CN108440756B - 包含具有硫醇基的反应性添加剂的聚合物复合材料和膜以用于提高量子点分散和阻隔性质 - Google Patents

包含具有硫醇基的反应性添加剂的聚合物复合材料和膜以用于提高量子点分散和阻隔性质 Download PDF

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CN108440756B
CN108440756B CN201810117992.4A CN201810117992A CN108440756B CN 108440756 B CN108440756 B CN 108440756B CN 201810117992 A CN201810117992 A CN 201810117992A CN 108440756 B CN108440756 B CN 108440756B
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polymer composite
molecular weight
quantum dots
polymer
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CN108440756A (zh
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J·Y·黄
Y·何
L·陈
X·陈
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Dow Global Technologies LLC
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Abstract

本发明提供其中分散有量子点的聚合物复合材料，如膜，其中所述聚合物包含(b)含有一到6个硫醇基的第一化合物的聚合单元，所述化合物的分子量为300到20,000，并且具有至少一个具有至少三个碳原子、或优选至少5个碳原子的连续非环烃基链；和(c)第二化合物的聚合单元，所述第二化合物的分子量为100到750并且包含至少两个可聚合乙烯基作为(甲基)丙烯酸酯基的一部分或直接连接到芳香环，并且其中所述第一化合物的所述分子量减所述第二化合物的所述分子量为至少100。所述聚合物复合材料提供更稳定分散并且更持久的量子点复合物以用于例如显示装置。

Description

包含具有硫醇基的反应性添加剂的聚合物复合材料和膜以用于提高量子点分散和阻隔性质
本发明涉及一种含有量子点(quantum dot)的聚合物复合材料，特别是含有无镉量子点的聚合物复合材料。
半导体量子点(QD)提供显著不同于块体材料的光学吸收和发射(光致发光PL或电致发光EL)特性。随着粒度减小，各可用能级之间的有效能带隙(energy bandgap，Eg)增加并且产生蓝移的PL光谱。相同材料内通过粒度相关的量子限制效应的此类光谱可调谐性提供优于常规块体半导体的关键优势。由于其独特的光学性质，QD在诸多显示和照明应用中引起关注。很多QD具有无机壳，其由较大带隙材料制成以将电子和空穴对限制于核心区域内并且防止任何表面电荷状态。外壳或QD自身随后通过有机配体封端以减少可导致量子产率(QY)降低的外壳俘获状态。QD周围的典型有机配体帮助QD分散于有机/水性溶剂中，且具有相对较长的烷基链，其提供非极性溶剂或单体中的高溶解度。不幸地，在光吸收和/或光转换过程期间QD非常易受光氧化影响。湿度也可有类似影响。QD通常囊封于聚合物基质中以保护它们免受水和氧气的不利影响；然而，聚合物基质应与QD和任何所用配体两者相容。
已知用于形成聚合物基质的单体，如三环癸烷二甲醇二丙烯酸酯或二甲基丙烯酸异冰片酯，具有良好的O2阻隔性质并且又有与QD的不良相容性，产生会引起更低量子产率的QD聚集。
Kang等人(Kang)的美国专利申请案第US 2013/0148057 A号公开液晶显示器(liquid crystal display，LCD)的背光单元，包括发光二极管(light emitting diode，LED)和将从LED中发射的光转换为白光的光转换层。光转换层包含量子点或半导体纳米粒子和聚合物基质。聚合物基质包含具有至少两个末端硫醇基的第一聚合单体和具有至少两个末端不饱和官能团的第二单体的聚合物。然而，Kang光转换层并不提供可接受的氧气渗透性或量子产率。
