Quantum dot synthesis using plasticizers and their use in polymeric compositions

Abstract

The present invention relates to a composition including quantum dots; a polymer; and, a plasticizer material, the plasticizer material providing dispersion of the quantum dots throughout the polymer whereby the composition is characterized as having lower haze and / or longer durability than a similar composition of quantum dots in the polymer in the absence of the plasticizer.

Description

[0001] QUANTUM DOT SYNTHESIS USING PLASTICIZERS AND THEIR USE IN POLYMERIC COMPOSITIONS CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Application No.63 / 511,236, filed June 30, 2023, the content of which is incorporated by reference herein in its entirety. FIELD OF THE DISCLOSURE The present invention is initially directed to: a composition including quantum dots; a polymer; and, a plasticizer material. The plasticizer materials are generally included to adjust the viscosity of the polymer compositions to make them more flexible, less brittle and generally more processable. Plasticizers with or without other solvents provide dispersion of the quantum dots throughout the polymer whereby the composition is characterized as having lower haze and / or longer durability than a similar composition of quantum dots in the polymer in the absence of the plasticizer with or without another solvent. The present invention is further directed to: a composition including quantum dots, each comprised of at least one semiconductor core and at least one semiconductor shell; and, a plasticizer material. The plasticizer materials can provide dispersion of the fluorophore particles throughout a polymer matrix such that a composition of fluorophore particles and plasticizer in combination with a polymer matrix is characterized by lower haze and / or longer durability than a similar composition of fluorophore particles in the polymer matrix in the absence of the plasticizer. Also, the present invention is directed at a process of preparing a core-shell quantum dot and plasticizer mixture comprising: admixing precursors for a quantum dot core at temperatures and for times sufficient to form a resultant quantum dot core; and, admixing the resultant quantum dot core with a combination of both (a) precursors for a shell about the quantum dot core and (b) a plasticizer material to form a core-shell quantum dot / plasticizer mixture. This admixture is capable of providing dispersion of resultant core-shell quantum dots into subsequent polymer matrixes.

[0002] 1 LEGAL02 / 44543790v1 BACKGROUND OF THE DISCLOSURE Commodity and specialty polymeric systems are generally processed through well-known methods such as extrusion, injection molding, thermoforming and blow molding. Newer technologies such as 3D printing also serve as highly useful processing technologies to develop versatile polymeric and nanocomposite systems and are gaining extensive industrial and academic use. In order to improve the compatibility between inorganic nanoparticles and processable polymeric systems, improving processibility via plasticization by compatibilizing agents is considered essential. Conventionally, colloidal quantum dots (QDs) are synthesized using high boiling solvents and capping agents. The QDs are isolated from their reaction mixture by precipitation and redispersion methods and then the QD surface is treated with compatibilizing agents or ligands for their use in polymers. In general, QDs are isolated by precipitation and redispersion methods, in which, anti- solvent (polar solvent) is added to the mixture that coagulates quantum dots and the coagulated quantum dots are precipitated by centrifugation process. Further, the QDs are redispersed in non- polar solvent, and again coagulated and precipitated by adding polar solvent and centrifugation. This process is repeated several more times or until the desired purity is achieved. This process is solvent and labor intense and generates plenty of hazardous waste and it is difficult to scale-up. Importantly, in this process ligands may be removed or ripped off of the QD surface, which reduces the photoluminescence quantum yield and long-term stability and can make the dots difficult to dissolve in monomer solutions for polymer processing. The compositions and approaches described herein can overcome some of the prior challenges and provide the improved resultant compositions. BRIEF DESCRIPTION OF THE DRAWINGS Fig.1 shows a picture of visible emitting CuInS2 / ZnS quantum dots in phthalate, sebacate, adipate and terephalate plasticizers (Examples 1-4). Fig. 2 shows a plot of absorption spectra of CuInS2 / ZnS QDs in different dispersion medium (Examples 1-4 Isolation methods A-C).

[0003] 2 LEGAL02 / 44543790v1 Fig. 3 shows a picture of extruder set-up showing liquid injection of QDLC and extruded QD strand (Examples 10-24). Fig.4 shows a picture of visible emitting CuInS2 / ZnS quantum dots in phthalate, octadecene and sebacate at 80% QD loading (Examples 5-9). Fig.5 shows a picture of extruded (a) QDs strands in ethylene vinyl acetate (EVA), extruded using QDs dispersed in octadecene (Example 15), (b) QDs pellets in ethylene vinyl alcohol (EVOH) extruded using QDs dispersed in sebacate plasticizer (Example 16), and (c) a picture of a blown film in EVA. Fig 6 shows photostability data of CuInS2 / ZnS QDs in EVOH films extruded using (1) powder QD, (2) QDs in sebacate plasticizer, and (3) 7.4% QD loading in EVOH obtained by letting down from 12% QD loaded EVOH pellets. (Example 16). Table 1. Showing selected optical properties of QD synthesized using different plasticizers (Examples 1-4). Table 2. Showing selected optical properties of laminated QD films using different plasticizers (Example 6-9). Table 3. Showing the quantum yield (QY) of near infrared (NIR) emitting dots in different dispersion medium (Examples 1-4 Isolation methods A-C). Table 4. Showing different concentrations of quantum dots in extruded ethylene vinyl acetate (EVA) film extruded using quantum dot syrup (Example 15). Table 5. Showing optical properties of quantum dots in extruded ethylene vinyl acetate (EVA) film extruded using QDLC (Example 15). Table 6. Showing optical properties of extruded QD films in different polymer matrices using QDs in different plasticizers (Examples 15-23) Fig. 7 shows pics of: (a) a 50:50 wt % isolate of NIR emitting CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt-octadecene) (PMAO); (b) a mixture of the NIR emitting CuInS2 / ZnS quantum dots, (2-dodecen-1-yl) succinic anhydride (DDSA), and, chloroform; (c) a 50:50 wt % isolate of the NIR emitting CuInS2 / ZnS quantum dots and polyethylene glycol monooleate; and,

