Polymer composite photonic crystal coating

Abstract

Polymer composite photonic crystal materials are disclosed as coatings that have high reflectivity (>30%) in a specific region of the electromagnetic spectrum, such as the ultraviolet (<400 nm), visible (Vis, 400 nm-700 nm), or near-infrared radiation region (NIR, 700-2000 nm), and relatively low reflectivity (<20% reflectivity) in a second, different region of the electromagnetic spectrum. Surprisingly, we have discovered that through formulation and additive approaches, the optical properties of polymer composite photonic crystal films can be selectively modified through a variety of different coating methods, including spray deposition.

Description

Technical Field

[0001] Related Applications This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application 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 hereby incorporated by reference in its entirety.

[0002] Government Support This invention was made with government support under grant numbers DE-AR0000881 and DE-AE0001261 awarded by the U.S. Department of Energy. The government has certain rights in the invention.

Background Art

[0003] There are challenges in the manufacture of nanostructured materials that can selectively reflect or transmit specific ranges of the electromagnetic spectrum without significantly altering the reflection or transmission of other ranges. For example, materials are needed that highly reflect while not significantly absorbing near-infrared (NIR, 700 - 2000 nm), while enabling high transmittance (>60%) of visible light (Vis, 400 - 700 nm) and / or ultraviolet (UV, <400 nm) radiation (J. Am. Chem. Soc. 2014, 136, 17374). Specifically, easy manufacturing procedures for accessing these materials have not yet been realized. Conventional manufacturing involves the extrusion of multilayer films (Polymer Engineering and Science, 1969, 9, 393), and current state-of-the-art technologies require intensive manufacturing processes such as lithography and alternating layer assemblies. Bottom-up processes such as block polymer self-assembly enable access to nanostructured materials from paintbrushes, drawdowns, wirebars, doctor blades, bird bars, roller coatings, screen printing, spray brushes, or spray gun coatings without the need for energy-intensive manufacturing and / or designer materials such as noble metal oxides as the main component. The ability to apply selective reflective coatings by easy coating methods opens up exciting possibilities for coating rough and curved surfaces where film and other top-down manufacturing processes cannot be used.

[0004] The current state-of-the-art technologies are represented by multilayer extruded thin films (U.S. Pat. Nos. 6,208,466 and 6,696,142) or alternating 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 investment in advanced manufacturing equipment / infrastructure and technology in addition to potentially high material costs. The reflective properties inherent in the disclosed materials are established via a bottom-up process through the self-assembly of BCPs that occurs rapidly under readily accessible conditions, i.e., ambient temperature or slightly elevated temperature, atmospheric pressure, and the presence of oxygen. The self-assembly process does not require special manufacturing techniques such as nanoimprinting or electron beam lithography, and alternating layer-by-layer deposition. The polymer components, polymer additives, and non-polymer additives used in the coating are inexpensive and can be “commodity” materials in preferred embodiments, maintaining low material costs.

[0005] Current approaches for the preparation of reflective materials require significant investment in advanced manufacturing equipment and technology, as well as high material costs. Accordingly, alternative compositions are needed that enable the preparation of more cost-effective reflective materials. SUMMARY OF THE INVENTION

[0006] The present disclosure relates to the discovery that the use of a brush block copolymer (BBCP) and an inorganic / organic composite material composed of either an inorganic additive system group, an organic additive system group, or some combination of the two can modify the optical characteristics of a photonic crystal material, e.g., but not limited to, reflectance (%R), wavelength (nm) of maximum reflection (λ max ), and full width at half maximum (FWHM) of the reflection peak, and haze (% haze) of the overall material. Here, the optical characteristics can be adjusted for primary and all higher-order reflections, and the relationship is given by the Bragg equation: λm = 2(n 1 d 1 +n 2 d 2) is derived from. Specifically, BBCP composed of various monomer units is blended with either inorganic particles or organic polymer additives to adjust the relative intensity of the higher-order reflection peak, resulting in high NIR reflection and low Vis reflection. The use of exogenous additives to directly adjust the relative intensity of the higher-order reflection peak of BBCP-derived photonic crystal materials is unique and enables the development of these materials for applications requiring selective NIR reflection and Vis transmission.

[0007] Accordingly, the present disclosure provides a photonic crystal composition comprising a pigment and a brush block copolymer (BBCP) of Formula IA or Formula IB.

Chemical formula

[0008] The present disclosure also provides a method of adjusting the electromagnetic radiation reflectance, absorbance and transmittance profiles of a substrate, comprising coating the substrate with a film of the above-described photonic crystal composition, wherein the pigments in the photonic crystal composition adjust the reflectance, absorbance and transmittance profiles of the substrate, and the electromagnetic radiation reflected by the coated substrate is increased by at least 5% compared to the corresponding uncoated substrate.