本发明人致力于提供具有经改良的氧气阻隔和量子产率性质的含有QD的聚合物复合材料以及其膜。
发明内容
本发明提供一种其中分散有量子点的聚合物复合材料，所述聚合物复合材料包含：(a)量子点；(b)第一化合物的聚合单元，所述第一化合物包含至少一个或优选一到6个硫醇基、或优选二到6个硫醇基，并且分子量为300到20,000或优选为300到6000，并且具有至少一个具有至少三个碳原子、或优选至少五个碳原子的连续非环烃基链；和(c)第二化合物的聚合单元，所述第二化合物的分子量为100到750，并且包含至少两个可聚合的乙烯基作为(甲基)丙烯酸酯基部分或直接连接到芳香环，并且其中第一化合物的分子量减第二化合物的分子量为至少100。
根据本发明的聚合物复合材料，(a)量子点不含镉，例如ZnS、ZnSe、ZnTe、HgS、HgSe、HgTe、GaN、GaP、GaAs、InP、InAs或其组合。
优选地，本发明的聚合物复合材料中的量子点具有核壳结构，其中壳材料比核材料的带隙更宽并且与核材料晶格失配小。更优选地，此类核壳量子点为不含镉的量子点，如优选为具有含铟的核的量子点，并且如优选为具有III-V纳米粒子核(如GaAs、InP或GaP)和II-VI纳米粒子壳(如ZnS、ZnSe)的量子点。
根据本发明的聚合物复合材料，用于制备聚合单元(b)的第一化合物进一步包含至少一个羟基。
根据本发明的聚合物复合材料，用于制备聚合单元(b)的第一化合物为：N-烷基胺硫醇或含有氨基酸(如半胱氨酸)的硫醇基与C12-C26脂肪族羟基羧酸的一个或多个加合物，如与N-烷基胺硫醇(如N-乙胺硫醇)的低聚(12-羟基硬脂酸)加合物；N-烷基胺硫醇或含有氨基酸的硫醇基与C12-C26脂肪族羧酸或其二聚物的加合物；硫代烷基羧酸(如巯基丙酸)与C12-C26脂肪族二醇或三醇或其二聚物的加合物；或接枝硫醇的化合物，其用例如硫代烷基羧酸与一个或多个(甲基)丙烯酸C4-C16羟烷基酯、或优选一个或多个(甲基)丙烯酸C5-C16羟烷基酯的低聚物的加合物制备。
根据本发明的聚合物复合材料，用于制备聚合单元(b)的第一化合物优选为具有末端硫醇基的羟基脂肪酸酰胺、具有末端硫醇基的低聚(羟基脂肪酸)酰胺，其中脂肪酸链在位于距脂肪酸链末端三个或更多个、或优选5到6个碳处含有羟基，如12-羟基硬脂酸的硫醇乙基酰胺或低聚(12-羟基硬脂酸)的硫醇乙基酰胺。
根据本发明的聚合物复合材料，用于制备聚合单元(c)的第二化合物包含从以下中选出的单体：(甲基)丙烯酸酯基连接到芳香环或环脂肪族基团的单体，如三环癸烷二甲醇二丙烯酸酯或二甲基丙烯酸异冰片酯，乙烯基直接连接到芳香环或环脂肪族基团的单体，如二乙烯基苯，或其混合物。
根据本发明的聚合物复合材料，其中用于制备聚合单元(c)的第二化合物从以下中选出：三环癸烷二甲醇二丙烯酸酯、二甲基丙烯酸异冰片酯、二乙烯基苯或其混合物。
根据本发明的聚合物复合材料，所有量按聚合物复合材料中的总固体计，所述聚合物复合材料包含：(a)0.001到5重量％、或优选0.01到5重量％、或更优选0.1到5重量％的量子点，(b)0.5到40重量％、或优选0.5到10重量％的第一化合物的聚合单元，和(c)55到95重量％、或55到94.999重量％、或55到94.99重量％、或55到94.9重量％、或优选65到92重量％的第二化合物的聚合单元。
根据本发明的聚合物复合材料，所述聚合物复合材料优选包含膜。
根据本发明的膜聚合物复合材料，所述聚合物复合材料包含一部分多层膜、层合物或在聚合物复合材料膜的每一侧上也包含外层的总成。优选地，外层为隔氧层，例如聚对苯二甲酸乙二醇酯(polyethylene terephthalate，PET)，其也抑制湿气通过。
除非另外规定，否则百分比是重量百分比(重量％)并且温度以℃为单位。
除非另外规定，否则操作和实例在室温(20-25℃)下进行。
除非另外规定，否则沸点在大气压(大约101kPa)下测量。
除非另外指示，否则含有圆括号的任何术语都可以替代地指全部术语，如同圆括号不存在和术语没有圆括号一样，以及每个替代方案的组合。因此，术语“(甲基)丙烯酸酯”意谓丙烯酸酯、甲基丙烯酸酯或其混合物。