[0004] 3 LEGAL02 / 44543790v1 (d) a 50:50 wt % isolate of the NIR emitting CuInS2 / ZnS quantum dots and polyethylene glycol distearate. Fig.8 shows the effect of octadecene in melt mixing poly(maleic anhydride-1-alt-octadecene) and the NIR emitting CuInS2 / ZnS quantum dots: (a) a composite sample in absence of any octadecene pressed between glass slides; and, (b) a composite sample in presence of octadecene pressed between glass slides. Fig.9 shows comparison of (a) native ethylene vinyl acetate (EVA); (b) NIR emitting CuInS2 / ZnS quantum dot composites with EVA in the absence of (2-dodecen-1-yl) succinic anhydride (DDSA); and (c) NIR emitting CuInS2 / ZnS quantum dot composites with EVA in the presence of (2-dodecen-1-yl) succinic anhydride (DDSA). Fig. 10 shows comparison of NIR emitting CuInS2 / ZnS quantum dot imbibed EVA films fabricated through the second methodology where: (a) is native ethylene vinyl acetate (EVA) films; (b) composite films of EVA with the NIR emitting CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt-octadecene; (c) ) composite films of EVA with the NIR emitting CuInS2 / ZnS quantum dots; and, (d) composite films of EVA with the NIR emitting CuInS2 / ZnS quantum dots and polyethylene glycol monooleate filaments. SUMMARY In one aspect, the present invention relates to a composition including: quantum dots; a polymer; and, a plasticizer material capable of providing dispersion of the quantum dots throughout the polymer whereby the composition is characterized as having lower haze and longer durability in comparison to a composition of quantum dots in the polymer in the absence of the plasticizer. In another aspect, the present invention relates to a composition including: fluorophore particles, each comprised of at least one semiconductor nanoparticle core and at least one semiconductor shell material upon at least a portion of the semiconductor nanoparticle core; and, a plasticizer material capable of providing dispersion of the fluorophore particles throughout a polymer matrix such that the composition of fluorophore particles and plasticizer in combination with a polymer matrix is characterized by lower haze and longer durability in comparison to a composition of fluorophore particles in a similar polymer matrix in the absence of the plasticizer.

[0005] 4 LEGAL02 / 44543790v1 In still another aspect, the present invention relates to process of preparing a core-shell quantum dot and plasticizer mixture comprising: admixing precursors for a quantum dot core at temperatures and for times sufficient to form a resultant quantum dot core; and, admixing the resultant quantum dot core with a combination of both (a) precursors for a shell about the quantum dot core and (b) a plasticizer material capable of providing dispersion of resultant core-shell quantum dots into polymer matrixes to form a core-shell quantum dot / plasticizer mixture. In another aspect, a process of preparing a quantum dots in polymers is provided. In an example embodiment, the process includes injecting a liquid quantum dots-plasticizer with or without other solvents making a concentrate mixture into a twin or single extruder along with the host polymers at temperature ranging from 90-250 C at a constant screw rpm of 20-1000 rpm. In an example embodiment, the polymer is an extrudable polymeric material selected from the group consisting of ethylene vinyl acetate (EVA), polyvinyl butyal (PVB), ethylene vinyl alcohol (EVOH), Nylon, low density polystyrene (LDPS), polyethylene (PE), polyamide (PA), thermoplastic polyurethane (TPU), maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, polyolefin(POE), polyvinyl difluoride (PVDF) or a mixture thereof. In an example embodiment, the extruder has a circular die, including a blown film system. In an example embodiment, the extruder has a slot die, including a cast film system. DETAILED DESCRIPTION The synthesis and direct utilization of selected quantum dots with suitable polymers is addressed herein. More particularly, a method is described herein in which selected quantum dots are synthesized using plasticizers / liquid / solvent that can be subsequently directly integrated with suitable polymers by wet-lamination or by extrusion without needing to initially isolate the quantum dots before their incorporation with polymers. Such an in-situ process saves on solvent cost, labor use and can generate less waste, e.g., hazardous waste. Importantly, the quantum yield of the quantum dots is retained in the polymer films and increased loading of QDs into the films can be achieved.

[0006] 5 LEGAL02 / 44543790v1 In yet another aspect, an understanding of interdisciplinary principles of surface chemistry in conjunction with polymer structure property relationships and industrial processing parameter selection. Fabrication of nanocomposite systems generally is faced with issues of dispersion due to opposing surface chemistries of the additive and dispersion matrix. Improving the dispersion can be beneficial to the end use application and yield improved desirable characteristics. Here the present study demonstrates improvement of solid-state solubility of inorganic quantum dots into polymeric systems that are used, e.g., in architectural glass, packing and greenhouse film applications. The following polymers were investigated as host matrices for inorganic quantum dots: ^ Ethylene Vinyl Acetate (EVA) ^ Ethylene Vinyl Alcohol (EVOH) ^ Poly Vinyl Butyral (PVB) ^ Polyethylene (PE- LDPE, LLDPE, HDPE, UHMWPE) ^ Acrylates ^ Ionomers ^ Polycarbonate ^ Polypropylene (PP) ^ Thermoplastic Polyurethane (TPU) ^ Polystyrene ^ Polyolefin (POE) ^ Nylon ^ Polyester The following materials are identified as compatibilizing agents: ^ Poly(maleic anhydride-1-alt-octadecene) ^ Poly(isobutylene-alt- maleic anhydride) ^ Poly(ethylene-alt- maleic anhydride) ^ Polypropylene-graft-maleic anhydride ^ Poly(sodium 4-styrenesulfonate) ^ Poly(potassium 4-styrenesulfonate)

