Polymer composite photonic crystal coatings

Abstract

To provide polymer composite photonic crystal coatings.SOLUTION: Polymer composite photonic crystal materials are disclosed as coatings which have high reflection (>30%) in a specific range of the electromagnetic spectrum, such as ultraviolet (<400 nm), visible (Vis, 400 nm to 700 nm), or near-infrared radiation range (NIR, 700 to 2000 nm), and relatively low reflection (<20% reflection) in a second, different range of the electromagnetic spectrum. Surprisingly, it was found that through a formulation and additives approach, the optical properties of polymer composite photonic crystal films can be selectively modified from a variety of different coating methods, including spray deposition.SELECTED DRAWING: None

Description

[Technical field]

[0001] Related Applications This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Applications Nos. 62 / 798,760 (filed January 30, 2019), 62 / 846,127 (filed May 10, 2019), and 62 / 887,186 (filed August 15, 2019), each of which is incorporated herein by reference.

[0002] government support This invention was made with Government support under Grant Nos. DE-AR0000881 and DE-AE0001261 ​​awarded by the U.S. Department of Energy. The Government has certain rights in this invention. [Background technology]

[0003] Challenges exist in the fabrication of nanostructured materials that can selectively reflect or transmit certain ranges of the electromagnetic spectrum without significantly altering the reflection or transmission of other ranges. For example, materials are needed that allow high transmission (>60%) of visible (Vis, 400-700 nm) and / or ultraviolet (UV, <400 nm) radiation while not significantly absorbing it and being highly reflective (J. Am. Chem. Soc. 2014, 136, 17374). Specifically, access to these materials using facile fabrication procedures has yet to be realized. Conventional fabrication involves the extrusion of multilayer films (Polymer Engineering and Science, 1969, 9, 393), and current state-of-the-art techniques require intensive fabrication processes such as lithography and layer-by-layer assembly. Bottom-up processes such as block polymer self-assembly allow access to nanostructured materials from paint brushes, drawdowns, wire bars, doctor blades, bird bars, roller applications, screen printing, spray brushes, or spray gun applications without the need for energy-intensive manufacturing and / or designer materials such as precious metal oxides as major components. The ability to selectively apply reflective coatings by facile application methods opens up exciting possibilities for application to rough and curved surfaces where films and other top-down manufacturing processes cannot be used.

[0004] The current state of the art is represented by multilayer extruded thin films (U.S. Patents. 6,208,466 and 6,696,142) or layer-by-layer deposited metal oxide nanoparticles or polyelectrolytes (Bioinspir. Biomim. 2013, 8,045005, and U.S. Patent Application Publication No. 2014 / 0218792). Both of these approaches require significant investments in advanced manufacturing equipment / infrastructure and technology, in addition to potentially high material costs. The reflective properties inherent to the disclosed materials are established in a bottom-up process via self-assembly of BCPs, which occurs rapidly under easily accessible conditions, i.e., ambient or slightly elevated temperature, atmospheric pressure, and the presence of oxygen. The self-assembly process does not require specialized manufacturing techniques such as nanoimprint or e-beam lithography, and layer-by-layer deposition. The polymeric components, polymeric additives, and non-polymeric additives used in the coating are inexpensive and, in preferred embodiments, can be "commodity" materials, maintaining low material costs.

[0005] Current approaches for the preparation of reflective materials require significant investment in advanced manufacturing equipment and techniques, as well as high material costs. Therefore, there is a need for alternative compositions that allow for the preparation of more cost-effective reflective materials. Summary of the Invention

[0006] The present disclosure provides a method for improving the optical characteristics of photonic crystal materials, such as, but not limited to, reflectance (%R), maximum reflectance (λ), and / or other optical properties, including but not limited to, the use of inorganic / organic composite materials composed of brush block copolymers (BBCPs) and either an inorganic additive family, an organic additive family, or some combination of the two. maxThis work relates to the discovery that the wavelength (nm) of the reflection peak, and the full width at half maximum (FWHM) of the reflection peak, as well as the overall haze (% haze) of the material can be modified. Here, the optical characteristics can be tuned for the first order reflection and all higher order reflections, the relationship of which is derived from the Bragg equation: λm=2(n1d1+n2d2). Specifically, BBCPs composed of various monomer units are blended with either inorganic particles or organic polymer additives to tune the relative intensities of the higher order reflection peaks, resulting in high NIR reflection and low Vis reflection. The use of extrinsic additives to directly tune the relative intensities of the higher order reflection peaks of BBCP-derived photonic crystal materials is unique and enables the deployment of these materials in applications requiring selective NIR reflection and Vis transmission.

[0007] Thus, the present disclosure provides a photonic crystal composition that includes a pigment and a brush block copolymer (BBCP) of formula IA or formula IB. [ka] During the ceremony, R x is -(C2-C6)alkyl-OC(=O)G 1 where G 1 comprises polyacrylate, polymethacrylate or polylactic acid, R y is -(C1-C8)alkyl-G 2 -G 3 where G 2 is -C(=O)O- or a nitrogen heterocycle, and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R 1 is an unbranched alkyl; R 2 is a branched alkyl; J 1 and G are each independently CH2 or C=O; each J 2are independently CH2 or C=O; each Q is independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; a and b are each independently 0 to about 1000; x and y are each independently 1 to about 1000; The blocks a, b, x and y can be in any order, with the ratio of x:a being from 1:0 to about 1:3, and the ratio of y:b being from 1:0 to about 1:3.

[0008] The present disclosure also provides a method for tailoring the electromagnetic radiation reflectance, absorbance and transmittance profile of a substrate, comprising coating the substrate with a film of the above-described photonic crystal composition, wherein pigments in the photonic crystal composition tailor the reflectance, absorbance and transmittance profile of the substrate such that electromagnetic radiation reflected by the coated substrate is at least 5% greater than a corresponding uncoated substrate.

[0009] The present disclosure further provides a method for forming a photonic coating, comprising: a) combining a solvent, a pigment, and a brush block copolymer (BBCP) to form a mixture, wherein the BBCP is of formula IA or formula IB, or formula IC, as above; [ka] During the ceremony, R x is -(C2-C6)alkyl-OC(=O)G 1 where G 1 comprises polyacrylate, polymethacrylate or polylactic acid, R y is -(C1-C8)alkyl-G 2 -G 3 where G 2 is -C(=O)O- or a nitrogen heterocycle, and G 3comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R 1 is an unbranched alkyl; R 2 is a branched alkyl; a and b are each independently 0 to about 1000; x and y are each independently 1 to about 1000; wherein the ratio of x:a is from 1:0 to about 1:3 and the ratio of y:b is from 1:0 to about 1:3; b) applying a layer of the mixture to a substrate; and c) drying the layer to form a film; A method is provided in which the film forms a photonic coating on a substrate.

[0010] The present invention provides novel compositions comprising Formulae I-III as disclosed herein, intermediates for synthesizing polymers of Formulae I-III, and methods for preparing compositions comprising polymers of Formulae I-III. The present invention also provides polymers of Formulae I-III that are useful as intermediates for the synthesis of other useful polymers and compositions. The present invention provides the use of polymers of Formulae I-III for the manufacture of reflective coatings.

[0011] The following drawings form part of the specification and are included to further demonstrate certain embodiments or various aspects of the present invention. In some cases, embodiments of the present invention can be best understood by referring to the accompanying drawings in combination with the detailed description presented herein. The description and accompanying drawings may emphasize certain examples or aspects of the present invention. However, one skilled in the art will understand that some of the examples or aspects may be used in combination with other examples or aspects of the present invention. [Brief description of the drawings]