[0009] Furthermore, the present disclosure provides a method for forming a photonic coating, a) combining a solvent, a pigment, and a brush block copolymer (BBCP) to form a mixture, wherein the BBCP is a BBCP of the above formula IA or formula IB, or formula IC,

Chemical formula

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

[0011] The following drawings form a 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 may be best understood by referring to the accompanying drawings in combination with the detailed description presented herein. The description and the accompanying drawings may highlight certain specific examples or aspects of the present invention. However, one of ordinary skill in the art will understand that some examples or aspects may be used in combination with other examples or aspects of the present invention.

Brief Description of the Drawings

[0012]

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Mode for Carrying Out the Invention

[0013] This application relates to the use of an inorganic / organic composite material composed of a block copolymer (BCP) and either an inorganic additive system group, an organic additive system group, or some combination of the two to modify the optical characteristics of a photonic crystal material, such as, but not limited to, reflectance (%R), the wavelength (nm) of the maximum reflection (λ max ), the full width at half maximum (FWHM) of the reflection peak, and the haze (% haze) of the resulting photonic crystal material. Here, the optical characteristics are adjusted with respect to primary and all higher-order reflections, and the relationship is derived from Equation 1 (Polymer Engineering and Science 1973, 13, 216). Equation 1: λm = 2(n 1 d 1 + n 2 d 2 ) Where m = order of reflection, n = refractive index, and d = domain size.

[0014] Specifically, a BCP composed of various monomer units is blended with either an inorganic additive, a small molecule organic additive, and / or a polymer additive to adjust the relative intensity of the higher-order reflection peaks, which in some cases results in high NIR reflection and low vis reflection. The use of exogenous additives to directly adjust the relative intensity of the higher-order reflection peaks of BCP-derived photonic crystal materials is unique in that approach and enables the development of these materials for applications that require selective reflection and transmission in different ranges of the electromagnetic spectrum.

[0015] Definitions For the specification and claims to be clearly and consistently understood, 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 would be understood by one of ordinary skill in the art. Such ordinary meanings can be obtained by reference to technical dictionaries such as Hawley’s Condensed Chemical Dictionary 14 th Edition New York, N.Y., 2001, etc.

[0016] References herein to "one embodiment", "an embodiment", etc. indicate that the described embodiment may include a particular aspect, trait, structure, part, or feature, but not all embodiments necessarily include that aspect, trait, structure, part, or feature. Further, such phrases may or may not, but may in some cases, refer to the same embodiment mentioned elsewhere in this specification. Further, when a particular aspect, trait, structure, part, or feature is described in relation to an embodiment, it is within the knowledge of one of ordinary skill in the art, with or without explicit description, that such aspect, trait, structure, part, or feature may affect or be related to other embodiments.

[0017] The singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "a compound" includes a plurality of such compounds, and as a result, "a compound X" includes a plurality of compound Xs. It should further be noted that the claims may be drafted to exclude any optional elements. Thus, this description is intended to function as a basis for the use of exclusive terms such as "solely", "only", etc., or the use of "negative" limitations in connection with the recitation of any elements described herein and / or elements of the claims.

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

[0019] As will be understood by those skilled in the art, all numbers, including those representing amounts of ingredients, properties (such as molecular weight), reaction conditions, etc., are approximate and are understood to be optionally modified in all instances by the term "about". These values can vary depending on the desired properties required to be obtained by those skilled in the art using the teachings of the description herein. It is also understood that such values inherently include variability that necessarily results from the standard deviations found in each of the test measurements. When a value is represented as an approximation by use of the preposition "about", it will be understood that the specific value without the modifier "about" also forms a further aspect.

[0020] The terms "about" and "approximately" are used interchangeably. Either term can refer to a variation of ±5%, ±10%, ±20%, or ±25% of the specified value. For example, "about 50" percent can, in some embodiments, be 45 to 55 percent, or can vary as otherwise defined by a particular claim. In the case of a range of integers, the term "about" can include one or two integers greater than and / or less than the integers recited at each end of the range. Unless otherwise indicated herein, the terms "about" and "approximately" are intended to include values close to the recited ranges that are equivalent in function to the individual components, compositions, or embodiments, for example, weight percentages. 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 from the perspective of providing a written description, all ranges described herein include any possible sub-ranges and combinations of such sub-ranges, as well as the individual values that make up the range, particularly integer values. Thus, it is understood that each individual number between two specific individual numbers is also disclosed. For example, if 10 - 15 is shown, 11, 12, 13, and 14 are also individually disclosed as part of the range. The recited ranges (e.g., weight percentages or carbon groups) include each specific value, integer, fraction, or the same value within the range. Each of the recited ranges can be readily recognized as fully describing and validating the same range that is divided into at least equal halves, thirds, fourths, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily decomposed into, for example, the lower third, middle third, and upper third. Also, as will be understood by those skilled in the art, all language such as "maximum", "at least", "greater than", "less than", "more than", "above", etc. includes the recited number, and such terms refer to ranges that can be later decomposed into sub-ranges as described above. Similarly, all partial ratios included within a broader ratio are included in all ratios described herein. Thus, the specific values recited for radicals, substituents, and ranges are for illustrative purposes only, and they do not exclude other defined values of the radicals and substituents or other values within the defined range. Further, it will be understood that the endpoints of each range are important both in relation to the other endpoint and independently of the other endpoint.