[0007] 6 LEGAL02 / 44543790v1 ^ Poly(ammonium 4-styrenesulfonate) ^ (2-Dodecen-1-yl) succinic anhydride ^ Polyethylene glycol(PEG) monooleate ^ Polyethylene glycol(PEG) dioleate ^ Polyethylene glycol(PEG) distearate Other materials sometimes referred to or identified as compatibilizers in conjunction with the above include: ^ 1-Octadecene ^ Mineral oil ^ Vegetable oil ^ Phthalate based plasticizers ^ Adipate based plasticizers ^ Sebacate based plasticizers ^ Terephthalate based plasticizers DEFINITIONS AND ABBREVIATIONS (per prior definitions) The following explanations of termss and abbreviations are provided to better describe the present disclosure and to guide those of ordinary skill in the art in the practice of systems, methodologies and compositions disclosed herein. As used herein, “comprising” means “including”, and the singular form “a” or “an” or “the” include plural references unless the context clearly indicates otherwise. Unless the context clearly indicates otherwise, the term “or” is inclusive, and thus refers to both a single element of stated alternative elements and a combination of two or more of those elements. Unless explained otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one or ordinary skill in the art to which this disclosure relates. Suitable methods and compositions are described herein for the practice or testing of the systems, methodologies and compositions described herein. However, it is to be understood that other methods and materials similar, or equivalent to, those described herein may be used in the practice

[0008] 7 LEGAL02 / 44543790v1 or testing of these systems, methodologies and compositions disclosed herein. Consequently, the systems, methodologies, compositions and examples disclosed herein are illustrative only, and are not intended to be limiting. Other features of the present disclosure will be apparent to those skilled in the art from the following detailed description and the appended claims. Unless otherwise indicated, all numbers expressing quantities of components, percentages, temperatures, times, and so forth as used in the specification or claims are to be understood as being modified by the term “about”. Unless otherwise indicated, non-numerical properties such as colloidal, continuous, crystalline, and so forth as used in the specification or claims are to be understood as being modified by the term “substantially”, meaning to a great extent or degree. Accordingly, unless otherwise indicated implicitly or explicitly, the numerical parameter and / or non-numerical properties set forth herein are approximations, and the optimal values of these properties and parameters may depend on the desired properties sought, the limits of detection under standard test conditions or methods, the limitations of the processing methods, and / or the nature of the property or parameter. When directly and explicitly distinguishing embodiments from disclosed prior art, the embodiment numbers are not approximations unless the word “about” is recited. Barrier Films: Often metallized polymer films to block or reduce oxygen passing through a pair of films to an interior material sandwiched between two of the barrier films. Exemplary films include aluminum coated polyester films where one surface of the film has an aluminum coating. The polymer can often be a polyester such as polyethylene terephthalate (PET). Other metals such as nickel may be used in place of the aluminum but aluminum is typically preferred. Colloidal suspension: A mixture consisting of a disperse phase (the suspended particles) and a continuous phase (the liquid medium of suspension), wherein the mixture either does not settle, or would take a very long time to settle appreciably. Dispersibility: The ability of QDs to form a colloidal suspension or a homogenous solution depending on the system. Emission spectrum: Those portions of the electromagnetic spectrum over which QDs (or a composition containing them) exhibit PL (in response to excitation by a light source) whose amplitude is at least 1% of the peak PL emission.

[0009] 8 LEGAL02 / 44543790v1 Nanoparticle: A nanoscale particle of a solid material. The nanoparticles disclosed herein are preferably crystalline and have a size of less than 500 nanometers in dimension. The nanoparticles disclosed herein may form a colloidal suspension. Embodiments of the disclosed nanoparticles may be of a single material or may include an inner core and an outer shell of differing materials. The nanoparticles may further include a plurality of ligands bound to the nanoparticle outer surface. Exemplary nanoparticles which may be utilized in the compositions, systems and methodologies described herein may comprise metals, metal oxides, metal chalcogenides, semiconductors, and insulators. Photoluminescence (PL): The emission of light (electromagnetic radiation, in the form of photons) after the absorption of light. It is one form of luminescence (light emission) and is initiated by photoexcitation (excitation by photons). Polymers (as well as polar polymers): A large molecule, or macromolecule, composed of many repeating subunits. Polymers range from familiar synthetic plastics such as polystyrene or poly(methyl methacrylate) (PMMA), to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many smaller molecules, e.g, monomers. Exemplary polymers include poly(methyl methacrylate) (PMMA), polystyrene, silicones, epoxy resins and the like. Quantum Dot (QD): A nanoscale particle that exhibits size-dependent electronic and optical properties due to quantum confinement. The quantum dots disclosed herein preferably have at least one dimension less than about 50 nanometers. The disclosed quantum dots may be colloidal quantum dots, i.e., quantum dots that may remain in suspension when dispersed in a liquid medium. Some of the quantum dots which may be utilized in the compositions, systems and methodologies described herein are made from a binary semiconductor material having a formula MX, where M is a metal and X typically is selected from sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony or mixtures thereof. Exemplary binary quantum dots which may be utilized in the compositions, systems and methodologies described herein include CdS, CdSe, CdTe, PbS, PbSe, PbTe, ZnS, ZnSe, ZnTe, InP, InAs, Cu2S, and In2S3. Other quantum dots which may be utilized in the compositions, systems and methodologies described herein are ternary, quaternary, and / or alloyed quantum dots including, but not limited to, ZnSeyS1-y, ZnTeySe1-y, ZnTeyS1-y, CdSeyS1-y, CdTeySe1-y, CdTeyS1-y, HgSeyS1-y, HgTeySe1-y, HgTeyS1-y, ZnCdS, ZnCdSe,