[0012] [Figure 1]Reflectance spectra of the polymer composite-coated glass substrate with a PLA-b-PS photonic crystal film containing inorganic additives (solid line) and a PLA-b-PS photonic crystal film without inorganic additives. [Figure 2A] Reflectance spectra of PLA-b-PS photonic crystal film-containing polymer composite coated glass substrate with 10 wt % (solid line) and 34 wt % (dashed line) poly(2-ethylhexyl methacrylate) additive. [Figure 2B] Reflectance (solid line) and transmittance (dashed line) spectra of a self-assembled film containing 10 wt % poly(2-ethylhexyl methacrylate) (from Figure 2A). [Diagram 3] Reflectance (solid line) and transmittance (dashed line) spectra of spray-deposited self-assembled PLA- b -PS photonic crystal films (left), a photograph of the film (top right), and the haze, visible light transmittance, solar heat gain coefficient, and color rendering index values ​​of the film (bottom right). [Figure 4] Reflectance (solid line) and transmittance (dashed line) of the PS-b-iBuMA photonic crystal film. [Diagram 5] Reflectance and transmittance spectra of PS-b-iBuMA photonic crystal film and acridine base-doped PS-b-iBuMA photonic crystal. [Figure 6] Reflectance and transmittance spectra of PS-b-iBuMA photonic crystal film and carmine-doped PS-b-iBuMA photonic crystal. [Figure 7] Reflectance and transmittance spectra of PS-b-iBuMA photonic crystal film and perylene-doped PS-b-iBuMA photonic crystal. [Figure 8] Reflectance and transmittance spectra of PS-b-iBuMA photonic crystal film and PS-b-iBuMA photonic crystal doped with acridine hydrate. [Figure 9] Reflectance and transmittance spectra of PS-b-iBuMA photonic crystal film and guaiazulene-doped PS-b-iBuMA photonic crystal. [Figure 10]Reflectance and transmittance spectra of PS-b-iBuMA photonic crystal film and PS-b-iBuMA photonic crystal doped with eosin Y. [Figure 11] Reflectance and transmittance spectra of the PS-b-iBuMA photonic crystal film and the bromothymol-doped PS-b-iBuMA photonic crystal. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present application relates to the use of inorganic / organic composite materials comprised of block copolymers (BCPs) and either a family of inorganic additives, a family of organic additives, or some combination of the two, to improve the optical characteristics of photonic crystal materials, such as, but not limited to, reflectance (%R), maximum reflectance (λ max This relates to the discovery that it is possible to modify the wavelength (nm) of the reflection peak, the full width at half maximum (FWHM), and the haze (% haze) of the resulting photonic crystal material, where the optical characteristics are adjusted for the first order reflection and all higher order reflections, the relationships being derived from Equation 1 (Polymer Engineering and Science 1973, 13, 216). Formula 1: λm=2(n1d1+n2d2) where m=order reflection, n=refractive index, and d=domain size.

[0014] Specifically, BCPs composed of various monomer units are blended with either inorganic additives, small molecule organic additives, and / or polymeric additives to tune the relative intensities of the higher order reflection peaks, resulting in high NIR reflectance and low vis reflectance, in some cases. The use of extrinsic additives to directly tune the relative intensities of the higher order reflection peaks of BCP-derived photonic crystal materials is unique in its approach, enabling the deployment of these materials in applications requiring selective reflection and transmission in different ranges of the electromagnetic spectrum.

[0015] definition In order to provide a clear and consistent understanding of the specification and claims, the following definitions are included. As used herein, the recited terms have the following meanings. All other terms and phrases used herein have their ordinary meanings as understood by one of ordinary skill in the art. Such ordinary meanings are set forth in Hawley's Condensed Chemical Dictionary 14 by R. J. Lewis, John Wiley & Sons. th This can be obtained by referring to technical dictionaries such as the 1991 Edition New York, NY, 2001.

[0016] References herein to "one embodiment," "an embodiment," and the like indicate that the described embodiment may include a particular aspect, feature, structure, moiety, or feature, but not all embodiments necessarily include that aspect, feature, structure, moiety, or feature. Moreover, such phrases may, but do not necessarily, refer to the same embodiment that is referenced elsewhere in this specification. Furthermore, when a particular aspect, feature, structure, moiety, or feature is described in connection with an embodiment, it is within the knowledge of one of ordinary skill in the art that such aspect, feature, structure, moiety, or feature affects or relates to other embodiments, whether or not explicitly described.

[0017] The singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, a reference to "a compound" includes a plurality of such compounds, such that a compound X includes a plurality of compounds X. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as a prelude to the use of exclusive terminology, such as "solely," "only," or the use of a "negative" limitation in connection with the recitation of any elements and / or claim elements described herein.

[0018] The term "and / or" means any one of the items, any combination of the items, or all of the items with which the term is associated. The phrases "one or more" and "at least one" are readily understood by those of ordinary skill in the art, especially when read in the context in which it is used. For example, the phrase can mean 1, 2, 3, 4, 5, 6, 10, 100, or any upper limit that is about 10-fold, 100-fold, or 1000-fold greater than the recited lower limit. For example, one or more substituents on a phenyl ring can refer to 1-5, or 1-4, for example, when the phenyl ring is disubstituted.

[0019] As will be understood by those of ordinary skill in the art, all numbers, including those expressing amounts of ingredients, properties (such as molecular weight), reaction conditions, and the like, are approximate and are understood to be optionally modified in all cases by the term "about." These values ​​may vary depending upon the desired properties sought to be obtained by one of ordinary skill in the art utilizing the teachings of the description herein. It is also understood that such values ​​inherently contain variability necessarily resulting from the standard deviation found in their respective testing measurements. When values ​​are expressed as approximations by use of the preposition "about," it will be understood that the particular value without the modifier "about" also forms a further aspect.

[0020] The terms "about" and "approximately" are used interchangeably. Both terms can refer to a variation of ±5%, ±10%, ±20%, or ±25% of the specified value. For example, "about 50" percent can vary in some embodiments by 45 to 55 percent, or as otherwise defined by a particular claim. In the case of integer ranges, the term "about" can include one or two integers greater than and / or less than the recited integers at each end of the range. Unless otherwise indicated herein, the terms "about" and "approximately" are intended to include values ​​close to the recited range, e.g., weight percent, that are equivalent with respect to the function of the individual components, compositions, or embodiments. The terms "about" and "approximately" can also modify the endpoints of the recited ranges, as described above in this paragraph.

[0021] As will be understood by those skilled in the art, for all purposes, particularly in terms of providing a written description, all ranges described herein include all possible subranges and combinations of subranges, as well as the individual values, particularly integer values, that make up the range. Thus, it is understood that each number between two specific numbers is also disclosed. For example, if 10 to 15 is stated, 11, 12, 13, and 14 are also individually disclosed as part of the range. A recited range (e.g., weight percentage or carbon group) includes each specific value, integer, decimal, or identical value within the range. Any recited range is readily recognizable as fully describing and enabling the same range to be divided into at least equal halves, thirds, quarters, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third, and upper third, etc. Also, as will be understood by those skilled in the art, all terms such as "up to," "at least," "greater than," "less than," "more than," "greater than," and "greater than or equal to" are inclusive of the recited numbers, and such terms refer to ranges that can subsequently be broken down into subranges as described above. Similarly, all ratios described herein include all subratios that fall within the broader ratio. Thus, the specific values ​​recited for radicals, substituents, and ranges are for illustrative purposes only, and they do not exclude alternative defined values ​​of radicals and substituents or other values ​​within the defined ranges. Furthermore, it will be understood that the endpoints of each range are significant in relation to the other endpoint and independently of the other endpoint.

[0022] The disclosure provides ranges, limits, and deviations for variables such as volume, mass, percentages, ratios, etc. Ranges such as "number 1" to "number 2" are understood by those skilled in the art to mean a continuous range of numbers, including integers and decimals. For example, 1 to 10 means 1, 2, 3, 4, 5, ... 9, 10. It also means 1.0, 1.1, 1.2, 1.3, ... 9.8, 9.9, 10.0, and also 1.01, 1.02, 1.03, etc. When a disclosed variable is a number less than "number 10", as above, this means a continuous range including integers and decimals less than the number 10. Similarly, when a disclosed variable is a number greater than "number 10", this means a continuous range including integers and decimals greater than the number 10. These ranges can be modified by the term "about", the meaning of which is explained above.

[0023] Those skilled in the art will also readily recognize that when members are grouped together in a common manner, such as Markush groups, the invention encompasses not only the entire recited group as a whole, but also each member of the group individually, and all possible subgroups of the main group. Moreover, for all purposes, the invention encompasses not only the main group, but also main groups in which one or more group members are absent. Thus, the invention contemplates the explicit exclusion of any one or more of the members of a recited group. Thus, provisos may be applied to any of the disclosed categories or embodiments, whereby any one or more of the recited elements, species, or embodiments may be excluded from such categories or embodiments, for example, for use in an express negative limitation.

[0024] The term "contacting" refers to the act of touching, bringing into contact, or bringing into close proximity, e.g., at the cellular or molecular level, e.g., in a solution, reaction mixture, to cause a physiological reaction, a chemical reaction, or a physical change.

[0025] "Effective amount" refers to an amount effective to produce a recited effect, for example, the amount required to form a product in a reaction mixture. Determining an effective amount is usually within the capabilities of those skilled in the art, especially in light of the detailed disclosure provided herein. The term "effective amount" is intended to include, for example, an amount of a compound or reagent described herein, or an amount of a combination of compounds or reagents described herein, that is effective to form a product in a reaction mixture. Thus, "effective amount" generally refers to an amount that provides a desired effect.