所有范围均具有包括性和可组合性。举例来说，术语“50到3000cp或100cp或更大的范围”将包括50到100cp、50到3000cp以及100到3000cp中的每一个。
如本文所使用，术语“ASTM”是指宾夕法尼亚州西康舍霍肯ASTM国际性组织(ASTMInternational,West Conshohocken,PA)的出版物。
如本文所使用，术语“带隙”是指如由紫外光电子光谱法(ultravioletphotoelectron spectroscopy，UPS)所测量的给定量子点或其层中的最高占用分子轨域(highest occupied molecular orbital，HOMO)与最低未占用分子轨域(lowestunoccupied molecular orbital，LUMO)之间的能隙。
如本文中所使用，术语“分子量”以道尔顿为单位测量，并且表示单体化合物的原子量的总和；对于低聚物、聚合化合物和其混合物，“分子量”表示重均分子量(weight-average molecular weight，Mw)，如由凝胶渗透色谱法针对丙烯酸单体的聚(甲基丙烯酸甲酯)、乙烯基单体的聚苯乙烯的聚合物标准物所测定；或对于用于制备聚合单元(b)的第一化合物，“分子量”通过核磁共振(nuclear magnetic resonance，NMR)光谱法测定。
如本文中所使用，术语“低聚物”意指具有两个或更多个重复单元、例如两个到一百个重复单元的化合物。如本文中所使用，术语“低聚物”可包括聚合物或与聚合物重叠。
如本文中所使用，术语“低聚(羟基脂肪酸)”是指通过由使羟基脂肪酸中的羟基与羧基反应而形成的酯连接的两个或更多个羟基脂肪酸分子的低聚酯。
如本文中所使用，术语“可靠的”或“可靠性”是指在例如60℃的高温下老化或使用例如30天或60天的较长时间后保持其量子产率的聚合物复合材料的品质。
根据本发明，聚合物复合材料含有充分并且稳定地分散于其中的量子点(QD)。聚合物复合材料包含由具有一个或多个硫醇基的第一化合物和丙烯酸或乙烯基单体的第二化合物的单体形成的聚合物，所述第二化合物具有两个或更多个可聚合的烯属不饱和基团(ethylenically unsaturated group)，如乙烯基或丙烯酸酯基。没有第一化合物的聚合物复合材料可具有良好的O2阻隔性质但与QD的相容性不良。聚合物与QD之间不良的相容性导致QD聚集，这使得在与天然溶剂或非极性单体中的QD相比时或在与具有相同厚度并且具有相同量的相同QD而无聚合的第一化合物的相同聚合物复合材料相比时，复合材料的量子产率(QY)或光致发光更低并且峰值波长红移。第一化合物与第二化合物单体并且与QD的相容性非常好，由此使得QY能够通过使聚合物复合材料中的QD聚集降到最低而提高。另外，第一化合物具有一个或多个与丙烯酸和乙烯基反应的硫醇基以在固化过程期间形成交联聚合物树脂。因为此为一种组分聚合物，所以聚合的第一化合物与聚合的第二化合物之间不存在相分离。因为QD均匀分散于固化的聚合物复合材料膜内部，膜随时间具有较短红移并且保持更佳的量子产率(QY)。另外，交联聚合物复合材料比多组分聚合物复合材料具有更高膜密度、更佳可靠性和氧气阻隔性质。
量子点为此项技术中所熟知，参见例如，Dubrow等人的美国专利公开案第US2012/0113672A号。优选地，本发明的聚合物复合材料中的量子点为不含镉的量子点，或更优选为不含镉的核-壳型量子点。
合适的量子点和核-壳型量子点可包括那些任何以下中所公开的任一者：Mushtaq等人的美国专利第7,588,828B2号；Guo等人的美国专利公开案第2015/0236195A1号中所公开的量子点，例如，含有富含铟的InP核的量子点，如由使InP与羧酸铟(即，羧酸铟(III))(如月桂酸铟)接触形成的那些；Mingjun等人的美国专利公开案第US2015/0166342A1号中所公开的那些；第III-IV族半导体纳米结构，如Scher等人的美国专利案第7557028B1号中、Scher等人的美国专利案第8062967B1号中、Scher等人的美国专利案第US8884273 B1号中、或Scher等人的美国专利案第US9469538 B1号中；具有含第IIIA族和第VA族元素的核的纳米晶体，如Clough等人的美国专利案第9136428B2号中；Breen等人的美国专利案第US9212056 B2号中所公开的纳米粒子；或Bawendi等人的US6322901 B1中所公开的纳米晶材料。
