶姻醚、取代的苯乙酮(诸如,2,2-二甲氧基-2-苯基苯乙酮)和取代的α-酮醇。优选的光引发剂为2-羟基-2-甲基-1-苯基-丙-1-酮(IRGACURE 1173TM, BASF)、2,2-二甲氧基-2-苯基苯乙酮(IRGACURE 651TM,BASF)、苯基双- (2,4,6-三甲基苯甲酰基)氧化膦(IRGACURE 819,BASF)。其它合适的光引发剂包括巯基苯并噻唑、巯基苯并噁唑和六芳基双咪唑。一般而言,引发剂的量小于5重量%,优选小于2重量%。
在一个实施方案中,最后再升温使得体系内残留的单体或反应性基团发生反应实现体系进一步的固化,优选升温到100-130℃下反应0.5-3h。
本发明还提供了一种量子点制品,所述量子点制品包括:
第一阻挡层;
第二阻挡层;以及
所述第一阻挡层和所述第二阻挡层之间的量子点层,所述量子点层包括本发明所述的量子点复合物。
第一阻挡层和第二阻挡层可由任何可用材料形成,该可用材料可保护量子点免于暴露在环境污染物(例如,氧气、水和水蒸气)中。合适的阻挡层包括但不限于聚合物膜、玻璃膜和介电材料膜。在一些实施方案中,用于第一阻挡层和第二阻挡层的合适的材料包括例如:玻璃和聚合物,诸如聚对苯二甲酸乙二醇酯(PET)、 PEN、聚醚或PMMA;氧化物,诸如氧化硅、氧化钛或氧化铝(例如,SiO2、TiO2或Al2O3);以及它们的合适的组合。期望阻挡层对选定波长的入射和发射的辐射至少90%,优选地至少95%是能够透射的。
量子点层包括本发明的量子点复合物,其中量子点被蓝光LED照射后,将 LED的蓝光降频转换为绿光和红光,可控制红光、绿光和蓝光的各自的部分来实现由含有量子点制品的显示装置发射的白光。所述量子点选自CdSe/ZnS、 InP/ZnS和CdS/ZnS。在示例性实施方案中,发光纳米晶体包括外部配体涂层,所述配体带有氨基、羧基或巯基,具体地例如为巯基丙酸、油酸、油胺、氨基取代的硅氧烷载体液体、末端带羧基的长链硫醚,优选末端带羧基的长链硫醚,如 H-[CH(CO2C12H25-n)CH2]3-S-CH(CO2H)CH2CO2H, H-[CH(CO2C12H25-n)CH2]5-S-CH(CO2H)CH2CO2H或、 n-C12H25-S-CH(CO2H)CH2CO2H。
本发明还提供了一种制备量子点制品的方法,该方法包括将本发明的量子点复合物涂覆在第一阻挡层上,并将第二阻挡层设置在量子点复合物层上,层压第二阻挡层,并且固化量子点复合物。
侵入(包括边缘侵入)被定义为由于湿气和/或氧气侵入基体中而造成量子点性能损失。在各种实施方案中,量子点制品在65℃和95%相对湿度下放置50 小时,根据CIE1931(x,y)规则具有小于约0.01的色移d(x,y),量子产率变化在10%范围内。
在各种实施方案中,量子点层的厚度为25微米至500微米,优选为40微米至250微米。
制备量子点复合物、量子点膜制品的一般方法1
通过以所需的当量比混合多硫醇、同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体,两种单体共20g,然后加入1g的量子点CdSe/ZnS、0.2g 光引发剂(2,2-二甲氧基-2-苯基苯乙酮)以及0.01g催化剂,在氮气箱中以1500rpm 的速度充分混合3分钟,制备下述每个实施例和比较例的量子点复合物。
然后,将上述制备的复合物在两个50μm的底漆PET阻挡膜之间以约100μm 的厚度刀涂,然后先在25℃下反应15分钟,然后在70℃下反应0.5h,再然后在紫外光下光照10分钟,最后在110℃下反应0.5h。
制备量子点复合物、量子点膜制品的一般方法2
通过以所需的当量比混合多硫醇、同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体以及催化剂DBU-Ant-BPh4,两种单体共20g,然后加入1g 的量子点CdSe/ZnS,在氮气箱中以1500rpm的速度充分混合3分钟得到量子点复合物。
然后,将上述制备的复合物在两个50μm的底漆PET阻挡膜之间以约100μm 的厚度刀涂,然后在紫外光下光照5分钟,最后在110℃下反应0.5小时。
用于测量量子产率(QY)的方法
所有量子产率通过使用绝对荧光量子产率光谱仪进行测量。
用于老化研究的方法
老化研究通过将下述实施例中制得的切割膜在65℃和95%相对湿度下放置 50小时后,测量量子产率和根据CIE1931(x,y)规则的色坐标位移d(x,y),评估老化稳定性。