[0022] This disclosure provides ranges, limits, and deviations for variables such as volume, mass, percentage, ratio, etc. Ranges such as "number 1" to "number 2" are understood by those skilled in the art to mean a continuous range of numerical values including integers and decimals. For example, 1 to 10 means 1, 2, 3, 4, 5, … 9, 10. Further, it means 1.0, 1.1, 1.2, 1.3, …, 9.8, 9.9, 10.0, and also means 1.01, 1.02, 1.03, etc. When the disclosed variable is a numerical value less than "number 10", as described above, this means a continuous range including integers and decimals less than number 10. Similarly, when the disclosed variable is a numerical value greater than "number 10", this means a continuous range including integers and decimals greater than 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 way such as a Markush group, the present invention encompasses not only the entire listed group as a whole, but also each individual member of the group and all possible subgroups of the main group. Further, for all purposes, the present invention encompasses not only the main group, but also main groups in which one or more group members are absent. Thus, the present invention is contemplated to explicitly exclude any one or more of the members of the listed group. Accordingly, the proviso applies to any of the disclosed categories or embodiments, whereby any one or more of the listed elements, species, or embodiments can be excluded from such category or embodiment, for example, for use in an explicit negative limitation.

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

[0025] "Effective amount" refers to an amount effective to bring about the recited effect, e.g., the amount necessary to form a product in a reaction mixture. Determination of an effective amount is generally within the ability of one of ordinary skill in the art, especially in light of the detailed disclosure provided herein. The term "effective amount" is intended to include, for example, the amount of a compound or reagent described herein that is effective to form a product in a reaction mixture, or the amount of a combination of compounds or reagents described herein. Thus, "effective amount" generally means an amount that provides the desired effect.

[0026] As used herein, the term "substantially" is a broad term and is used in its ordinary sense and includes, without limitation, that which is not necessarily complete but is nearly so as specified. For example, the term can refer to a numerical value that may not be 100% complete. The complete numerical value can be less by 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 methods for making the compounds and compositions of the 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 detailed in standard organic chemistry reference texts such as 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; as well as March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th Ed. (John Wiley & Sons, New York, 2001) by M. B. Smith and J. March; Comprehensive Organic Synthesis. Selectivity, Strategy & Efficiency in Modern Organic Chemistry. In 9 Volumes, edited by Barry M. Trost (Pergamon Press, New York, 1993); Advanced Organic Chemistry, Part B: Reactions and Synthesis, Second Edition, Cary and Sundberg (1983); etc.

[0028] The formulas and compounds described herein can be modified using protecting groups. Suitable amino and carboxy protecting groups are known to those skilled in the art (e.g., Protecting Groups in Organic Synthesis, Second Edition, Greene, T.W., and Wutz, P.G.M., John Wiley & Sons, New York, and the references cited therein; Philip J. Kocienski; Protecting Groups (Georg Thieme Verlag Stuttgart, New York, 1994) and the references cited therein); and see Comprehensive Organic Transformations, Larock, R.C., Second Edition, John Wiley & Sons, New York (1999), and the references cited therein).

[0029] As used herein, the term "substituted" or "substituent" is intended to indicate that one or more (e.g., in various embodiments, 1 to 20, in other embodiments, 1 to 10, 1, 2, 3, 4 or 5, in some embodiments, 1, 2, or 3, in other embodiments, 1 or 2) hydrogens on a group represented by an expression using "substituted" (or "substituent") are selected from the groups shown or replaced with suitable groups known to those skilled in the art, provided that the substitution does not exceed the normal valence of the indicated atom and 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. Further, non-limiting examples of substituents that can be attached to a substituted carbon (or other) atom include F, Cl, Br, I, OR’, OC(O)N(R’) 2 , CN, CF 3 , OCF 3 , R’, O, S, C(O), S(O), methylenedioxy, ethylenedioxy, N(R’) 2 , SR’, SOR’, SO 2 R’, SO 2 N(R’) 2 , SO 3 , R’, C(O)R’, C(O)C(O)R’, C(O)CH 2 C(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 , (CH 2 ) 0-2 NHC(O)R’, N(R’)N(R’)C(O)R’, N(R’)N(R’)C(O)OR’, N(R’)N(R’)CON(R’) 2 , N(R’)SO 2R’, N(R’)SO 2 N(R’) 2 , N(R’)C(O)OR’, N(R’)C(O)R’, N(R’)C(S)R’, N(R’)C(O)N(R’) 2 , N(R’)C(S)N(R’) 2 , N(COR’)COR’, N(OR’)R’, C(=NH)N(R’) 2 , C(O)N(OR’)R’, or C(=NOR’)R’, wherein R’ may be hydrogen or a carbon-based moiety, and the carbon-based moiety itself may 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, from 1 to 20 carbon atoms, often from 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms, or, for example, a range of carbon atoms in the range of 1 to 20, such as 2 to 6, 3 to 6, 2 to 8 or 3 to 8 carbon atoms. As used herein, the term "alkyl" also includes "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, etc. Alkyl may be unsubstituted or substituted, for example, with substituents described below. Alkyl may optionally be partially or fully unsaturated. Thus, the listing of alkyl groups can include both alkenyl and alkynyl groups. Alkyl may be a monovalent hydrocarbon radical as described and exemplified above, or a divalent hydrocarbon radical (i.e., alkylene).