[0010] 9 LEGAL02 / 44543790v1 ZnCdTe, ZnHgS, ZnHgSe, ZnHgTe, CdHgS, CdHgSe, CdHgTe, ZnCdSexS2-x, ZnCdSexTe2-x, ZnHgSexTe2-x, ZnHgSexS2-x, CdHgSexS2-x, CdHgSeTe, CuInS2, CuInSe2, CuAlS2, CuAlSe2, CuInTe2, CuInGaSe2, CuInZnS2, CuZnSnSe2, CuInSexS2-x, CuInZnSexS2-x, (CuyAg1-y)InSexS2-x,AgInS2, AgInSe2, and AgInSexS2-x quantum dots, where 0≤x≤2 and 0≤y≤1, although the use of non-toxic quantum dots is preferred. Embodiments of the disclosed quantum dots may be of a single material, or may comprise an inner core and an outer shell (e.g., a thin outer shell / layer formed by any suitable method, such as cation exchange). The quantum dots may further include a plurality of ligands bound to the quantum dot surface. Solubility: When used in reference to QDs, the ability of QDs to form a colloidal suspension or a clear homogenous solution without haze caused by formation of aggregates. Numerous free radical photoinitiators are well known to those skilled in the art for photocuring of a polymer mixture by use of a suitable light such as UV-radiation. Examples of photoinitiators can include phosphine oxide, phenones, ethers, ketals and thio-xanthanes One especially suitable photoinitiator, a free radical photoinitiator, is a composite of 2, 4, 6- trimethylbenzoyl-diphenyl-phosphine oxide (50%) and 2-hydroxy-2-methyl-1-phenylpropanone (50%) (available from IGM Resins under the tradename Omnirad 4265). It is useful for UV radiation curing systems wherein UV radiation is applied in the wavelength range of from about 200 to 400 nm. Plasticizers are generally be included to adjust the viscosity of the polymer compositions to make them more flexible, less brittle and generally more processable. There are numerous examples of plasticizers well known to those skilled in the art including one or more phthalates, terephthalates, adipates, sebacates, glycolates, dipropylene glycol dibenzoate, mineral oils and combinations thereof Among particular plasticizers presently explored were included: dioctyl terephthalatee, diisodecyl phthalate, bis(ethylhexyl) adipate, glycolates, dipropylene glycol dibenzoate, 2,2'- ethylenedioxydiethyl bis(2-ethylhexanoate), and bis(ethylhexyl) sebacate. Others such as mineral oil or vegetable oil will readily be apparent to those skilled in the art. A plasticizer or combination of plasticizers can generally be added in amounts of 0.1 wt % to 50 wt %, or from 5 wt % to 40 wt %, or 10 wt % to 30 wt %, where wt % is based on the total weight of the particular composition.

[0011] 10 LEGAL02 / 44543790v1 Alternatively, thermal curing may be used as is well known to those skilled in the art. EXAMPLES The following examples are non-limiting and are merely intended to further illustrate the compositions, systems and methodologies described herein. Example 1 Synthesis of CuInS2 / ZnS quantum dots using dioctyl terephthalate In a deaerated round bottom flask, a 0.5 molar ratio of copper iodide and indium acetate was heated in a mixture of dodecanethiol and oleylamine within a temperature range of about 200oC to 300oC and maintained for from about 5 to about 60 minutes. The resultant solution was then combined with a solution containing zinc acetate, oleic acid, dioctyl terephthalate and dodecanethiol within a temperature range of about 200oC to 300oC and maintained for from about 10 minutes to about 1000 minutes to form a shell around the QD core. Subsequently, several different isolation methods were used for the resultant quantum dots. Isolation method A: In this method of isolation, the reaction solution was mixed with 20mL of hexane and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant QD solution was distilled under reduced pressure to remove hexane. The remaining QD concentrate was taken for the production of QD film. Isolation method B: In this method of isolation, the reaction solution was mixed with 20mL of 1- octadecene and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film. Isolation method C: In this method of isolation, the reaction solution was mixed with 20mL of isobornyl acrylate and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the

[0012] 11 LEGAL02 / 44543790v1 bottom of the flask which is then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film. Example 2 Synthesis of CuInS2 / ZnS quantum dots using diisodecylterephthalate In a deaerated round bottom flask, a 0.5 molar ratio of copper iodide and indium acetate was heated in a mixture of dodecanethiol and oleylamine within a temperature range of about 200oC to 300oC and maintained for from about 5 to about 60 minutes. The resultant solution was then combined with a solution containing zinc acetate, oleic acid, diisodecylterephthalate and dodecanethiol within a temperature range of about 200oC to 300oC and maintained for from about 10 minutes to about 1000 minutes to form a shell around the QD core. As before, several different isolation methods were used for the resultant quantum dots. Isolation method A: In this method of isolation, the reaction solution was mixed with 20mL of hexane and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant QD solution was distilled under reduced pressure to remove hexane. The remaining QD concentrate was taken for the production of QD film. Isolation method B: In this method of isolation, the reaction solution was mixed with 20mL of 1- octadecene and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film. Isolation method C: In this method of isolation, the reaction solution was mixed with 20mL of isobornyl acrylate and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which is then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film.

[0013] 12 LEGAL02 / 44543790v1 Example 3 Synthesis of CuInS2 / ZnS quantum dots using bis(ethylhexyl) adipate In a deaerated round bottom flask, a 0.5 molar ratio of copper iodide and indium acetate was heated in a mixture of dodecanethiol and oleylamine within a temperature range of about 200oC to 300oC and maintained for from about 5 to about 60 minutes. The resultant solution was then combined with a solution containing zinc acetate, oleic acid, bis(ethylhexyl) adipate and dodecanethiol within a temperature range of about 200oC to 300oC and maintained for from about 10 minutes to about 1000 minutes to form a shell around the QD core. As before, several different isolation methods were used for the resultant quantum dots. Isolation method A: In this method of isolation, the reaction solution was mixed with 20mL of hexane and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant QD solution was distilled under reduced pressure to remove hexane. The remaining quantum dot concentrate (syrup) was taken for the production of QD film. Isolation method B: In this method of isolation, the reaction solution was mixed with 20mL of 1- octadecene and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film. Isolation method C: In this method of isolation, the reaction solution was mixed with 20mL of isobornyl acrylate and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which is then separated from the solution by filtration. The resultant quantum dot solution (syrup) is taken for the production of QD film. Example 4 Synthesis of CuInS2 / ZnS quantum dots using bis(ethylhexyl) sebacate In a deaerated round bottom flask, a 0.5 molar ratio of copper iodide and indium acetate was heated in a mixture of dodecanethiol and oleylamine within a temperature range of about 200oC to 300oC