用于测定边缘侵入的方法
在切割膜如上所述老化之后,通过放大镜下的直尺从基体膜的切割边缘测量具有两个阻挡膜的固化基体的边缘侵入。如果在老化期间量子点被氧气和/或湿气劣化并且不发出绿色和/或红色光,则边缘处的量子点在蓝色光下显示黑线。
实施例或对比例用到的单体化合物:
化合物1:乙二醇双(巯基乙酸酯)
化合物2:三羟甲基丙烷三(巯基乙酸酯)
化合物12:1,8-二氮杂双环(5.4.0)十一-7-烯-蒽-四苯基硼酸酯 (DBU-Ant-BPh4)
实施例1-8和比较例1-4
根据上述用于制备量子点复合物、量子点膜制品的一般方法1,制备实施例 1-8和比较例1-4量子点膜制品,具体制备条件见表1。
实施例9-10和比较例5
根据上述用于制备量子点复合物、量子点膜制品的一般方法2,制备实施例 9-10和比较例5量子点膜制品,具体制备条件见表1。
使用上述测试方法,对所制备的样品在老化之前和老化之后测量量子产率,以及老化之后的边缘侵入测试。
表1
下表2总结了在制备样品时的QY数据和所选实施例的相同样品在老化之后的QY数据和边缘入侵。
表2
通过以上结果表明,使用本发明的硫醇和同时含有≥1官能度的多烯基和≥ 1官能度的异氰酸酯基的单体来制备量子点的基质,具有优异的阻隔水氧的能力,使得量子点制品的颜色稳定,可延长显示器应用中量子点制品的使用寿命。同时,含磷化合物和丙烯酸酯化合物构成的共催化体系可以进一步提升基质的阻挡性能。
尽管结合具体特征及其实施例对本发明进行了描述,显而易见的,在不脱离本发明的精神和范围的情况下,可对其进行各种修改和组合。相应地,本说明书仅仅是所附权利要求所界定的本发明的示例性说明,且视为已覆盖本发明范围内的任意和所有修改、变化、组合或等同物。显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包括这些改动和变型在内。
Claims (5)
1.一种量子点复合物,所述复合物包含分散于一种聚合物基质中的量子点,其特征在于,所述聚合物基质由至少一种具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体制备得到;
所述至少一种具有≥2官能度的多硫醇单体为乙二醇双(巯基乙酸酯);
所述至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体为
所述多硫醇单体的硫醇基团、所述多烯基的双键基团、以及所述异氰酸酯基团的化学计量摩尔比为1.2:1:1;
所述聚合物基质由至少一种具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体反应制备时,包含由含磷化合物和丙烯酸酯化合物构成的共催化剂;
所述含磷化合物为:
丙烯酸酯化合物为:丙烯酸丙酯;
丙烯酸酯化合物与含磷化合物的摩尔比为2:1;
所述量子点为CdSe/ZnS。
2.根据权利要求1所述的一种量子点复合物,其特征在于:丙烯酸酯化合物使用量占所有单体总量的0.005-0.05wt%,含磷化合物使用量占所有单体总量的0.005-0.05wt%。
3.一种制备权利要求1-2任一项所述的量子点复合物的方法,其特征在于:包含以下步骤:
i) 提供量子点材料、一种具有≥2官能度的多硫醇单体和至少一种同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体;
ii) 将量子点材料和具有≥2官能度的多硫醇单体、同时含有≥1官能度的多烯基和≥1官能度的异氰酸酯基的单体以及含磷化合物、丙烯酸酯化合物和光引发剂进行混合,在10-60℃下反应10-30分钟;
iii) 然后在65-100℃下反应0.5-2小时;
iv) 将步骤iii)得到的中间体在紫外光下光照10-20分钟,最后在100-130℃下反应0.5-3小时。
4.一种量子点制品,其特征在于,所述量子点制品包括:
第一阻挡层;
第二阻挡层;以及
所述第一阻挡层和所述第二阻挡层之间的量子点层,所述量子点层包括权利要求1-2任一项所述的量子点复合物。
5.一种形成权利要求4所述的量子点制品的方法,其特征在于,所述方法包括以下步骤:将权利要求1-2中任一项所述的量子点复合物涂覆在第一阻挡层上,层压第二阻挡层,并且固化。
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