[0032] The term "cycloalkyl" refers to a cyclic alkyl group having a single cyclic ring or multiple fused rings, for example, a cyclic alkyl group of 3 to 10 carbon atoms. Examples of cycloalkyl groups include monocyclic structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, etc., or polycyclic structures such as adamantyl. Cycloalkyl may be unsubstituted or substituted. The cycloalkyl group may be monovalent or divalent and may optionally be substituted as described for alkyl groups. The cycloalkyl group can optionally contain one or more sites of unsaturation. For example, the cycloalkyl group can contain one or more carbon-carbon double bonds, such as 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, etc.

[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 at least one heteroatom selected from 1 to 3 heteroatoms in at least one ring. Each ring is preferably 3 to 10 membered, more preferably 4 to 7 membered. 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 can be a terminal group or a bridging group.

[0034] The term "aryl" refers to an aromatic hydrocarbon group derived from the removal of at least one hydrogen atom from a single carbon atom of a parent aromatic ring system. The radical bonding site can be at a saturated or unsaturated carbon atom of the parent ring system. An aryl group can have from 6 to 30 carbon atoms, for example from about 6 to 10 carbon atoms. In other embodiments, an aryl group can have from 6 to 60 carbon atoms, from 6 to 120 carbon atoms, or from 6 to 240 carbon atoms. An aryl group can have a monocyclic (e.g., phenyl) or multiple fused (condensed) rings, with at least one ring being 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. 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 having at least one nitrogen, oxygen, or sulfur atom in the aromatic ring. Heteroaryl may be unsubstituted or may be substituted with one or more, particularly 1 to 3, substituents as described, for example, in the definition of "substituted". Typical heteroaryl groups contain 2 to 20 carbon atoms in the ring skeleton in addition to 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, imidazolinyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxazolyl, perimidyl, 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" means a monocyclic aromatic ring containing 5 or 6 ring atoms including carbon and 1, 2, 3, or 4 heteroatoms independently selected from non-peroxide oxygen, sulfur, and N(Z), where Z is absent or is H, O, alkyl, aryl, or (C 1 -C 6 )alkylaryl. In some embodiments, heteroaryl denotes an ortho-fused bicyclic heterocycle of about 8 to 10 ring atoms, particularly a benz derivative, or one derived by condensing a propylene, trimethylene, or tetramethylene diradical.

[0036] The "solvent" described in this specification can include water or an organic solvent. Examples of organic solvents include hydrocarbons such as toluene, xylene, hexane, and heptane; 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; aprotic polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and dimethyl sulfoxide (DMSO). Other examples of solvents include halogenated aromatic compounds or halogenated phenyl compounds, such as fluorinated or polyfluorinated phenyl compounds, such as 4-chlorobenzotrifluoride. The 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 those skilled in the art 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 up to 1 to 4, when the phenyl ring is disubstituted, for example. One or more subunits (i.e., repeating units or blocks) of a polymer can refer to about 5 to about 100,000, or any number of subunits.

[0038] The substituents of the compounds and polymers described herein may be present to a recursive extent. In this context, a "recursive substituent" means that the substituent can enumerate another example of itself. Due to the recursive nature of such substituents, theoretically, there could be a large number in any given claim. One of ordinary skill in organic chemistry understands 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 present invention. One of ordinary skill in organic chemistry understands the generality of such substituents. To the extent that recursive substituents are present in the claims of the present invention, the total number in the repeating units of the polymer examples can be, for example, about 1 to 50, about 1 to 40, about 1 to 30, about 1 to 20, about 1 to 10, or about 1 to 5.

[0039] As used herein, the terms "repeat unit", "repeating unit", or "block" refer to a repeating portion of a polymer. A repeat unit can include one or more repeat units labeled, for example, as repeat unit x, repeat unit y, repeat unit a, repeat unit b, etc. Repeat units x, y, a, and b can 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 can be bonded to form the (linked) repeat units of a polymer or copolymer.