不含镉的量子点材料的可接受效率(PLQY)高于40％、或优选高于60％、或更优选75％或更高，如75％到95％。
优选地，第一化合物(b)的分子量为300到20,000，优选是至少400，优选是至少500，优选是至少600，优选是至少700，优选是至少800，优选是至少1,000；优选不超过15,000，优选不超过10,000，优选不超过8,000，优选不超过6,000，优选不超过5,000，优选不超过3,000。
合适的第一化合物可包括例如，N-烷基胺硫醇与C12-C26脂肪族羟基羧酸或含有氨基酸(如半胱氨酸)的硫醇基的单体或低聚物加合物，如与N-烷基胺硫醇(如N-乙胺硫醇)的低聚(12-羟基硬脂酸)加合物；N-烷基胺硫醇或含有氨基酸的硫醇基与C12-C26脂肪族羧酸的加合物；硫代烷基羧酸(如巯基丙酸)与C12-C26脂肪族二醇(由此含有两个硫醇基)、与C12-C26脂肪族三醇(由此含有三个硫醇基)或与C12-C26脂肪族三醇的二聚物(由此含有四个硫醇基)中的任一者的加合物。
当用于制备聚合单元(b)的第一化合物为其中各重复单元含有硫醇基的低聚物，如硫代烷基羧酸与(甲基)丙烯酸C4-C16羟烷基酯低聚物的加合物时，第一化合物中硫醇基的数目为低聚物分布中的单体的重复单元的平均数目。
当用于制备聚合单元(b)的第一化合物为通过将含有化合物的硫醇基加合到分子上制备的单体时，硫醇基的数目通过分子上加合位点的数目测定。举例而言，硫代烷基羧酸与C12-C26脂肪族二醇的加合物具有两个硫醇基；并且硫代烷基羧酸与C12-C26脂肪族三醇的加合物具有三个硫醇基。
当用于制备聚合单元的第一化合物包含接枝到第一化合物上或化学连接到第一化合物中(如通过酰胺化、肽化或酯化)的硫醇基时，第一化合物中硫醇基的数目为如通过核磁共振(NMR)光谱法测定的数量。
用于制备聚合单元(b)的第一化合物具有至少一个具有至少三个碳原子或优选至少五个碳原子的连续非环烃基链，即，具有至少五个亚甲基、烯烃碳或其组合并且无杂原子的直链或分支链(优选直链)。优选地，连续非环烃基链具有至少六个碳原子，优选是至少七个，优选是至少八个；优选不超过十五个，优选不超过十四个，优选不超过十三个。更优选地，连续非环烃基链仅含有亚甲基。
优选地，用于制备聚合单元(b)的第一化合物仅有碳原子、氢原子、氧原子、硫原子和氮原子。
更优选地，用于制备聚合单元(b)的第一化合物仅有碳原子、氢原子、氧原子和硫原子。
优选地，用于制备聚合单元(b)的第一化合物为脂肪族化合物。
优选地，用于制备聚合单元(c)的第二化合物的分子量为至少150，优选是至少200，优选是至少250；优选不超过650，优选不超过500，优选不超过400，优选不超过350。
优选地，第一化合物的分子量减第二化合物的分子量为至少300，优选是至少500，优选是至少700，优选是至少900，优选是至少1,100；优选不超过19,900，优选不超过15,000，优选不超过10,000，优选不超过5,000。
当本发明的聚合物复合材料包含超过一种第一化合物和/或超过一种第二化合物时，分子量差别上的前述限制仅适用于第一化合物和第二化合物最普遍的组合，按复合材料的总固体重量计，所述组合的量总计为至少50重量％，优选为至少75重量％。
当在用于制备聚合单元(c)的第二化合物中时，可聚合的乙烯基连接到芳香环(例如，苯环、萘环或吡啶环)，芳香环优选具有三到二十个碳原子，或优选五到十五个碳原子。优选地，芳香环不含杂原子并且具有六到十五个碳原子，优选为六到十二个碳原子。
优选地，用于制备聚合单元(c)的第二化合物具有二到六个可聚合的乙烯基，或更优选不超过四个。
优选地，第二化合物中可聚合的乙烯基为(甲基)丙烯酸酯基(CH2＝C(R)C(O)O-，其中R为H或CH3；也称为(甲基)丙烯酰氧基)。
优选地，第二化合物仅有碳原子、氢原子、氧原子和氮原子；或更优选仅有碳原子、氢原子和氧原子。
优选地，第二化合物具有(甲基)丙烯酸酯基，或第二化合物为二乙烯基苯(divinylbenzene，DVB)。