[0014] 13 LEGAL02 / 44543790v1 and maintained for from about 5 to about 60 minutes. The resultant solution was then combined with a solution containing zinc acetate, oleic acid, bis(ethylhexyl) sebacate and dodecanethiol within a temperature range of about 200oC to 300oC and maintained for from about 10 minutes to about 1000 minutes to form a shell around the QD core. As before, several different isolation methods were used for the resultant quantum dots. Isolation method A: In this method of isolation, the reaction solution was mixed with 20mL of hexane and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant QD solution was distilled under reduced pressure to remove hexane. The remaining quantum dot concentrate (syrup) was taken for the production of QD film. Isolation method B: In this method of isolation, the reaction solution was mixed with 20mL of 1- octadecene and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which was then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film. Isolation method C: In this method of isolation, the reaction solution was mixed with 20mL of isobornyl acrylate and set aside for 30 minutes. After 30 minutes, white precipitate appeared at the bottom of the flask which is then separated from the solution by filtration. The resultant quantum dot solution (syrup) was taken for the production of QD film. Example 5 Preparation of QD liquid concentrate (QDLC) in dioctyl terephthalate QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in dioctyl terephthalate at 70-95% QD concentration by weight to produce QD liquid concentrate in dioctyl terephthalate. Example 6

[0015] 14 LEGAL02 / 44543790v1 Preparation of QD liquid concentrate (QDLC) in diisodecyl phthalate QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in diisodecyl phthalate at 70-95% QD concentration by weight to produce QD liquid concentrate in diisodecyl phthalate. Example 7 Preparation of QD liquid concentrate (QDLC) in bis(ethylhexyl) adipate QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in bis(ethylhexyl) adipate at 70-95% QD concentration by weight to produce QD liquid concentrate in bis(ethylhexyl) adipate. Example 8 Preparation of QD liquid concentrate (QDLC) in bis(ethylhexyl) sebacate QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in bis(ethylhexyl) sebacate at 70-95% QD concentration by weight to produce QD liquid concentrate in bis(ethylhexyl) sebacate. Example 9 Preparation of QD liquid concentrate (QDLC) in octadecene QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in octadecene at 70-95% QD concentration by weight to produce QD liquid concentrate in octadecene.

[0016] 15 LEGAL02 / 44543790v1 Example 10: Preparation of QD liquid concentrate (QDLC) in tetradecene or tetradecane QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in tetradecene or tetradecane at 70-85% QD concentration by weight to produce QD liquid concentrate in tetradecene or tetradecane. Example 11: Preparation of QD liquid concentrate (QDLC) in dodecene or dodecane QD prepared by example 1 was mixed with acetone and the mixture was centrifuged at 4300 rcf. The resultant precipitate was separated from the supernatant and the precipitate was dissolved in dodecene or dodecane at 70-85% QD concentration by weight to produce QD liquid concentrate in dodecene or dodecane. Example 12 Wet-lamination of QD-plasticizer solution In separate flasks, a quantum dot mixture from each of examples 1-4 was mixed with isobornyl acrylate monomer, styrene-b-ethylene-butadiene-styrene powder, butyl acrylate and omnirad 4265 at room temperature. Each resulting mixture was coated between two sheets of metallized PET as barrier films using a drawdown coater and then photocured using 320-390 nm UV- light for the preparation of laminated films. Example 13 Wet-lamination of QD-dioctyl terephthalate solution In a flask, quantum dot liquid concentrate from example 5 mixed with isobornyl acrylate monomer, styrene-b-ethylene-butadiene-styrene, butyl acrylate and omnirad 4265 at room temperature. The resulting mixture was coated between two sheets of barrier films of metallized polyethylene terephthalate (PET) using a drawdown coater and then photocured using 320-390 nm UV- light

[0017] 16 LEGAL02 / 44543790v1 for the preparation of laminated films. Fig.1 shows a picture of the visible emitting CuInS2 / ZnS quantum dots in various plasticizers. Example 14 Wet-lamination of QD- diisodecyl terephthalate solution In a flask, quantum dot liquid concentrate from example 6 mixed with isobornyl acrylate monomer, styrene-b-ethylene-butadiene-styrene, butyl acrylate and omnirad 4265 at room temperature. The resulting mixture was coated between two sheets of barrier films of metallized polyethylene terephthalate (PET) using a drawdown coater and then photocured using 320-390 nm UV-light for the preparation of laminated films. Example 15 Wet-lamination of QD-bis(ethylhexyl) adipate solution In a flask, quantum dot liquid concentrate from example 7, mixed with isobornyl acrylate monomer, styrene-b-ethylene-butadiene-styrene, butyl acrylate and omnirad 4265 at room temperature. The resulting mixture was coated between two sheets of barrier films of metallized polyethylene terephthalate (PET) using a drawdown coater and then photocured using 320-390 nm UV- light for the preparation of laminated films. Example 16 Wet-lamination of QD- bis(ethylhexyl) sebacate solution In a flask, quantum dot liquid concentrate from example 8, mixed with isobornyl acrylate monomer, styrene-b-ethylene-butadiene-styrene, butyl acrylate and omnirad 4265 at room temperature. The resulting mixture was coated between two sheets of barrier films of metallized polyethylene terephthalate (PET) using a drawdown coater and then photocured using 320-390 nm UV- light for the preparation of laminated films.