[0040] As used herein, the term "molecular weight" of a copolymer refers to the number average molecular weight (Mn). The corresponding weight average molecular weight (Mw) can be determined from other disclosed parameters by methods known to those of skill 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" in the bonding between the repeating units of the copolymer. Thus, the arrangement of x units and x-a units is random throughout the length of the copolymer of Formula I, and the total number of x units and x-a units is defined by x and a of Formula I, which are randomly arranged along the length of the copolymer.

[0042] In various embodiments, the ends of the copolymer (i.e., the starting end or the ending end) are low molecular weight moieties (e.g., less than 500 Da), such as H, OH, OOH, CH 2 OH, CN, NH 2 , or hydrocarbons, such as alkyl (e.g., butyl or 2-cyanoprop-2-yl moieties at the starting and ending ends), alkene or alkyne, or moieties as a result of an elimination reaction at the first and / or last repeating units in the copolymer.

[0043] Self-organization is a process in which a disordered system of existing components forms an organized structure or pattern due to specific local interactions between the components themselves without external instructions. For the self-organization of molecules, first, the adsorbed molecules form a population of disordered molecules with a low molecular density on the surface or form an ordered two-dimensional "lying down phase", and over a period of minutes to hours, they begin to form a three-dimensional morphology on the substrate surface with a higher molecular coverage. The "head groups" aggregate on the substrate, while the tail groups aggregate away from the substrate. The regions of dense molecules serve as nuclei and grow until the surface of the substrate is covered with a single layer.

[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 graft chains. At this time, the limited space results in a strong elongation of the chains. Branching occurs by replacing a substituent on a monomer subunit, such as a hydrogen atom, with another covalent chain of the polymer or, in the case of a graft copolymer, 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 are organic compounds, organometallic compounds, or inorganic compounds.

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

[0047] The following abbreviations have their usual meanings to those skilled in the art. D = dispersity, kDa = kilodalton, M n = number average molecular weight, M W = weight average molecular weight.

[0048] Embodiments of the present invention The present disclosure provides a photonic crystal composition comprising a pigment or dye and a brush block copolymer (BBCP) of Formula IA or Formula IB.

Chemical formula

[0049] In various embodiments, the nitrogen heterocycle is the triazole or heterocycle disclosed above. In various additional embodiments, the pigment is an acid dye, basic dye, azo dye, acridine dye, perylene dye, sulfur dye, pH indicator, food dye, fluorescent brightener, anthraquinone dye, arylmethane dye, triarylmethane dye, phthalocyanine dye, quinoneimine dye, azine dye, indophenol dye, oxazine dye, oxazone dye, thiazine dye, thiazole dye, safranine dye, xanthene dye, perylenediimide dye, rhodamine dye, or combinations thereof. In some embodiments, the pigment or dye is, but not limited to, acridine, bromothymol, carmine, eosin Y, guaiacazulene, perylene, or combinations 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 still 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 reflects 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 is M n = 1110.3 kDa, MW Characterized by blue color in the composition comprising Formula I or II when M = 1196.1 kDa, D = 1.08, and a = x = y = b = approximately 164. In some embodiments, preferably, a = x = y = b = 140 - 180. In other embodiments, more preferably, a = x = y = b = 150 - 170.

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

[0054] In some embodiments, the composition is M n = 1795.3 kDa, M W = 2010.4 kDa, D = 1.12, and a = x = y = b = approximately 252, characterized by orange color in the composition comprising Formula I or II. 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 is M n = 2063.1 kDa, M W = 2384.8 kDa, D = 1.16, and a = x = y = b = approximately 289, characterized by wavelengths reflected in the near-infrared in the composition comprising Formula I or II. 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 percent of BBCP in the resulting coating is from about 25% to about 99.9%, and the weight percent of pigment or dye is from about 0.1% to about 10%. In some embodiments, the weight percent of BBCP is about 85%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%. In still other embodiments, the weight percent 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 linear poly(methacrylate), linear polylactic acid, linear polystyrene, or a combination thereof. In still some other embodiments, the composition further comprises zirconium dioxide nanocrystals, titanium oxide nanocrystals, or hafnium oxide nanocrystals.

[0058] In further embodiments, the BBCP of formula IA is the BBCP of formula IC or formula II, [Chemical formula] wherein R 3 and R 4 are each independently H or unbranched or branched -(C 1 -C 6 ) alkyl, m and n are each independently from 1 to 100.

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

[0060] In further embodiments, the BBCP of formula I is the BBCP of formula III, [Chemical formula] In the formula, R 5 is H or unbranched or branched -(C 1 -C 6 ) alkyl, q and t are each independently 1 to 100.

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

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

[0063] In some embodiments, the electromagnetic radiation reflected by the 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 that of the 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 profiles of the substrate include reflected electromagnetic radiation having wavelengths from about 280 nanometers to about 400 nanometers. In other embodiments, the reflectance, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation having wavelengths from about 400 nanometers to about 700 nanometers. In still other embodiments, the reflectance, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation having wavelengths from about 700 nanometers to about 1550 nanometers.