[0026] The term "substantially" as used herein is a broad term and is used in its ordinary sense, including, without limitation, nearly, but not necessarily completely, what is specified. For example, the term can refer to a numerical value that may not be 100% complete. The complete numerical value may be less than about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, or about 20%.

[0027] The present disclosure provides a method for preparing the compounds and compositions of the present invention.The compounds and compositions can be prepared by any of the applicable techniques described herein, optionally in combination with standard techniques of organic synthesis.Many techniques, such as etherification and esterification, are well known in the art. However, many of these techniques are covered in the Compendium of Organic Synthetic Methods (John Wiley & Sons, New York), Vol. 1, Ian T. Harrison and Shuyen Harrison, 1971; Vol. 2, Ian T. Harrison and Shuyen Harrison, 1974; Vol. 3, Louis S. Hegedus and Leroy Wade, 1977; Vol. 4, Leroy G. Wade, Jr., 1980; Vol. 5, Leroy G. Wade, Jr., 1984; and Vol. 6, by M. B. Smith and J. March, March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th Ed. (John Wiley & Sons, New York, 2001); Comprehensive Organic Synthesis. Selectivity, Strategy & Efficiency in Modern Organic Chemistry. In 9 Volumes, Barry These are described in detail in standard organic chemistry reference texts, such as Advanced Organic Chemistry, Part B: Reactions and Synthesis, Second Edition, Cary and Sundberg (1983);

[0028] The formula and compounds described herein can be modified using protective group.Suitable amino and carboxy protective group is known to those skilled in the art (for example, see Protecting Groups in Organic Synthesis, Second Edition, Greene, TW, and Wutz, PGM, John Wiley&Sons, New York, and references cited therein; Philip J. Kocienski; Protecting Groups (Georg Thieme Verlag Stuttgart, New York, 1994) and references cited therein); and Comprehensive Organic Transformations, Larock, RC, Second Edition, John Wiley&Sons, New York (1999), and references cited therein.

[0029] As used herein, the term "substituted" or "substituents" is intended to indicate that one or more (e.g., in various embodiments, 1-20; in other embodiments, 1-10, 1, 2, 3, 4, or 5; in some embodiments, 1, 2, or 3; in other embodiments, 1 or 2) hydrogens on the group indicated using the phrase "substituted" (or "substituents") are replaced with a group selected from the indicated group, or with a suitable group known to one of ordinary skill in the art, provided that the replacement does not exceed the normal valence of the indicated atom and only if the substitution results in a stable compound. Suitable indicated groups include, for example, alkyl, alkenyl, alkynyl, alkoxy, halo, haloalkyl, hydroxy, hydroxyalkyl, aryl, heteroaryl, heterocycle, cycloalkyl, alkanoyl, alkoxycarbonyl, amino, alkylamino, dialkylamino, trifluoromethylthio, difluoromethyl, acylamino, nitro, trifluoromethyl, trifluoromethoxy, carboxy, carboxyalkyl, keto, thioxo, alkylthio, alkylsulfinyl, alkylsulfonyl, and cyano. Additionally, non-limiting examples of substituents that may be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR', OC(O)N(R')2, CN, CF3, OCF3, R', O, S, C(O), S(O), methylenedioxy, ethylenedioxy, N(R')2, SR', SOR', SOR', SOR', SOR', SOR', C(O)R', C(O)C(O)R', C(O)CH2C(O)R', C(S)R', C(O)OR', OC(O)R', C(O)N(R')2, OC(O)N(R')2, C(S)N(R')2, (CH2) 0-2and NHC(O)R', N(R')N(R')C(O)R', N(R')N(R')C(O)OR', N(R')N(R')CON(R'), N(R')SOR', N(R')SON(R'), N(R')C(O)OR', N(R')C(O)R', N(R')C(S)R', N(R')C(O)N(R'), N(R')C(S)N(R'), N(COR')COR', N(OR')R', C(=NH)N(R'), C(O)N(OR')R', or C(=NOR')R', where R' may be hydrogen or a carbon-based moiety which may itself be further substituted.

[0030] The term "halo" or "halide" refers to fluoro, chloro, bromo, or iodo. Similarly, the term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0031] The term "alkyl" refers to a branched or unbranched hydrocarbon having, for example, 1 to 20 carbon atoms, often 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms, or, for example, in the range of 1 to 20 carbon atoms, for example, in the range of 2 to 6, 3 to 6, 2 to 8, or 3 to 8 carbon atoms. As used herein, the term "alkyl" also encompasses "cycloalkyl," as defined below. Examples include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl (isopropyl), 1-butyl, 2-methyl-1-propyl (isobutyl), 2-butyl (sec-butyl), 2-methyl-2-propyl (t-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, hexyl, octyl, decyl, dodecyl, and the like. Alkyl can be unsubstituted or substituted, for example, with the substituents described below. Alkyl can be optionally partially or fully unsaturated. Thus, the recitation of an alkyl group can include both alkenyl and alkynyl groups. Alkyl may be a monovalent hydrocarbon radical, as described and exemplified above, or it may be a divalent hydrocarbon radical (i.e., alkylene).

[0032] The term "cycloalkyl" refers to cyclic alkyl groups, e.g., of 3 to 10 carbon atoms, having a single cyclic ring or multiple condensed rings. Cycloalkyl groups include, by way of example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and the like, or multiple ring structures such as adamantyl. Cycloalkyl groups can be unsubstituted or substituted. Cycloalkyl groups can be monovalent or divalent and can be optionally substituted as described for alkyl groups. Cycloalkyl groups can optionally include one or more sites of unsaturation, e.g., cycloalkyl groups can include one or more carbon-carbon double bonds, e.g., 1-cyclopent-1-enyl, 1-cyclopent-2-enyl, 1-cyclopent-3-enyl, cyclohexyl, 1-cyclohex-1-enyl, 1-cyclohex-2-enyl, 1-cyclohex-3-enyl, and the like.

[0033] The term "heterocycloalkyl" refers to a saturated or partially saturated monocyclic, bicyclic or polycyclic ring containing at least one heteroatom selected from nitrogen, sulfur, oxygen, preferably 1 to 3 heteroatoms in at least one ring. Each ring is preferably 3 to 10 members, more preferably 4 to 7 members. Examples of suitable heterocycloalkyl substituents include pyrrolidyl, tetrahydrofuryl, tetrahydrothiofuranyl, piperidyl, piperazyl, tetrahydropyranyl, morpholino, 1,3-diazapane, 1,4-diazapane, 1,4-oxazepane, and 1,4-oxathiapane. The group may be a terminal group or a bridging group.

[0034] The term "aryl" refers to an aromatic hydrocarbon group derived from removing at least one hydrogen atom from a single carbon atom of a parent aromatic ring system. The radical attachment site may be at a saturated or unsaturated carbon atom of the parent ring system. An aryl group may have 6 to 30 carbon atoms, for example about 6 to 10 carbon atoms. In other embodiments, an aryl group may have 6 to 60 carbon atoms, 6 to 120 carbon atoms, or 6 to 240 carbon atoms. An aryl group may have a single ring (e.g., phenyl) or multiple condensed (fused) rings, in which at least one ring is aromatic (e.g., naphthyl, dihydrophenanthrenyl, fluorenyl, or anthryl). Typical aryl groups include, but are not limited to, radicals derived from benzene, naphthalene, anthracene, biphenyl, and the like. An aryl may be unsubstituted or optionally substituted.

[0035] The term "heteroaryl" refers to a monocyclic, bicyclic or tricyclic ring system containing one, two or three aromatic rings and containing at least one nitrogen, oxygen or sulfur atom in the aromatic ring. Heteroaryl may be unsubstituted or substituted with one or more, particularly one to three, substituents, e.g., as described in the definition of "substituted". Typical heteroaryl groups contain from 2 to 20 carbon atoms in the ring backbone in addition to the one or more heteroatoms. Examples of heteroaryl groups include, but are not limited to, 2H-pyrrolyl, 3H-indolyl, 4H-quinolizinyl, acridinyl, benzo[b]thienyl, benzothiazolyl, β-carbolinyl, carbazolyl, chromenyl, cinnolinyl, dibenzo[b,d]furanyl, furazanyl, furyl, imidazolyl, imidizolyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, and aryl groups. Examples of heteroaryl include aryl, oxazolyl, perimidinyl, phenanthridinyl, phenanthrolinyl, phenarsazinyl, phenazinyl, phenothiazinyl, phenoxathiinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolyl, quinoxalinyl, thiadiazolyl, thianthrenyl, thiazolyl, thienyl, triazolyl, tetrazolyl, and xanthenyl. In one embodiment, the term "heteroaryl" refers to a monocyclic aromatic ring containing 5 or 6 ring atoms, including carbon, and 1, 2, 3, or 4 heteroatoms independently selected from nonperoxide oxygen, sulfur, and N(Z), where Z is absent or is H, O, alkyl, aryl, or (C1-C6)alkylaryl. In some embodiments, heteroaryl refers to an ortho-fused bicyclic heterocycle derived therefrom of about 8-10 ring atoms, particularly a benz derivative, or one derived by fusing a propylene, trimethylene, or tetramethylene diradical.