尤其优选的第二化合物包括三环[5.2.1.02,6]癸烷二甲醇二丙烯酸酯、双酚A二甲基丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二甲基丙烯酸酯、1,10--双(丙烯酰氧基)癸烷和
Figure GDA0003449018180000091
优选地，聚合物复合材料进一步包含第三化合物的聚合单元(d)，所述第三化合物具有一个(甲基)丙烯酸酯基并且分子量为100到270；优选是至少140，优选是至少160；优选不超过250，优选不超过230。优选地，第三化合物为脂肪族或环脂族单体，如丙烯酸异冰片酯(IBOA)。
尤其优选的第三化合物包括丙烯酸异冰片酯、丙烯酸3,5,5-三甲基己酯、丙烯酸十二烷酯、丙烯酸癸酯、丙烯酸十三烷酯、丙烯酸异癸酯、丙烯酸L-薄荷酯、丙烯酸三环[5.2.1.02,6]癸基甲酯、甲基丙烯酸3,3,5-三甲基环己酯和甲基丙烯酸3,3,5-三甲基环己酯。
优选地，本发明的聚合物复合材料为一部分多层膜、层合物或在聚合物复合材料膜的每一侧上也包含外层的总成。优选地，外层为隔氧层，其也抑制湿气通过。优选地，外层包含聚合物复合材料，优选地包含聚对苯二甲酸乙二醇酯(PET)、聚芳基醚酮、聚酰亚胺、聚烯烃、聚碳酸酯、聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯或其组合的聚合物复合材料。优选地，外层进一步包含氧化物或氮化物，优选为氧化硅、二氧化钛、氧化铝、氮化硅或其组合。优选地，将氧化物或氮化物涂布于面朝QD层的聚合物复合材料的表面上。优选地，各外层包含厚度为25到150微米(优选为50到100微米)的聚合物复合材料和厚度为10到100nm(优选为30到70nm)的氧化物层/氮化物层。
根据本发明，多层膜、层合物或总成的外层优选包含至少两个聚合物复合材料层和/或至少两个氧化物层/氮化物层。在本发明的任一多层膜中，不同层可具有不同的复合物。优选地，外层的氧气透过率非常低(oxygen transmission rate，OTR，<10-1cc/m2/天)并且水蒸气透过率非常低(water vapor transmission rate，WVTR，<10-2g/m2/天)。
优选地，外层中聚合物复合材料的Tg为60到200℃；或更优选为至少90℃，或最优选为至少100℃。
优选地，根据本发明的聚合物复合材料的厚度范围为20到500微米，优选是至少50微米，优选是至少70微米，优选是至少80微米，优选是至少90微米；优选不超过400微米，优选不超过300微米，优选不超过250微米，优选不超过200微米，优选不超过160微米。优选地，各外层的厚度是20到100微米，优选为25到75微米。
优选地，本发明的聚合物复合材料通过树脂的自由基聚合制备，所述树脂通过使第一化合物、第二化合物、任何其它单体、一个或多个QD和任何任选添加剂混合来制备。优选地，树脂在固化之前通过典型方法(例如旋转涂布、槽模涂布、凹版印刷、喷墨和喷涂)涂布于第一外层上。优选地，固化通过将树脂曝露于紫外光或热量、优选为紫外光、优选为UVA范围内的紫外光而引发。
优选地，本发明的聚合物复合材料包含0.01到5重量％、优选是至少0.03重量％、优选是至少0.05重量％、优选不超过4重量％、或优选不超过3重量％、或更优选不超过2重量％的量子点。优选地，量子点包含CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgSe、HgTe、GaN、GaP、GaAs、InP、InAs或其组合。优选地，量子点不含镉。更优选地，量子点为核-壳型量子点，如核-壳型不含镉的量子点，尤其为含有含铟的核的核-壳型量子点。
本发明的量子点优选包含非极性配体。优选地，量子点无机部分周围的配体具有非极性组分，如脂肪族烃基。优选的配体包括例如三辛基氧化膦、十二硫醇和脂肪酸盐(例如，硬脂酸盐、油酸盐)。
可并入本发明的聚合物复合材料中的其它添加剂包括用于提高光提取的紫外(UV)稳定剂、抗氧化剂、散射剂和用于增加黏度的增稠剂(例如，丙烯酸氨基甲酸酯低聚物)。
优选的增稠剂包括丙烯酸氨基甲酸酯、纤维素醚、纤维素丙烯酸酯、聚苯乙烯聚合物、聚苯乙烯嵌段共聚物、丙烯酸类树脂和聚烯烃弹性体。优选地，聚苯乙烯、丙烯酸和聚烯烃增稠剂的Mw的范围为50,000到400,000、优选为100,000到200,000。优选地，纤维素醚的Mw的范围为1,000到100,000。