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

[0067] Furthermore, the present disclosure is 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 a BBCP of formula IA, formula IB, formula II, formula III, or formula IC, [Chemical formula] wherein: R x is -(C 2 -C 6 )alkyl-OC(=O)G 1 where G 1 includes polyacrylate, polymethacrylate, or polylactic acid, R y is -(C 1 -C 8 )alkyl-G 2 -G 3exists, and here G 2 is -C(=O)O- or a nitrogen heterocycle, and G 3 includes polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid, R 1 is unbranched alkyl, R 2 is branched alkyl, a and b are each independently 0 to 1000, x and y are each independently 1 to 1000, where the ratio of x:a is 1:0 to about 1:3, and the ratio of y:b is 1:0 to about 1:3, a process; b) a step of applying a layer of the mixture to a substrate; and c) a step of drying the layer to form a film, A method for forming a photonic coating on a substrate by the film is provided.

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

[0069] In further embodiments, the weight percent of the pigment or dye is from about 0.1% to about 3% in 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% in the mixture. In other embodiments, the weight percent of the BBCP is from about 2.5% to about 50% in the mixture, or about 1%, 5%, 10%, 15%, 20%, 25%, 30% or 40% in the mixture.

[0070] In various other embodiments of the compositions and methods, the BBCP has a number average molecular weight of from about 500 kDa to about 4000 kDa, or from 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, 1700 kDa, 1800 kDa, 1900 kDa, 2000 kDa, 2100 kDa, 2200 kDa, 2300 kDa, 2400 kDa, 2500 kDa, 2600 kDa, 2700 kDa, 2800 kDa, 2900 kDa, 3000 kDa, 3500 kDa, 4000 kDa, 4500 kDa or 5000 kDa.

[0071] In still further embodiments 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 linear poly(methacrylate), linear polylactic acid, linear polystyrene, or a combination thereof. In further embodiments of the above method, applying a layer of the mixture to a 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, slot die coating, screen printing, spray deposition, or paint brush / roller of the mixture onto the substrate.

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

[0073] A photonic crystal material comprising either an inorganic or an organic additive, and adding at least one inorganic or organic component to an organic additive composed of different monomer units as compared with a polymer-based photonic crystal or a composition of polymer components.

[0074] The photonic crystal is formed from a linear block polymer, a brush block polymer, a star polymer, a polymer colloidal crystal array, or any repeating dielectric structure.

[0075] The polymer is assembled or manufactured into spheres, cylinders, gyroids, thin plates, or any periodic structure available by polymer self-assembly.

[0076] The polymer composite photonic crystal material, or a single brush block copolymer, is deposited by spin-down, wire bar, doctor blade, or bird bar.

[0077] The polymer composite photonic crystal material, or a single brush block copolymer, is deposited by paint brush or roller coating.

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

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

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

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

[0082] The photonic crystal coating has a high near-infrared reflectance and a low visible reflectance.

[0083] The photonic crystal coating has a high visible reflectance and a low ultraviolet reflectance.

[0084] The inorganic component is in the form of alkali (earth) metal at the nanoscale (generally including molecular complexes and fine particles).

[0085] The inorganic component is in the form of Group IV metals such as titanium, zirconium, or hafnium, and / or their oxides, or the nanoscale form (generally including molecular complexes and fine particles) of a combination of any element with Group IV metals and / or oxides.

[0086] The inorganic component is in the form of Group V metals such as vanadium, niobium, and tantalum, and / or their oxides, or the nanoscale form (generally including molecular complexes and fine particles) of a combination of any element with Group V metals and / or oxides.

[0087] The inorganic component is in the form of Group VI metals such as chromium, molybdenum, and tungsten, and / or their oxides, or the nanoscale form (generally including molecular complexes and fine particles) of a combination of any element with Group VI metals and / or oxides.

[0088] The inorganic component is in the form of Group VII metals such as manganese, technetium, and rhenium, and / or their oxides, or the nanoscale form (generally including molecular complexes and fine particles) of a combination of any element with Group VII metals and / or oxides.

[0089] The inorganic component is in the form of nanoscale of group VIII metals such as iron, ruthenium, and osmium, and / or their oxides, or a combination of any element with group VIII metals and / or oxides (generally including molecular complexes and fine particles).

[0090] The inorganic component is in the form of nanoscale of group IX metals such as cobalt, rhodium, and iridium, and / or their oxides, or a combination of any element with group IX metals and / or oxides (generally including molecular complexes and fine particles).

[0091] The inorganic component is in the form of nanoscale of group X metals such as nickel, palladium, and platinum, and / or their oxides, or a combination of any element with group X metals and / or oxides (generally including molecular complexes and fine particles).

[0092] The inorganic component is in the form of nanoscale of group XI metals such as copper, silver, and gold, and / or their oxides, or a combination of any element with group XI metals and / or oxides (generally including molecular complexes and fine particles).