[0036] A "solvent" as described herein can include water or an organic solvent. Examples of organic solvents include hydrocarbons such as toluene, xylene, hexane, heptane, etc.; chlorinated solvents such as methylene chloride, chloroform, and dichloroethane; ethers such as diethyl ether, tetrahydrofuran, and dibutyl ether; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; alcohols such as methanol, ethanol, and tert-butanol; and aprotic polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and dimethylsulfoxide (DMSO). Other examples of solvents include halogenated aromatic compounds or halogenated phenyl compounds, such as fluorinated or polyfluorinated phenyl compounds, such as 4-chlorobenzotrifluoride. Solvents may be used alone or two or more of them may be mixed for use to provide a "solvent system."

[0037] The phrase "one or more" is readily understood by one of ordinary skill in the art, especially when read in the context in which it is used. For example, one or more substituents on a phenyl ring refers to 1 to 5, or 1 to 4, for example, when the phenyl ring is disubstituted. One or more subunits (i.e., repeat units or blocks) of a polymer can refer to about 5 to about 100,000, or any number of subunits.

[0038] Substituents of the compounds and polymers described herein may be present to a recursive extent. In this context, "recursive substituent" means that a substituent may recite another instance of itself. Because of the recursive nature of such substituents, theoretically, a large number may be present in any given claim. One of ordinary skill in the art of organic chemistry will understand that the total number of such substituents is reasonably limited by the desired properties of the intended compound. Such properties include, by way of example and not limitation, physical properties such as molecular weight, solubility or log P, application properties such as activity against the intended target, and practical properties such as ease of synthesis. Recursive substituents are an intended aspect of the invention. One of ordinary skill in the art of organic chemistry will understand the versatility of such substituents. To the extent that recursive substituents are present in the claims of the invention, the total number in the repeating units of the exemplary polymers may be, for example, about 1-50, about 1-40, about 1-30, about 1-20, about 1-10, or about 1-5.

[0039] The terms "repeat unit", "repeating unit", or "block" as used herein refer to a repeating portion of a polymer. A repeat unit may include one or more repeat units, for example, labeled repeat unit x, repeat unit y, repeat unit a, repeat unit b, etc. Repeat units x, y, a, and b may, for example, be linked in any order and covalently bonded together to form a linked repeat unit. A monomer or a combination of one or more different monomers may be linked to form a (linked) repeat unit of a polymer or copolymer.

[0040] The term "molecular weight" of the copolymers disclosed herein refers to the number average molecular weight (Mn). The corresponding weight average molecular weight (Mw) can be determined from the other disclosed parameters by methods known to those skilled in the art (e.g., by calculation).

[0041] The copolymers disclosed herein can include random copolymers or block copolymers. Random copolymers can be indicated by "r" on the bond between the repeat units of the copolymer. Thus, the arrangement of x and xa units is random throughout the length of the copolymer of formula I, and the total number of x and xa units is defined by the x and a of formula I that are randomly arranged along the length of the copolymer.

[0042] In various embodiments, the ends of the copolymer (i.e., the beginning or ending ends) are low molecular weight moieties (e.g., less than 500 Da), such as H, OH, OOH, CHOH, CN, NH, or hydrocarbons, such as alkyl (e.g., butyl or 2-cyanoprop-2-yl moieties at the beginning and ending ends), alkenes or alkynes, or moieties resulting from elimination reactions at the first and / or last repeat units in the copolymer.

[0043] Self-assembly is the process by which a disordered system of pre-existing components forms an organized structure or pattern due to specific local interactions between the components themselves, without external guidance. For molecular self-assembly, the adsorbed molecules initially form a disordered collection of molecules with low molecular density on the surface, or an ordered two-dimensional "lying down phase", and over a period of minutes to hours, begin to form a three-dimensional form on the substrate surface with higher molecular coverage. The "head groups" assemble on the substrate, while the tail groups assemble away from the substrate. Regions of densely packed molecules nucleate and grow until the surface of the substrate is covered with a single monolayer.

[0044] Brush block copolymer molecules are a special form of branched polymers that contain a main chain with linear, unbranched side chains. Brushes are often characterized by a high density of grafted chains. The limited space then results in a strong extension of the chains. Branching occurs by replacing a substituent, e.g., a hydrogen atom, on a monomer subunit with another covalently bonded chain of the polymer or, in the case of graft copolymers, with another type of chain. Branching can result from the formation of carbon-carbon or various other types of covalent bonds. Branching by ester and amide bonds is typically by condensation reactions.

[0045] The term "pigment" is used interchangeably with dye. A pigment is a material, such as a solid, solution, or liquid, that changes the color of reflected or transmitted light as a result of wavelength-selective absorption. Pigments or dyes may be organic, organometallic, or inorganic compounds.

[0046] The substrate can be any material that can be coated with the compositions disclosed herein. For example, the substrate can be glass, metal, alloy, polymer, composite, wood, dry paint, or any type of surface.

[0047] The following abbreviations have their usual meaning to those of ordinary skill in the art: D = dispersity, kDa = kilodaltons, M n = number average molecular weight, M W = weight average molecular weight.

[0048] EMBODIMENTS OF THE PRESENT DISCLOSURE The present disclosure provides a photonic crystal composition that includes a pigment or dye and a brush block copolymer (BBCP) of Formula IA or Formula IB. [ka] During the ceremony, R x is -(C2-C6)alkyl-OC(=O)G 1 where G 1 comprises polyacrylate, polymethacrylate or polylactic acid, Ry is -(C1-C8)alkyl-G 2 -G 3 where G 2 is -C(=O)O- or a nitrogen heterocycle, and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R 1 is an unbranched alkyl; R 2 is a branched alkyl; J 1 and G are each independently CH2 or C=O; each J 2 are independently CH2 or C=O; each Q is independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; a and b are each independently 0 to about 1000; x and y are each independently 1 to about 1000; wherein the blocks a, b, x and y are in any order, the ratio of x:a is from 1:0 to about 1:3, and the ratio of y:b is from 1:0 to about 1:3.

[0049] In various embodiments, the nitrogen heterocycle is a triazole or heterocycle disclosed above. In various additional embodiments, the pigment is an acid dye, a basic dye, an azo dye, an acridine dye, a rylene dye, a sulfur dye, a pH indicator, a food dye, an optical brightener, an anthraquinone dye, an arylmethane dye, a triarylmethane dye, a phthalocyanine dye, a quinoneimine dye, an azine dye, an indophenol dye, an oxazine dye, an oxazone dye, a thiazine dye, a thiazole dye, a safranine dye, a xanthene dye, a perylene diimide dye, a rhodamine dye, or a combination thereof. In some embodiments, the pigment or dye is, but is not limited to, an acridine, a bromothymol, a carmine, an eosin Y, a guaiazulene, a perylene, or a combination thereof.

[0050] In other embodiments, a and b are each independently 1 to 300, 5 to 50, 50 to 100, 100 to 150, 150 to 200, 200 to 250, 250 to 300, 300 to 400, 400 to 500, 500 to 600, 600 to 700, 700 to 800, 800 to 900, 900 to 1000, or 1000 to 2000. In other embodiments, x and y are each independently 1 to 300, 5 to 50, 50 to 100, 100 to 150, 150 to 200, 200 to 250, 250 to 300, 300 to 400, 400 to 500, 500 to 600, 600 to 700, 700 to 800, 800 to 900, 900 to 1000, or 1000 to 2000. In further embodiments, the ratio of x:a is about 1:0.5 to about 1:1, 1:1.5, 1:2, or 1:2.5. In yet other embodiments, the ratio of y:b is about 1:0.5 to about 1:1, 1:1.5, 1:2, or 1:2.5.

[0051] In further embodiments, the composition reflects blue, green, orange, red, or near infrared wavelengths. In various embodiments, the BBCP has a number average molecular weight of about 500 kDa to about 4000 kDa.