[0018] 17 LEGAL02 / 44543790v1 Example 17 Extrusion of QDs in EVA In an extruder (shown in Fig. 3), ethylene vinyl acetate (EVA) pellets at a feed rate of around 120g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 terephthalate was introduced at a feed rate of 12 mL / h into the extruder at 150 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Example 18 Extrusion of QDs in EVOH In an extruder (shown in Fig.3), ethylene vinyl alcohol (EVOH) pellets at a feed rate of around 230g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 was introduced at a feed rate of 23 mL / h into the extruder at 220 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Table 6 shows results for EVOH plus the sebacate. Photostability measurements: The pressed samples from this experiment were put in a photostability chamber at 50 °C and illuminated using 400 nm. The photoluminescence (PL) intensity was collected as a function of time. Figure 6 shows a graph of PL intensity over the time from the samples obtained by the QD liquid concentrate extrusion and QD power extrusion (as a control) and also from the sample that was obtained from letting down 12% QD loading to 7.4% through the extruder. Example 19

[0019] 18 LEGAL02 / 44543790v1 Extrusion of QDs in LDPE In an extruder (shown in Fig.3), low density polyethylene (LDPE) pellets at a feed rate of around 234g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 was introduced at a feed rate of 23.4 mL / h into the extruder at 180 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Table 6 shows results for LDPE plus the octadecene. Example 20 Extrusion of QDs in maleic anhydride grafted LDPE (PE-MAH) In an extruder (shown in Fig.3), maleic anhydride grafted LDPE (PE-MAH) pellets at a feed rate of around 254g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 was introduced at a feed rate of 25.4 mL / h into the extruder at 180 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Table 6 shows results for PE-MAH plus the octadecene. Example 21 Extrusion of QDs in maleic anhydride grafted EVA (EVA-MAH) In an extruder (shown in Fig.3), maleic anhydride grafted EVA (EVA-MAH) pellets at a feed rate of around 254g / h is introduced through the hopper and in another port, QD liquid concentrate from examples 5-9 was introduced at a feed rate of 25.4 mL / h into the extruder at 180 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Example 22

[0020] 19 LEGAL02 / 44543790v1 Extrusion of QDs in thermoplastic polyurethane (TPU) In an extruder (shown in Fig.3), thermoplastic polyurethane (TPU) pellets at a feed rate of 107g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 was introduced at a feed rate of 10.7 mL / h into the extruder at 160 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Table 6 shows results for TPU plus the sebacate. Example 23 Extrusion of QDs in nylon In an extruder (shown in Fig.3), nylon pellets at a feed rate of 74 g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5- 9 was introduced at a feed rate of 7.5 mL / h into the extruder at 205 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed at 190oC to form about 50-100 µm thick films for optical characterization. In case of this polymer, it was noted that feed rate, temperature, RPM and hot-pressing temperatures played a critical role for brighter films. Table 6 shows results for nylon plus sebacate. Example 24 Extrusion of QDs in PVB In an extruder (shown in Fig.3), polyvinyl butyral (PVB) pellets at a feed rate of around 120g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 was introduced at a feed rate of 12 mL / h into the extruder at 150 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Example 25

[0021] 20 LEGAL02 / 44543790v1 Extrusion of QDs in polystyrene In an extruder (shown in Fig. 3), polystyrene (PS) pellets at a feed rate of around 150g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 is introduced at a feed rate of 15 mL / h into the extruder at 225 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Example 26 Extrusion of QDs in polyolefin In an extruder (shown in Fig.3), polyolefin (POE) pellets at a feed rate of 162g / h was introduced through the hopper and in another port, QD liquid concentrate from each individual sample from examples 5-9 was introduced at a feed rate of 16 mL / h into the extruder at 90 °C and the resultant strands were chopped to produce pellets of composite material. The pellets were hot pressed to form about 50-100 µm thick films for optical characterization. Example 27 Preparation of a NIR emitting CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt- octadecene) composite a. In a typical process, CuInS2 / ZnS quantum dots (from Strem, catalogue no: 29-8540) and poly(maleic anhydride-1-alt-octadecene) PMAO (50:50) were dissolved in excess 1-octadecene (ODE) and heated up to about 200oC while stirring vigorously for about 3 hours whereupon a dark black sludge was obtained (Mixture A). b. The process for the isolation of the CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt-octadecene) blend was as follows. To remove the ODE, excess acetone was added to mixture A and centrifuged for 15 minutes to precipitate the quantum dot- polymer composite. This process was repeated 3 times to obtain wet precipitate which

[0022] 21 LEGAL02 / 44543790v1 was then placed under high vacuum for 48 hours to remove trace acetone. The product was obtained as a brittle dark solid – see Fig.7 (a). Example 28 Preparation of a NIR emitting CuInS2 / ZnS quantum dots and (2-dodecen-1-yl) succinic anhydride blend In a typical process, (2-dodecen-1-yl) succinic anhydride (DDSA) (50% by weight) was melted by placing in a convection oven at 70oC for about 15 minutes. To this melt, the NIR emitting CuInS2 / ZnS quantum dots (50%by weight) were added and mixed vigorously via a vortex shaker. Mixing was assisted by adding excess chloroform to form a thick black sludge–- see Fig.7(b). The chloroform was removed under high vacuum. Example 29 Preparation of a NIR emitting CuInS2 / ZnS quantum dots and polyethylene glycol monooleate blend In a typical process, polyethylene glycolmonooleate (PEG-O, 50% by weight) was melted by placing in a convection oven at 70oC for about 15 minutes. To this melt, the NIR emitting CuInS2 / ZnS quantum dots (50% by weight) were added and mixed vigorously via a vortex shaker. Mixing was assisted by adding excess chloroform to form a thick black sludge. The chloroform was removed under high vacuum to form a viscous black paste – see Fig. I). Example 30 Preparation of a NIR emitting CuInS2 / ZnS quantum dots and polyethylene glycol distearate blend In a typical process, polyethylene glycol distearate (PEG-DS, 50% by weight) was melted by placing in a convection oven at 70oC for about 15 minutes. To this melt, the NIR emitting CuInS2 / ZnS quantum dots (50% by weight) were added and mixed vigorously via a vortex shaker. Mixing was assisted by adding excess chloroform to form a thick black sludge. The chloroform was removed under high vacuum to form a viscous black paste – see Fig.7(d).