[0093] The inorganic component is in the form of nanoscale of group XII metals such as zinc, cadmium, and mercury, and / or their oxides, or a combination of any element with group XII metals and / or oxides (generally including molecular complexes and fine particles).

[0094] The inorganic component is functionalized with surface ligands. When the inorganic component is functionalized with surface ligands, the inorganic component can be functionalized with surface polymer-based ligands.

[0095] The organic or inorganic additive component has a refractive index greater than or less than 0.05 and is derived from a homopolymer that would be derived from the monomer units constituting the BCP.

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

[0097] 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] The inorganic or organic additive absorbs ultraviolet A or B light (280 - 400 nm).

[0101] The inorganic or organic additive changes the absorption rate or transmittance profile of the photonic crystal in the ultraviolet A or B light region (280 - 400 nm).

[0102] The inorganic or organic additive absorbs visible light (400 - 700 nm).

[0103] The inorganic or organic additive changes the absorption rate or transmittance profile of the photonic crystal in the visible light region (400 - 700 nm).

[0104] The inorganic or organic additive absorbs near-infrared, IR-A, light in the region of 700 - 1400 nm.

[0105] The inorganic or organic additive changes the absorption rate or transmittance profile of the photonic crystal in the near-infrared, IR-A, light region of 700 - 1400 nm.

[0106] Results and Discussion Incorporating inorganic materials at specific weight percentages has been found to have the effect of selectively reducing the %R of the (even-numbered) order reflections from a polymer-based photonic crystal while maintaining or increasing the %R of the 1st and 3rd (odd-numbered) reflections (Figure 1). As observed in Figure 1, by using an inorganic additive, the second-order %R selectively decreases from 31%R at 519 nm, which is easily observable as green to the human eye, to 4.7%R at 525 nm, which is not easily observable to the human eye.

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

[0108] Both observations can be explained through an operation of the optical thickness called the "f-ratio" (f), which can be defined by Equation 2 (Polymer Engineering and Science 1969, 9, 404). Equation 2:

Number

[0109] Here, when the f-value is close to or equal to 0.5 (equivalent optical thickness), even-order reflections (m = 2, 4, 6...) are suppressed, and when the f-value is close to or equal to 0.33, odd-order reflections (m = 1, 3, 5, 7...) are suppressed. By adding organic or inorganic components that conform to the BCP, it is possible to target specific wavelength regions (UV, Vis, NIR) and adjust the %R. In the case of a visually transparent UV and / or NIR reflective coating, the %R within the visible region can be suppressed.

[0110] Innovations in the polymer materials themselves, polymer composite mixtures, and the facile process by which these materials self-organize to form functional optical coatings deposited by various methods such as paintbrush, drawdown, wire bar, doctor blade, bird bar, roller coating, screen printing, spray brush, or spray gun coating provide significant advantages over the state of the art (Figure 3).

[0111] Figure 1 compares the reflectivities of two PLA-b-PS photonic crystal films. The solid line trace contains inorganic additives, and the dashed line trace contains no additives. Comparing the intensities (reflection %) of the different peaks, it can be seen that when inorganic additives are included, the relative intensities of the primary, secondary, and tertiary reflections change significantly. Specifically, when inorganic additives are included, the tertiary reflection increases relative to the primary, and the secondary reflection decreases relative to the primary. This result is important because visible reflection is selectively suppressed while maintaining UV and NIR reflection. Compared to the closest prior art, similar optical characteristics are achieved by coextruding multiple layers of different polymer materials. In contrast to coextrusion, similar optical properties are now available by simple compounding and coating.

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

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

[0114] Furthermore, the present disclosure relates to the discovery that self-assembled polymer photonic crystal coatings composed of brush block copolymers (BBCPs), and optically active additives in the form of externally 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 fabricated from a model system using poly(styrene)-block-poly(isobutyl methacrylate) brush block copolymer (BBCP). The BBCP was synthesized by a graft-through approach via ring-opening metathesis polymerization from norbornene-based poly(styrene) and poly(isobutyl methacrylate) macromonomers. The BBCP was completely dissolved in solution to 25 wt % solids. Additives were either not included or 0.4 wt % pigment or dye was added relative to the total solution mass (Figs. 4-11). The composition of the formulations is shown in Table 1.

Table 1

[0116] A bird bar was used to cast the films at a wet film thickness of 4.0 mils. Fig. 4 shows the reflectance and transmittance of the PC films on microscope glass slide substrates. In Figs. 5-11, the films contain dye or pigment and are compared to the control in Fig. 4. In Figs. 5-11, the dye or pigment changes the optical properties and thus 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. One of ordinary skill in the art will readily recognize that the examples suggest many other ways in which the invention can be practiced. It is to be understood that many variations and modifications can be made while remaining within the scope of the present invention.

[0118] Example Example 1. Materials and Methods The composition of the polymer composite material was prepared from a brush block copolymer, 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 hereby incorporated by reference in its entirety.