[0052] In some embodiments, the composition comprises M n = 1110.3 kDa, M W = 1196.1 kDa, D = 1.08, and a = x = y = b = about 164. In some embodiments, preferably a = x = y = b = 140 to 180. In other embodiments, more preferably a = x = y = b = 150 to 170.

[0053] In some embodiments, the composition comprises M n = 1275.7 kDa, M W = 1403.2 kDa, D = 1.10, and a = x = y = b = about 179, the green color of the composition comprising Formula I or II is characterized. In some embodiments, preferably, a = x = y = b = 160 to 190. In other embodiments, more preferably, a = x = y = b = 165 to 185.

[0054] In some embodiments, the composition comprises M n = 1795.3 kDa, M W = 2010.4 kDa, D = 1.12, and a = x = y = b = about 252. In some embodiments, preferably a = x = y = b = 230-270. In other embodiments, more preferably a = x = y = b = 240-260.

[0055] In some embodiments, the composition comprises M n = 2063.1 kDa, M W = 2384.8 kDa, D = 1.16, and a = x = y = b = about 289. In some embodiments, preferably a = x = y = b = 270-300. In other embodiments, more preferably a = x = y = b = 275-295.

[0056] In various other embodiments, the weight percentage of BBCP in the resulting coating is about 25% to about 99.9%, and the weight percentage of pigment or dye is about 0.1% to about 10%. In some embodiments, the weight percentage of BBCP is about 85%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%. In still other embodiments, the weight percentage of pigment or dye is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or 15%.

[0057] In further embodiments, the composition further comprises a metal oxide, a linear polymer additive, or a combination thereof. In some embodiments, the linear polymer additive is a linear poly(methacrylate), a linear polylactic acid, a linear polystyrene, or a combination thereof. In yet some other embodiments, the composition further comprises zirconium dioxide nanocrystals, titanium oxide nanocrystals, or hafnium oxide nanocrystals.

[0058] In a further embodiment, the BBCP of formula IA is a BBCP of formula IC or formula II, [ka] During the ceremony, R 3 and R 4 are each independently H or unbranched or branched -(C1-C6)alkyl; m and n each independently represent an integer of 1 to 100.

[0059] In other embodiments, m and n are each independently 1-10, 10-50, 10-20, 20-30, 30-40, 40-50, or 50-100.

[0060] In a further embodiment, the BBCP of formula I is a BBCP of formula III, [ka] During the ceremony, R 5 is H or unbranched or branched -(C1-C6)alkyl; q and t each independently represent an integer from 1 to 100.

[0061] In some embodiments, q and t are each independently 1-10, 10-50, 10-20, 20-30, 30-40, 40-50, or 50-100.

[0062] The present disclosure also provides a method of tailoring the electromagnetic radiation reflectance, absorbance and transmittance profile of a substrate, comprising coating the substrate with a film of a photonic crystal composition disclosed herein, wherein a pigment or dye in the photonic crystal composition tailors the reflectance, absorbance and transmittance profile of the substrate such that electromagnetic radiation reflected by the coated substrate is at least 5% greater than a corresponding uncoated substrate.

[0063] In some embodiments, electromagnetic radiation reflected by a coated substrate is about 5% to about 25%, about 25% to about 50%, about 50% to about 75%, or about 75% to about 95% more than a corresponding uncoated substrate.

[0064] In various embodiments, the film has an optical thickness f-ratio of about 0.25 to about 0.55, or an f-ratio of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9.

[0065] In some embodiments, the reflectance, absorbance and transmittance profile of the substrate includes reflected electromagnetic radiation with wavelengths from about 280 nanometers to about 400 nanometers. In other embodiments, the reflectance, absorbance and transmittance profile of the substrate includes reflected electromagnetic radiation with wavelengths from about 400 nanometers to about 700 nanometers. In yet other embodiments, the reflectance, absorbance and transmittance profile of the substrate includes reflected electromagnetic radiation with wavelengths from about 700 nanometers to about 1550 nanometers.

[0066] In further embodiments, the reflectance, absorbance and transmittance profile of the substrate comprises reflected electromagnetic radiation at wavelengths between about 200 nm and about 300 nm, between about 300 nm and about 400 nm, between about 400 nm and about 500 nm, between about 500 nm and about 600 nm, between about 600 nm and about 700 nm, between about 700 nm and about 800 nm, between about 800 nm and about 900 nm, between about 900 nm and about 1000 nm, between about 1000 nm and about 1100 nm, between about 1100 nm and about 1200 nm, between about 1200 nm and about 1300 nm, between about 1300 nm and about 1400 nm, or between about 1400 nm and about 1600 nm.

[0067] The present disclosure further provides a method for forming a photonic coating, comprising: a) combining a solvent, a pigment or dye, and a brush block copolymer (BBCP) to form a mixture, wherein the BBCP is of formula IA, IB, II or III, or IC as above; [ka] During the ceremony, R x is -(C2-C6)alkyl-OC(=O)G 1 where G 1 comprises polyacrylate, polymethacrylate or polylactic acid, R y is -(C1-C8)alkyl-G 2 -G 3 where G 2 is -C(=O)O- or a nitrogen heterocycle, and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R 1 is an unbranched alkyl; R 2 is a branched alkyl; a and b each independently represent 0 to 1000; x and y are each independently 1 to 1000; wherein the ratio of x:a is from 1:0 to about 1:3 and the ratio of y:b is from 1:0 to about 1:3; b) applying a layer of the mixture to a substrate; and c) drying the layer to form a film; The film provides a method for forming a photonic coating on a substrate.

[0068] In some embodiments, the solvent is 4-chlorobenzotrifluoride. In various embodiments, the method includes a BBCP of formula II or formula III above. In further embodiments, the pigment or dye is an acid dye, a basic dye, an azo dye, an acridine dye, a rylene dye, a sulfur dye, a pH indicator, a food dye, an optical brightener, an anthraquinone dye, an arylmethane dye, a triarylmethane dye, a phthalocyanine dye, a quinoneimine dye, an azine dye, an indophenol dye, an oxazine dye, an oxazone dye, a thiazine dye, a thiazole dye, a safranine dye, a xanthene dye, a perylene diimide dye, a rhodamine dye, or a combination thereof. In further embodiments, the pigment or dye is, but is not limited to, an acridine, a bromothymol, a carmine, an eosin Y, a guaiazulene, a perylene, or a combination thereof.

[0069] In further embodiments, the weight percentage of the pigment or dye is about 0.1% to about 3% of the mixture, or about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 4%, 5%, or 10% of the mixture. In other embodiments, the weight percentage of the BBCP is about 2.5% to about 50% of the mixture, or about 1%, 5%, 10%, 15%, 20%, 25%, 30%, or 40% of the mixture.

[0070] In various other embodiments of the compositions and methods, the BBCP has a number average molecular weight of about 500 kDa to about 4000 kDa, or about 900 kDa to about 1100 kDa. In other embodiments, the BBCP has a number average molecular weight of about 100 kDa, 200 kDa, 300 kDa, 400 kDa, 500 kDa, 600 kDa, 700 kDa, 800 kDa, 900 kDa, 1000 kDa, 1100 kDa, 1200 kDa, 1300 kDa, 1400 kDa, 1500 kDa, 1600 kDa, 170 kDa, 2 ...50 kDa, 260 kDa, 270 kDa, 280 kDa, 290 kDa, 300 kDa, 350 kDa, 360 kDa, 370 kDa, 380 kDa, 390 kDa, 400 kDa, 400 kDa, 400 kDa, 500 kDa, 600 kDa, 700 kDa, 800 k 0kDa, 1800kDa, 1900kDa, 2000kDa, 2100kDa, 2200kDa, 2300kDa, 2400kDa, 2500kDa, 2600kDa, 2700kDa, 2800kDa, 2900kDa, 3000kDa, 3500kDa, 4000kDa, 4500kDa or 5000kDa.

[0071] In yet another embodiment of the above method, step a) further comprises adding a metal oxide, a linear polymer additive, or a combination thereof to the mixture. In various embodiments, the linear polymer additive is a linear poly(methacrylate), a linear polylactic acid, a linear polystyrene, or a combination thereof. In a further embodiment of the above method, applying a layer of the mixture to the substrate includes, but is not limited to, spray deposition of the mixture onto the substrate, or other deposition methods disclosed herein, such as drawdown coating of the mixture onto the substrate, slot die coating, screen printing, spray deposition, or paint brush / roller.

[0072] Various aspects of the present disclosure include the following.