[0023] 22 LEGAL02 / 44543790v1 Example 31 Role of octadecene (ODE) in blend compatibility of the NIR emitting CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt-octadecene): The presence of ODE was required to ensure appropriate compatibility between the NIR emitting CuInS2 / ZnS quantum dots and the and poly(maleic anhydride-1-alt-octadecene) (PMAO). Upon comparing high temperature melt mixing (as described in Example A above) of both the PMAO and the CuInS2 / ZnS quantum dots and the PMAO and the CuInS2 / ZnS quantum dots with ODE, it was observed that the latter provided (ensures) improved mixing. Upon melt pressing the composites using a hot plate between two glass slides, the presence of ODE clearly indicated higher mixing capability as shown in Fig.8. EXAMPLE 32 Drop casting and subsequent melt pressing of ethylene vinyl acetate with the NIR emitting CuInS2 / ZnS quantum dots A dot-polymer isolate was capable of synthesizing a composite material with EVA via co- dispersion in a suitable solvent. For example, an appropriate amount of the NIR emitting CuInS2 / ZnS quantum dots and (2-dodecen-1-yl) succinic anhydride blend was dispersed in 10% by weight ethylene vinyl acetate in toluene solution through sonication and heating in oven at 90oC. Post dispersion, the highly viscous blended gel was drop casted onto a glass slide to evaporate the excess toluene. Post evaporation, 2 films were overlayed and melt pressed between two glass slides. Melt pressing involved subjecting the glass-film(s)-glass sandwich to a temperature of about 170oC at high pressure. The sandwich was then quickly immersed in a water bath containing ice to quench the temperature. Quenching can be vital in ensuring an immediate temperature drop to below the glass transition temperatures to avoid crystallization, resulting in excellent clarity and low opacity induced haze. Fig. 9 shows comparison of (b) NIR emitting CuInS2 / ZnS quantum dot composites with ethylene vinyl acetate in the absence of (2-dodecen-1- yl) succinic anhydride (DDSA) (Fig. 9 b); and (c) NIR emitting CuInS2 / ZnS quantum dot

[0024] 23 LEGAL02 / 44543790v1 composites with ethylene vinyl acetate in the presence of (2-dodecen-1-yl) succinic anhydride (DDSA) (Fig.9 c). For comparison, Fig.9 (a) shows native ethylene vinyl acetate. Characterization of polymer-dot and polymer-dot-compatibilizer composite was carried out by measuring both optical haze and in-device quantum yield. Incorporation of dots in both cases led to an increase in film haze. This can be attributed to non-trivial morphological changes to the composite due to solvent evaporation. Differential evaporation can also lead to thickness variation in films resulting in variation of observed haze values. An example film was characterized as having haze less than 5% and quantum yield greater than 80%. Example 33 Co-extrusion of the NIR emitting CuInS2 / ZnS quantum dots in ethylene vinyl acetate (EVA) and subsequent melt pressing The compatibilizer-quantum dot composites from examples A-D can be conveniently co-extruded with a desired polymer matrix in accordance with the processing parameters of the polymer. It was imperative, at this stage, to select for compatibilizers that have melting parameters conducive to co-extrusion with the primary matrix. Therefore, all the compatibilizers (with the exception of PMAO) discussed below were screened for having a melt temperature well below the extrusion melt temperature of the parent polymer matrix. The protocol for extrusion of compatibilizer-dot-polymer was as follows. In a typical process, the desired additive (quantum dot or quantum dot-compatibilizer blend) was dry mixed with ethylene vinyl acetate. Mixing was carried out in a plastic sample bag by extensive shaking but the same can also be carried out with an appropriate mixing apparatus such as a tumble mixer / brabender compounding machine. Post mixing, the polymer was fed through a typical feeding mechanism in a twin-screw extruder. Extruded filaments of polymer-dot composites could then be collected for post processing melt pressing. Melt pressing of polymer-quantum dot composites was conducted as follows.500 milligram (mg) of filament was cut and pressed as thin films between two glass slides as described above. The melt temperature was kept constant at 170oC for 6 minutes at the highest-pressure setting. Post press, the glass-polymer-glass sandwich was quickly immersed in freezing cold water and the films

[0025] 24 LEGAL02 / 44543790v1 were separated from the glass slides. The process was repeated once more to retrieve two films which can then be overlayed to form the final film. Fig.10 shows dot imbibed EVA films fabricated through this process. In this study, native EVA films were fabricated and compared to films fabricated out of EVA+NIR dot+PMAO , NIR dot and EVA+NIR dot+PEG-O filaments (Figure 10 (b), (c) and (d) respectively). In Fig.10 is shown the comparison of NIR emitting CuInS2 / ZnS quantum dot imbibed EVA films where: (a) is native ethylene vinyl acetate (EVA) films; (b) composite films of EVA with the NIR emitting CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt-octadecene; (c) composite films of EVA with the NIR emitting CuInS2 / ZnS quantum dots; and, (d) composite films of EVA with the NIR emitting CuInS2 / ZnS quantum dots and polyethylene glycol monooleate filaments. Poor dispersion was observed in the case of the ethylene vinyl acetate, NIR emitting CuInS2 / ZnS quantum dots and poly(maleic anhydride-1-alt-octadecene) blend, presumably due to the high processing temperatures of PMAO compared to EVA. This can easily be mitigated in subsequent runs by retaining trace amounts of ODE as described above to ensure appropriate bridging of the quantum dot-PMAO complex with the primary EVA matrix. Extensive mixing was observed in co-extruded dot-EVA and dot-EVA-PEG-O systems (Fig. 10(c) and 10(d)) with the latter being clearly more conducive to dispersive mixing. Although the present invention has been described with reference to specific details, it is not intended that such details should be regarded as limitations upon the scope of the invention. Various modifications, substitutions, combinations, and ranges of parameters may be made or utilized in the compositions, and methodologies described herein.

[0026] 25 LEGAL02 / 44543790v1

Claims

WHAT IS CLAIMED IS:

1. A solid composition including: fluorescent quantum dots; a polymer; and, a plasticizer material capable of providing dispersion of the quantum dots throughout the polymer.

2. The composition of claim 1, wherein said composition is characterized as having haze less than 5%.

3. The composition of claim 1, wherein said composition is characterized as maintaining its level of fluorescence within 80% of its initial value over one year of sunlight exposure.