丙烯酸氨基甲酸酯低聚物在其含有的丙烯酸酯基之间可具有聚酯、聚醚、聚丁二烯或聚己内酯骨架。其可具有双官能、三官能、六官能反应性。此类低聚物的黏度在50℃下可以在1000到200,000cP的范围内。对于非极性配体QD，优选为聚丁二烯丙烯酸氨基甲酸酯低聚物。
聚合物复合材料的优选形式包括例如复合材料、珠粒、条带、杆、方块和板。聚合物复合材料适用于多种应用，包括例如显示、照明和医疗应用。优选的显示应用包括公众信息显示器、标牌、电视、监视器、移动电话、平板计算机、膝上型计算机、汽车和其它仪表盘以及手表。
实例：以下实例说明本发明。除非另外指示，否则所有温度单位为室温并且所有压力单位为标准气压或101kPa。
使用以下测试方法：
所指示的聚合薄膜的O 2渗透性(cc/m/天/atm)使用Mocon OX-TRAN型号2/21装置(Mocon,Inc.,Minneapolis,MN)测量。在23℃下使用3％O2和97％N2的测试气体在ASTM方法D3985(《使用库仑感应器通过塑料膜和薄片的氧气透过率的标准测试方法(Standard TestMethod for Oxygen Gas Transmission Rate through a Plastic Film and SheetingUsing a Coulometric Sensor)》，1981年1月30日)中概述方法细节。测量值取自以下文所公开的方式制备并且具有10重量％负载量的所指示的第一化合物的膜。
薄膜厚度通过用测微计测量固化膜并且随后减去任何阻隔膜厚度的厚度来测定。
光致发光量子产率(PLQY)使用450nm激发LED光源和Hamamatsu AbsoluteTM PL量子产率光谱仪(Hamamatsu Photonics KK,Shizuoka,Japan)用常规累计球来测量。对于每一报导实例，总共三(3)个测量值取自每一分析物衬底中三(3)个随机选择的点，并且所指示的PLQY表示所得测量值的平均值。
峰值发射波长(peakemissionwavelength，PWL)使用Hamamatsu累计球测定；对于以下实例中的绿色QD，目标波长为520到540nm；对于红色QD，目标波长为620到640nm。
实例中所用缩写：
OHS为低聚(12-羟基硬脂酸)，Mw＝1,500；OHS-SH为含有单个硫醇基的低聚(12-羟基硬脂酸)，Mw＝1,500；C为半胱氨酸；IBOA为丙烯酸异冰片酯；SR833为三环[5.2.1.02,6]癸烷二甲醇二丙烯酸酯；I-819和I-651为IRGACURE光敏聚合引发剂(BASF AG,Leverkusen,DE)；FinexTM氧化锌粒子(Sakai Chemical Industry co.,LTD.,Japan)；并且CFQD表示不含镉的量子点。绿色CFQD包含具有含铟的核的核-壳型QD，并且呈现73.9％QY(PLQY)、44.1nmFWHM和534.4nm PWL(在吸光率＝0.3下)。所有量子点进一步包含非极性配体。
具有一个羧酸基和一个羟基的OHS通过借助肽反应并入半胱氨酸的硫醇基来修饰。为制备OHS-SH，在N2氛围下于40mL无水甲苯中将OHS(9.115g，6.2mmol)和N-羟基丁二酰亚胺(NHS，1.8g，15.5mmol，2.5摩尔当量)混合在一起。使用等压加料漏斗缓慢添加乙二胺四乙酸二钠二水合物(EDTA二钠盐，3g，15.5mmol，2.5摩尔当量)于二甲基甲酰胺(dimethylformamide，DMF)(60mL)中的溶液。将溶液维持在20℃下24小时以完成所有羧基的活化。将3.8g半胱氨酸(31mmol，5摩尔当量)溶解于无水DMF(120ml)中并且随后与三甲胺(1.6g，15.5mmol，2.5摩尔当量)混合。在N2下将所得混合物缓慢装入NHS-活化的聚合物溶液中并且再搅拌24小时。随后去除DMF，并且将最终产物用甲苯萃取，并且用饱和NaCl溶液洗涤。最终，在N2吹扫下去除甲苯，并且将产物在真空烘箱中于室温下干燥过夜。