[0073] A photonic crystal material containing either inorganic or organic additives, comprising adding at least one inorganic or organic component to a polymer-based photonic crystal, or an organic additive that is composed of different monomer units compared to the composition of the polymer component.

[0074] Photonic crystals may be formed from linear block polymers, brush block polymers, star polymers, polymer colloidal crystal arrays, or any repeating dielectric structure.

[0075] The polymers can be assembled or fabricated into spheres, cylinders, gyroids, thin plates, or any periodic structure available through polymer self-assembly.

[0076] The polymer composite photonic crystal material, or the brush block copolymer alone, is deposited by drawdown, wire bar, doctor blade, or bird bar.

[0077] The polymer composite photonic crystal material, or the brush block copolymer alone, is deposited by paint brush or roller application.

[0078] The polymer composite photonic crystal material, or the brush block copolymer alone, is deposited by screen printing.

[0079] The polymer composite photonic crystal material, or the brush block copolymer alone, is deposited by dip coating.

[0080] The polymer composite photonic crystal material, or the brush block copolymer alone, is deposited by hydrographic printing.

[0081] The polymer composite photonic crystal material, or the brush block copolymer alone, is deposited by spray brush, spray gun, rotary bell atomizer, or other spray application methods including, but not limited to, air atomized, airless, electrostatic, high volume, low pressure.

[0082] Photonic crystal coatings have high near infrared reflectance and low visible reflectance.

[0083] Photonic crystal coatings have high visible reflectance and low ultraviolet reflectance.

[0084] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of alkaline (earth) metals.

[0085] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group IV metals such as titanium, zirconium, or hafnium, and / or their oxides, or combinations of any element with a Group IV metal and / or oxide.

[0086] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group V metals such as vanadium, niobium, and tantalum, and / or their oxides, or combinations of any element with Group V metals and / or oxides.

[0087] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group VI metals, such as chromium, molybdenum, and tungsten, and / or their oxides, or combinations of any element with Group VI metals and / or oxides.

[0088] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group VII metals, such as manganese, technetium, and rhenium, and / or their oxides, or combinations of any element with a Group VII metal and / or oxide.

[0089] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group VIII metals, such as iron, ruthenium, and osmium, and / or their oxides, or combinations of any of the elements with Group VIII metals and / or oxides.

[0090] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group IX metals such as cobalt, rhodium, and iridium, and / or their oxides, or combinations of any element with Group IX metals and / or oxides.

[0091] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group X metals, such as nickel, palladium, and platinum, and / or their oxides, or combinations of any element with the Group X metals and / or oxides.

[0092] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group XI metals such as copper, silver, gold, and / or their oxides, or combinations of any element with Group XI metals and / or oxides.

[0093] The inorganic components are nanoscale forms (generally including molecular complexes and particulates) of Group XII metals, such as zinc, cadmium, and mercury, and / or their oxides, or combinations of any of the elements with Group XII metals and / or oxides.

[0094] The inorganic component is functionalized with a surface ligand. If the inorganic component is functionalized with a surface ligand, the inorganic component can be functionalized with a surface polymer-based ligand.

[0095] The organic or inorganic additive component has a refractive index greater than or less than 0.05, which may be derived from the homopolymer that may be derived from the monomer units that make up the BCP.

[0096] The organic or inorganic additive components are used to change the f-value of the composition to 0.50±0.03.

[0097] The organic or inorganic additive components are used to change the f-value of the composition to 0.33±0.03.

[0098] The inorganic or organic additive is a dye.

[0099] The inorganic or organic additive is a pigment.

[0100] Inorganic or organic additives absorb ultraviolet A or B light (280-400 nm).

[0101] Inorganic or organic additives change the absorption or transmittance profile of the photonic crystal in the ultraviolet A or B light region (280-400 nm).

[0102] Inorganic or organic additives absorb visible light (400-700 nm).

[0103] Inorganic or organic additives change the absorption or transmittance profile of the photonic crystal in the visible light region (400 to 700 nm).

[0104] Inorganic or organic additives absorb in the near infrared, IR-A, light region (700-1400 nm).

[0105] Inorganic or organic additives change the absorption or transmittance profile of the photonic crystal in the near infrared, IR-A, and optical regions (700-1400 nm).

[0106] Results and Discussion The incorporation of inorganic materials at specific weight percentages has been found to have the effect of selectively decreasing the %R of the (even numbered) order reflections from polymer-based photonic crystals while maintaining or increasing the %R of the first and third order (odd numbered) reflections (Figure 1). As observed in Figure 1, by using inorganic additives, the second order %R is selectively decreased from 31%R at 519 nm, which is readily observed by the human eye as green, to 4.7%R at 525 nm, which is not readily observed by the human eye.

[0107] Incorporation of certain organic materials at specific weight percentages has been found to have the effect of increasing the long-range order of nanostructured materials, as evidenced by well-defined 1st, 2nd, 3rd... etc. reflections, and low %R outside of the main reflection peaks (Figure 2). As observed in Figure 2, by using organic material additives, high NIR reflectance (>60%), low Vis reflectance (<10%), and high Vis transmittance (>85%) can be achieved.

[0108] Both observations can be explained through a manipulation of the optical thickness called the “f ratio” (f), which can be defined by Equation 2 (Polymer Engineering and Science 1969, 9, 404): Formula 2:

number

[0109] Here, even order reflections (m=2,4,6...) are suppressed when the f-value is close to or equal to 0.5 (for equivalent optical thickness), and odd order reflections (m=1,3,5,7...) are suppressed when the f-value is close to or equal to 0.33. The %R can be tailored to target specific wavelength regions (UV, Vis, NIR) by adding organic or inorganic components compatible with the BCP. For visually transparent UV and / or NIR reflective coatings, the %R in the visible range can be suppressed.

[0110] Key advantages exist over the state of the art due to innovations in the polymer materials themselves, polymer composite mixtures, and the facile processes by which these materials self-assemble to form functional optical coatings deposited by a variety of methods, including paint brush, drawdown, wire bar, doctor blade, bird bar, roller application, screen printing, spray brush, or spray gun application (Figure 3).

[0111] Figure 1 compares the reflectivity of two PLA-b-PS photonic crystal films. The solid trace includes inorganic additives and the dashed trace includes no additives. Comparing the intensities of the different peaks (% reflectance), it can be seen that the relative intensities of the 1st, 2nd and 3rd order reflections change significantly when inorganic additives are included. Specifically, the inclusion of inorganic additives increases the 3rd order reflection relative to the 1st and decreases the 2nd order reflection relative to the 1st. This result is significant because the visible reflection is selectively suppressed while maintaining the UV and NIR reflections. Compared to the closest prior art, similar optical characteristics are achieved by multilayer coextrusion of different polymeric materials. In contrast to coextrusion, similar optical properties are now available by simple formulation and coating.

[0112] Figure 2 compares the reflectance of two PLA-b-PS photonic crystal films. The dashed trace contains a 34 wt% loading of PEHMA polymer additive, and the black trace contains a 10 wt% loading of PEHMA polymer additive. Note that if BBCP is removed from the composition, there is no reflection. Similar to Figure 1, Figure 2 shows the change in optical properties of a polymer composite photonic crystal film with the addition of additive. Specifically, by increasing the loading of PEHMA from 10 wt% to 34 wt%, the reflectance can be dramatically changed. Figure 2B shows the transmittance in addition to the reflectance.

[0113] Figure 3 shows the transmittance (dashed line) and reflectance (solid line) traces of the spray-deposited polymer composite PLA-b-PS photonic crystal film. This result is significant because it represents the first spray-deposited brush block copolymer photonic crystal film.

[0114] Additionally, the present disclosure relates to self-assembled polymer photonic crystal coatings composed of brush block copolymers (BBCPs), and the discovery that exogenously added pigments or dyes can be used to modify the optical properties of the resulting coatings.

[0115] The polymer-based 1D PCs disclosed herein were made from a model system using poly(styrene)-block-poly(isobutyl methacrylate) brush block copolymers (BBCPs). The BBCPs were synthesized by a graft-through approach via ring-opening metathesis polymerization from norbornene-based poly(styrene) and poly(isobutyl methacrylate) macromonomers. The BBCPs were completely dissolved in solution to a solid content of 25 wt %. No additives were included or 0.4 wt % pigment or dye was added based on the total solution mass (Figures 4-11). The formulation compositions are shown in Table 1. [Table 1]

[0116] Films were cast at a wet film thickness of 4.0 mils using a bird bar. Figure 4 shows the reflectance and transmittance of a PC film on a glass microscope slide substrate. In Figures 5-11, the film contains a dye or pigment and is contrasted with the control in Figure 4. In Figures 5-11, the dye or pigment changes the optical properties and therefore the appearance of the coating on the glass.