4. The composition of claim 1, wherein said polymer is extruded.

5. The composition of claim 1, wherein said polymer is a thermoplastic polymer. The composition of claim 1, wherein said polymer is selected from the group consisting of ethylene vinyl acetate (EVA), polyvinyl butyal (PVB), ethylene vinyl alcohol (EVOH), low density polystyrene (LDPS), nylon, polyethylene (PE), polyamide (PA), thermoplastic polyurethane (TPU), maleic anhydride grafted polyethylene (PE-MAH), maleic anhydride grafted ethylene vinyl acetate (EVA-MAH), polyolefin (POE), ionomers, polyvinyl difluoride (PVDF) or a mixture thereof.

7. The composition of claim 1, wherein said polymer further includes acrylate monomer, a styrene-butadiene copolymer, and a photoinitiator.

8. The composition of claim 1, wherein said plasticizer is selected from the group consisting of phthalates, terephthalates, adipates, sebacates, glycolates, dipropylene glycol dibenzoate, octadecene, tetradecene, dodecene, tetradecane, dodecane, dioctyl terephthalate, diisodecyl phthalate, bis(ethylhexyl) adipate, dipropylene glycol dibenzoate, 1-octadecene, 2,2'-Ethylenedioxydiethyl bis(2-ethylhexanoate), bis(ethylhexyl) sebacate, and combinations thereof.

9. The composition of claim 1, wherein said quantum dots comprise a material selected from the group consisting of CuInS2, CuInSe2, CuAlS2, CuAlSe2, CuInGaS2, CuInZnSe2,26 LEGAL02 / 44543790v1CuInSexS2-x, CuIn(Se,S)2, CuInZn(Se,S)2, AgInS2, AgInSe2, AgIn(Se,S)2, ZnS, ZnSe, CdS, CdSe, and combinations thereof.

10. The composition of claim 1, wherein said plasticizer is selected from the group consisting of poly(maleic anhydride-1-alt-octadecene), poly(isobutylene-alt- maleic anhydride), poly(ethylene-alt- maleic anhydride), polypropylene-graft-maleic anhydride, poly(sodium 4-styrenesulfonate), poly(potassium 4-styrenesulfonate), poly(ammonium 4- styrenesulfonate), (2-Dodecen-1-yl) succinic anhydride, polyethylene glycol(PEG) monooleate, polyethylene glycol(PEG) dioleate, polyethylene glycol(PEG) distearate, and combinations thereof.

11. A liquid composition including: fluorescent quantum dots, each comprising of at least one semiconductor core and at least one semiconductor shell material; and, a liquid plasticizer material capable of providing dispersion of the quantum dots throughout a polymer matrix such that the composition of quantum dot and plasticizer in combination with the polymer matrix is characterized by haze of less than 5% in comparison to a composition of quantum dots in the polymer matrix in the absence of the plasticizer.

12. The composition of claim 11, wherein said semiconductor cores comprise a material selected from the group consisting of CuInS2, CuInSe2, CuAlS2, CuAlSe2, CuInGaS2, CuInZnSe2, CuInSexS2-x, CuIn(Se,S)2, CuInZn(Se,S)2, AgInS2, AgInSe2, and AgIn(Se,S)2, and combinations thereof.

13. The composition of claim 11, wherein said semiconductor shell material is ZnS, ZnSe, GaS, GaSe, CdS, CdSe, or combinations thereof.

14. The composition of claim 11, wherein said plasticizer is selected from the group consisting of phthalates, terephthalates, adipates, sebacates, glycolates, dipropylene glycol dibenzoate, octadecene, tetradecane, dodecane, tetradecane, dodecane, and combinations thereof.

15. The composition of claim 11, wherein said plasticizer is selected from the group consisting of dioctyl terepthalate, diisodecyl phthalate, bis(ethylhexyl) adipate, dipropylene glycol27 LEGAL02 / 44543790v1dibenzoate, 1-octadecene, 2,2'-Ethylenedioxydiethyl bis(2-ethylhexanoate) and bis(ethylhexyl) sebacate.

16. The composition of claim 11, wherein said plasticizer is a compatibilizing agent is selected from the group of poly(maleic anhydride-1-alt-octadecene), poly(isobutylene-alt- maleic anhydride), poly(ethylene-alt- maleic anhydride), polypropylene-graft-maleic anhydride, poly(sodium 4-styrenesulfonate), poly(potassium 4-styrenesulfonate), poly(ammonium 4- styrenesulfonate), (2-Dodecen-1-yl) succinic anhydride, polyethylene glycol(PEG) monooleate, polyethylene glycol(PEG) dioleate, polyethylene glycol(PEG) distearate, and combinations thereof.

17. The composition of claim 11, further including an extrudable polymeric material selected from the group consisting of ethylene vinyl acetate (PVAc), polyvinyl butyal (PVB), ethylene vinyl alcohol (EVOH), nylon, low density polystyrene (LDPS), polyethylene (PE), polyamide(PA), thermoplastic polyurethane(TPU), maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, polyolefin, polyvinyl difluoride (PVDF), and combinations thereof.

18. A process of preparing a core-shell quantum dot and plasticizer mixture comprising: precursors for a quantum dot core at temperatures and for times sufficient to form a resultant quantum dot core; and, admixing the resultant quantum dot core with a combination of both (a) precursors for a shell about the quantum dot core and (b) a plasticizer material capable of providing dispersion of resultant core-shell quantum dots into polymer matrixes to form a core-shell quantum dot / plasticizer mixture.

19. The process of claim 18 further comprising: admixing the core-shell quantum dot / plasticizer mixture with a solvent selected from among tetradecene, dodecene, and octadecene.

20. The process of claim 18, wherein said plasticizer is selected from the group consisting of phthalates, terephthalates, adipates, sebacates, glycolates, dioctyl terephthalate, diisodecyl phthalate, bis(ethylhexyl) adipate, dipropylene glycol dibenzoate, 2,2'-28 LEGAL02 / 44543790v1ethylenedioxydiethyl bis(2-ethylhexanoate), bis(ethylhexyl) sebacate, tetradecene, dodecene, tetradecane, dodecane, and octadecene, and combinations thereof.29 LEGAL02 / 44543790v1

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