实例1：所有所指示的聚合物复合材料为通过在两个i组分PET阻隔膜之间层叠所指示的树脂配制物制备的膜。将大约2mL树脂分配于底部膜上并且用间隙为250到300(10密耳-12密耳)的间隙涂布棒向下拉，以确保所需膜厚度。所有配制物在500mJ/cm2UV固化强度下使用DRS-10/12QNH(Fusion UV Systems,Inc.,Gaithersburg,MD)进行固化。
配制物示于下表1中。此类配制物通过以下制得：将所指示的第二化合物单体与光引发剂掺合在一起，随后使第一化合物或不含硫醇基的比较化合物与第二化合物单体混合，并且将所得混合物加热到50℃维持15分钟。随后将第二化合物单体IBOA(丙烯酸异冰片酯)与所指示的QD掺合成混合物。如先前段落中所公开，使混合物形成或倾入膜中，并且随后在UV光下固化约3s。量子产率结果展示于下表2中。
实例3和比较实例3A：在各实例中，针对使用下表1中的配制物并且以上文中实例1中所公开的方式制备的两个膜中的每一个测定氧气渗透性，但膜用10重量％负载量的第一化合物或所指示的比较化合物配制。所报导的结果为两个膜的平均值。氧气渗透性结果展示于下表3中。
表1：配制物
Figure GDA0003449018180000131
*-表示比较实例。
表2：量子产率结果
Figure GDA0003449018180000132
Figure GDA0003449018180000141
*-表示比较实例。
如上表2中所展示，实例2中本发明聚合物膜的量子产率优于对照组。峰值波长在实例2和1A中类似，表明本发明的复合物中合理的低红移。此外，本发明实例2的膜的峰值吸收率优于比较实例1A的膜的峰值吸收率，表明QD在实例2中比实例1B中分散地更好。
表3：氧气渗透性
Figure GDA0003449018180000142
*-表示比较实例。
如上表3中所展示，根据本发明制备的膜的氧气渗透性显著低于具有羟基脂肪酸第一化合物而无硫醇基的相同复合物的膜。结果表明QD复合物良好分散于固化聚合物复合材料中，并且比比较实例3A的复合物更加可靠。

Claims (3)

1.一种其中分散有量子点的聚合物复合材料，所述聚合物复合材料包含：(a)量子点；(b)第一化合物的聚合单元，所述第一化合物包含一到6个硫醇基，并且分子量为300到20,000，并且具有至少一个具有至少三个碳原子的连续非环烃基链；和(c)第二化合物的聚合单元，所述第二化合物的分子量为100到750，并且包含至少两个可聚合乙烯基作为(甲基)丙烯酸酯基的一部分或直接连接到芳香环，并且其中所述第一化合物的所述分子量减所述第二化合物的所述分子量为至少100；其中用于制备所述聚合单元(b)的所述第一化合物还包含至少一个羟基；其中用于制备所述聚合单元(b)的所述第一化合物为12-羟基硬脂酸的硫醇乙基酰胺或低聚(12-羟基硬脂酸)的硫醇乙基酰胺；其中用于制备所述聚合单元(c)的所述第二化合物从以下中选出：三环癸烷二甲醇二丙烯酸酯、二甲基丙烯酸异冰片酯或其混合物。
2.根据权利要求1所述的聚合物复合材料，其中所述(a)量子点为不含镉的量子点。
3.根据权利要求1所述的聚合物复合材料，其中所述聚合物复合材料包含(a)0.001到5重量％的量子点，(b)0.5到40重量％的所述第一化合物的聚合单元，和(c)55到94.999重量％的所述第二化合物的聚合单元。
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US10508232B2 (en) 2019-12-17
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US20180265774A1 (en) 2018-09-20
JP7274260B2 (ja) 2023-05-16
DE102018102712A1 (de) 2018-08-16
GB201802441D0 (en) 2018-03-28
KR102461533B1 (ko) 2022-10-31
GB2562339A8 (en) 2018-12-19
GB2562339A (en) 2018-11-14
JP2018131608A (ja) 2018-08-23
TW201831585A (zh) 2018-09-01
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