[0117] The following examples are intended to illustrate the above invention and should not be construed as narrowing its scope. Those skilled in the art will readily recognize that the examples suggest many other ways in which the invention can be practiced. It should be understood that many variations and modifications can be made while remaining within the scope of the invention.

[0118] example Example 1. Materials and Methods Polymer composite compositions were prepared from brush block copolymers, linear poly(lactic acid), linear poly(styrene), linear poly(2-ethylhexyl methacrylate), zirconium dioxide nanocrystals (average diameter 7 nm, from Pixelligent Technologies LLC), or combinations thereof. For linear polymer additives, see J. Am. Chem. Soc. 2014, 136, 17374. The disclosure of U.S. Patent Application Publication No. 2018 / 0258230 is incorporated herein by reference in its entirety.

[0119] Polymer films were deposited on glass microscope slides and reflectance and transmittance spectra were recorded on a Cary 5000 UV-Vis-NIR spectrophotometer equipped with a diffuse reflectance accessory. Linear poly(lactic acid): [ka]

[0120] To a 200 mL Schlenk flask equipped with a stir bar that had been degassed, filled with nitrogen, and flame dried three times, freshly sublimed lactide (51.8 g) and tin(II) 2-ethylhexanoate were added, and finally anhydrous hexanol (1.948 mL) was injected. The reaction was heated to 135°C. As the reaction proceeded, lactide sublimed onto the side walls of the flask, which was melted back into solution with a heat gun to ensure quantitative consumption of the monomer. After 3.5 h, the reaction was diluted with dichloromethane (DCM), filtered through a plug of Celite, and precipitated into methanol. Yield: 75%, M n =3,050Da, PDI=1.07. Linear poly(styrene): [ka]

[0121] To a 1 L Schlenk flask equipped with a stir bar that had been degassed, filled with nitrogen, and flame dried three times, was added dry and degassed toluene (700 mL). The reaction flask was placed in an ice bath and 1.4 M sec-butyllithium in cyclohexane (25 mL, 2.24 g, 0.035 mol, 1 equiv.) was added to the stirring toluene. After stirring the solution for 20 min, freshly dried and distilled styrene over CaH2 (120 mL, 109 g, 1.05 mol, 29.9 equiv.) was added in a fairly rapid manner via a 60 mL syringe. No significant exotherm was observed and the solution quickly changed from clear to orange / red. After 2 h, the reaction was quenched by injection of approximately 50 mL of methanol.

[0122] Workup: The solution was concentrated on a rotary evaporator to remove residual toluene, methanol, cyclohexane and propylene oxide. The polymer was dissolved in THF and precipitated into a stirring methanol solution at room temperature. Yield: 98%, M n = 3,100 Da, PDI = 1.05 Linear poly(2-ethylhexyl methacrylate): [ka]

[0123] To a 100 mL Schlenk flask equipped with a stir bar that had been degassed, filled with nitrogen, and flame dried three times, DCM solvent, 2-ethylhexyl methacrylate monomer, and methyl trimethylsilyl dimethyl ketene acetal were added. The TMS-triflimide catalyst was added to initiate the polymerization. The polymerization was allowed to proceed at room temperature for 3 h. 1 Quenching was performed when >99% conversion was confirmed by H NMR. After quenching with acidified methanol, the solution was filtered through an alumina plug to remove residual catalyst and decomposed catalyst products and concentrated under reduced pressure. Yield: 89%, M n =3,100Da, PDI=1.11.

[0124] Example 2. Synthesis of polystyrene macromonomer [ka]

[0125] Alcohol-terminated polystyrene: To a 1 L Schlenk flask equipped with a stir bar that had been degassed, filled with nitrogen, and flame-dried three times, dry and degassed toluene (700 mL) was added. The reaction flask was placed in an ice bath and 1.4 M sec-butyllithium in cyclohexane (25 mL, 2.24 g, 0.035 mol, 1 equiv.) was added to the stirring toluene. After stirring the solution for 20 minutes, freshly dried and distilled styrene over CaH2 (120 mL, 109 g, 1.05 mol, 29.9 equiv.) was added in a fairly rapid manner via a 60 mL syringe. No significant exotherm was observed and the solution immediately changed from clear to orange / red. After 2 hours, propylene oxide (2.816 mL, 0.0403 mol, 1.15 equiv.) was added to terminate the polystyrene chains and provide the appropriate functionality. The reaction was stirred overnight and then quenched by injecting approximately 50 mL of methanol. Work-up: The solution was concentrated on a rotary evaporator to remove residual toluene, methanol, cyclohexane and propylene oxide. The polymer was dissolved in THF and precipitated into a stirring methanol solution at room temperature. 98% recovery, M n = 3,153 Da, PDI = 1.05. [ka]

[0126] Coupling of polystyrene alcohol with norbornene carboxylic acid: To a 1 L Schlenk flask equipped with a stir bar that had been degassed, filled with nitrogen, and flame dried three times, propylene oxide terminated polystyrene (60.0 g, 0.019 mmol, 1 equiv.), norbornene carboxylic acid A (6.24, 0.228 mmol, 1.2 equiv.), and DMAP (2.32 g, 0.190 mmol, 1.0 equiv.) were added. The mixture was dissolved in approximately 650 mL of dry DCM and stirred on an ice bath for 30 min. DCC (7.87 g, 0.038 mmol, 2.0 equiv.) was then added to the solution over 10 min under a positive nitrogen stream. The reaction was allowed to react overnight.

[0127] Workup: After 24 hours, the solution was re-cooled to 0° C. and filtered through a medium frit to remove dicyclohexylurea. The filtered solution was then cooled once more to −20° C. and the remaining dicyclohexylurea precipitate was filtered a second time. Once filtered, the solution was concentrated on a rotary evaporator, then dissolved in THF and precipitated five times at room temperature into a stirred methanol solution. Yield=75%.

[0128] Example 3. Synthesis of isobutyl methacrylate macromonomer [ka]

[0129] Synthesis of N-(ethyl methacrylate)-cis-5-norbornene-exo-2,3-dicarboximide: To a flame-dried, nitrogen-filled 1 L Schlenk flask was added N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide (83.4 g, 403 mmol, 1.0 equiv), 4-(dimethylamino)pyridine (29.5 g, 241 mmol, 0.6 equiv), methacrylic acid (44.0 mL, 519 mmol, 1.3 equiv), and 650 mL of anhydrous DCM. The heterogeneous solution was allowed to mix on an ice bath for 20 min, then 1-ethyl-3-(d-dimethylaminopropyl)carbodiimide (93.8 g, 604 mmol, 1.5 equiv) was added slowly under positive nitrogen. The reaction was allowed to proceed for 2 days after which the organic layer was washed with 0.5M HCl, saturated NaHCO3 solution, water, brine, dried over MgSO4, and then passed through 200 g of alumina to remove additional methacrylic acid. The organic layer was then concentrated in the dark to give a white solid (46 g, 42% yield) as the product is light sensitive in solution. [ka]

[0130] Group Transfer Polymerization: A 250 mL Erlenmeyer flask equipped with a 24 / 40 adapter and stir bar was oven dried and placed in a hot glove box. Inside the glove box, 75 mL of anhydrous DCM from the solvent system was added. To this was added degassed dimethylphenylsilane (573 μL, 3.74 mmol, 1.03 equiv), followed by the addition of once sublimed tris(pentafluorophenyl)borane (18.6 mg, 0.0363 mmol, 0.01 equiv). This solution was stirred for 1 min, after which a solution of N-(ethyl methacrylate)-cis-5-norbornene-exo-2,3-dicarboximide (1.00 g, 3.36 mmol, 1.0 equiv) in 10 mL of DCM (0.5 M) was added dropwise over 5 min (>100 drops total). The solution was stirred for an additional 15 min, whereupon CaH2-dried, distilled butyl methacrylate (10.49 mL, 0.0653 mmol, 18 equiv.) was injected into the stirred solution. Finally, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (51 μL, 0.1456 mmol, 0.04 equiv.) was added. n = 2,940 Da, PDI = 1.07.

[0131] Example 4. Synthesis of brush block copolymer (BBCP) [ka]

[0132] BBCP1: To a vial containing isobutyl methacrylate macromonomer (200 equiv.) and a stir bar, CHCl was added to give a 0.05 M solution. Polymerization was initiated by the addition of Grubbs 3rd generation catalyst (1.0 equiv.). After stirring for 1 h at room temperature, a solution of CHCl and pyridine (1.0 mM, 5.0 equiv.) was added. In a separate vial, a solution of the second block was prepared by adding styrene macromonomer (200 equiv.) to CHCl (0.05 M). Using a plastic syringe, the second block was introduced in one shot into the first block reaction mixture. The resulting mixture was stirred at room temperature for an additional 5 h. The reaction was quenched by the addition of an excess of ethyl vinyl ether, and the block copolymer was isolated by precipitation into methanol at -78 °C. [ka]

[0133] BBCP2 (see J. Am. Chem. Soc. 2017, 139, 17683): ​​PLA-MM (1173 mg, 0.325 mmol, M n To a 30 mL amber vial containing a 1000 MPa (0.025 Da) polymerized with d,x-DME (68.32 mg, 0.325 mmol, 0.05 M in 6.5 mL) was added a solution of d,x-DME in CH2Cl2 (68.32 mg, 0.325 mmol, 0.05 M in 6.5 mL). 170 -r-DME 170 The reaction was started by the addition of Grubbs' third generation catalyst ((H2IMes)-(pyr)2(Cl)2RuCHPh, 1.91 μmol) targeting the 3-amino-3-propanediol (Amd)-2-propanediol (Pd)-2-methyl ... nThe second block was prepared by dissolving d,x-DiPE (molecular mass % = 3500 Da) in a solution of d,x-DiPE (86.56 mg, 0.325 mmol, 0.05 M in 6.5 mL) in CH2Cl2. The second block was then introduced in one shot into the first block reaction mixture using a 12 mL plastic syringe. The resulting mixture was stirred at room temperature for an additional 12 h. The reaction was quenched by adding 0.5 mL of ethyl vinyl ether, and the block copolymer was isolated by precipitation into methanol at -78 °C. M n = 1,020,000 Da, PDI = 1.09. Yield: 92%.

[0134] Although particular embodiments have been described above with reference to disclosed embodiments and examples, such embodiments are merely illustrative and do not limit the scope of the present invention. Changes and modifications may be made by those skilled in the art without departing from the invention in its broader aspects, as defined in the following claims.

[0135] All publications, patents, and patent documents are incorporated herein by reference as if individually incorporated by reference. No limitations that conflict with the present disclosure should be recognized therefrom. The present invention has been described with reference to various specific preferred embodiments and techniques. However, it should be understood that many changes and modifications can be made while remaining within the spirit and scope of the invention.

Claims

1. 1. A photonic crystal composition comprising a pigment and a brush block copolymer (BBCP) of formula IA or formula IB, 【Chemistry 1】 During the ceremony, R ｘ is -(C ２ -C ６ ) alkyl-OC(=O)G １ where G １ comprises polyacrylate, polymethacrylate or polylactic acid, R ｙ is -(C １ -C ８ ) Alkyl-G ２ -G ３ where G ２ is -C(=O)O- or a nitrogen heterocycle; G ３ comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R １ is an unbranched alkyl; R ２ is a branched alkyl; J １ and G each independently represent CH ２ or C=O, Each J ２ is independently CH ２ or C=O, each Q is independently alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; a and b are each independently 0 to about 1000; x and y are each independently from 1 to about 1000; A photonic crystal composition wherein the blocks a, b, x and y are in any order, the ratio of x:a is from 1:0 to about 1:3, and the ratio of y:b is from 1:0 to about 1:

3.

2. 2. The composition of claim 1, wherein the pigment is an acid dye, a basic dye, an azo dye, an acridine dye, a rylene dye, a sulfur dye, a pH indicator, a food dye, an optical brightener, an anthraquinone dye, an arylmethane dye, a triarylmethane dye, a phthalocyanine dye, a quinoneimine dye, an azine dye, an indophenol dye, an oxazine dye, an oxazone dye, a thiazine dye, a thiazole dye, a safranine dye, a xanthene dye, a perylene diimide dye, a rhodamine dye, or a combination thereof.

3. 2. The composition of claim 1, wherein the pigment is acridine, bromothymol, carmine, eosin Y, guaiazulene, perylene, or a combination thereof.

4. 2. The composition of claim 1, wherein a and b are each independently from 1 to about 300; or x and y are each independently from 1 to about 300.

5. 2. The composition of claim 1, wherein the ratio of x:a is from about 1:0.5 to about 1:

1.

6. 2. The composition of claim 1, wherein the ratio of y:b is from about 1:0.5 to about 1:

1.

7. The composition of claim 1, wherein the weight percentage of BBCP is from about 25% to about 99.9% and the weight percentage of said pigment is from about 0.1% to about 10%.

8. The composition of claim 1 further comprising a metal oxide, a linear polymer additive, or a combination thereof.

9. The composition of claim 1 further comprising zirconium dioxide nanocrystals.

10. The BBCP of formula IA is a BBCP of formula IC or formula II, 【Chemistry 2】 During the ceremony, R ３ and R ４ are each independently H or unbranched or branched -(C １ -C ６ ) alkyl; 2. The composition of claim 1, wherein m and n are each independently from 1 to about 100.

11. The composition of claim 10, wherein m and n are each independently from 10 to about 50.

12. said BBCP of formula IA is a BBCP of formula III 【Chemistry 3】 During the ceremony, R ５ is H or unbranched or branched -(C １ -C ６ ) alkyl; The composition of claim 1, wherein q and t are each independently from 1 to about 100.

13. 11. A method for tailoring the electromagnetic radiation reflectance, absorbance and transmittance profile of a substrate, comprising coating a substrate with a film of the photonic crystal composition of claim 1, wherein pigments in the photonic crystal composition tailor the reflectance, absorbance and transmittance profile of the substrate such that electromagnetic radiation reflected by the coated substrate is at least 5% greater than a corresponding uncoated substrate.

14. The method of claim 13, wherein the film has an optical thickness f ratio of about 0.25 to about 0.

55.

15. the reflectance, absorbance and transmittance profile of the substrate comprises reflected electromagnetic radiation at wavelengths between about 280 nanometers and about 400 nanometers; or the reflectance, absorbance and transmittance profile of the substrate comprises reflected electromagnetic radiation at wavelengths between about 400 nanometers and about 700 nanometers; or The method of claim 13, wherein the reflectance, absorbance, and transmittance profile of the substrate comprises reflected electromagnetic radiation at wavelengths from about 700 nanometers to about 1600 nanometers.

16. 1. A method for forming a photonic coating, comprising: a) combining a solvent, a pigment, and a brush block copolymer (BBCP) to form a mixture, wherein the BBCP is a BBCP of formula IC; 【Chemistry 4】 During the ceremony, R ｘ is -(C ２ -C ６ ) alkyl-OC(=O)G １ where G １ comprises polyacrylate, polymethacrylate or polylactic acid, R ｙ is -(C １ -C ８ ) Alkyl-G ２ -G ３ Here, G ２ is -C(=O)O- or a nitrogen heterocycle; G ３ comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R １ is an unbranched alkyl; R ２ is a branched alkyl; a and b are each independently 0 to about 1000; x and y are each independently from 1 to about 1000; wherein the ratio of x:a is from 1:0 to about 1:3 and the ratio of y:b is from 1:0 to about 1:

3. b) applying a layer of the mixture to a substrate; and c) drying the layer to form a film; The method wherein the film forms the photonic coating on the substrate.

17. 17. The method of claim 16, wherein the pigment is an acid dye, a basic dye, an azo dye, an acridine dye, a rylene dye, a sulfur dye, a pH indicator, a food dye, an optical brightener, an anthraquinone dye, an arylmethane dye, a triarylmethane dye, a phthalocyanine dye, a quinoneimine dye, an azine dye, an indophenol dye, an oxazine dye, an oxazone dye, a thiazine dye, a thiazole dye, a safranine dye, a xanthene dye, a perylene diimide dye, a rhodamine dye, or a combination thereof.

18. The method of claim 16, wherein the mixture comprises from about 0.1% to about 3% by weight of the pigment.

19. 17. The method of claim 16, wherein the weight percentage of BBCP in the mixture is from about 2.5% to about 50%.

20. 17. The method of claim 16, wherein the BBCP has a number average molecular weight of about 500 kDa to about 4000 kDa.

21. 17. The method of claim 16, wherein step a) further comprises adding a metal oxide, a linear polymer additive, or a combination thereof to the mixture.

22. 17. The method of claim 16, wherein applying a layer of the mixture to a substrate comprises spray depositing, drawdown coating, slot die coating, screen printing, spray depositing, or paint brush / roller of the mixture onto the substrate.

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