[0119] The polymer film was deposited on a microscope glass slide, and reflectance and transmittance spectra were recorded with a Cary 5000 UV-Vis-NIR spectrophotometer equipped with a diffuse reflectance accessory. Linear poly(lactic acid):

Chemical formula

[0120] To a 200 mL Schlenk flask equipped with a magnetic 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 mixture was heated to 135 °C. Since the reaction proceeded, lactide sublimed on the side walls of the flask, which was melted back into the solution with a heat gun to ensure quantitative consumption of the monomer. After 3.5 hours, the reaction mixture was diluted with dichloromethane (DCM), filtered through a Celite plug, and precipitated into methanol. Yield: 75%, M n = 3,050 Da, PDI = 1.07. Linear poly(styrene):

Chemical formula

[0121] A 1 L Schlenk flask equipped with a stir bar, which had been degassed, filled with nitrogen, and flame-dried three times, was charged with 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 stirred toluene. After stirring the solution for 20 minutes, 2 freshly dried and distilled styrene (120 mL, 109 g, 1.05 mol, 29.9 equiv) was added via a 60 mL syringe in a fairly rapid manner. No significant exotherm was observed and the solution immediately changed from clear to orange / red. After 2 h, approximately 50 mL of methanol was injected to quench the reaction.

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

[0123] A 100 mL Schlenk flask equipped with a stir bar, which had been degassed, filled with nitrogen, and flame-dried three times, was charged with DCM solvent, 2-ethylhexyl methacrylate monomer, and methyltrimethylsilyldimethylketene acetal. A TMS-triflimide catalyst was added to initiate the polymerization. The polymerization was allowed to proceed at room temperature and, after 3 h, 1 when >99% conversion as confirmed by 1H NMR, it was quenched. 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 = 3,100 Da, PDI = 1.11.

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

[0125] Alcohol-terminated polystyrene: Degassed, filled with nitrogen, and flame-dried three times. To a 1 L Schlenk flask equipped with a stir bar, 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 equivalent) was added to the stirring toluene. After stirring the solution for 20 minutes, CaH 2 Freshly dried and distilled styrene (120 mL, 109 g, 1.05 mol, 29.9 equivalents) was added rather rapidly 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 equivalents) was added to terminate the polystyrene chains and provide the appropriate functionality. The reaction mixture was stirred overnight, then approximately 50 mL of methanol was injected to quench the reaction. Workup: The solution was concentrated on a rotary evaporator to remove the remaining toluene, methanol, cyclohexane, and propylene oxide. The polymer was dissolved in THF and precipitated at room temperature into a stirring methanol solution. 98% recovery, M n = 3,153 Da, PDI = 1.05. [Chemical]

[0126] Coupling of Polystyrene Alcohol and Norbornene Carboxylic Acid: A 1 L Schlenk flask equipped with a magnetic stir bar that was degassed, filled with nitrogen, and flame-dried three times was charged with 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). The mixture was dissolved in approximately 650 mL of dry DCM and stirred for 30 minutes on an ice bath. Then, under a positive nitrogen flow, DCC (7.87 g, 0.038 mmol, 2.0 equiv) was added to the solution over 10 minutes. The reaction was allowed to proceed overnight.

[0127] Workup: After 24 hours, the solution was recooled to 0 °C and filtered through a medium frit to remove dicyclohexylurea. The filtered solution was then cooled again to -20 °C and the remaining dicyclohexylurea precipitate was filtered off a second time. After filtration, the solution was concentrated on a rotary evaporator and then dissolved in THF and precipitated 5 times at room temperature in a stirred methanol solution. Yield = 75%.

[0128] Example 3. Synthesis of Isobutyl Methacrylate Macromonomer [Chemical formula]

[0129] Synthesis of N-(ethyl methacrylate)-cis-5-norbornene-exo-2,3-dicarboximide: In a 1 L Schlenk flask that was flame-dried and filled with nitrogen three times, 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 were added. The heterogeneous solution was mixed on an ice bath for 20 minutes, and then 1-ethyl-3-(d-dimethylaminopropyl)carbodiimide (93.8 g, 604 mmol, 1.5 equiv) was slowly added under positive nitrogen. After allowing the reaction to proceed for 2 days, the organic layer was washed with 0.5 M HCl, saturated NaHCO 3 solution, water, and brine, dried over MgSO 4 , and then passed through 200 g of alumina to remove further methacrylic acid. The organic layer was then concentrated in the dark to obtain a white solid (46 g, 42% yield) because the product is photosensitive in solution.

Chemical formula

[0130] Group transfer polymerization: A 250 mL Erlenmeyer flask equipped with a 24 / 40 adapter and a stir bar was dried in an oven and placed in a high-temperature glove box. 75 mL of anhydrous DCM from the solvent system was added into the glove box. To this, degassed dimethylphenylsilane (573 μL, 3.74 mmol, 1.03 equiv) was added, and then sublimed tris(pentafluorophenyl)borane (18.6 mg, 0.0363 mmol, 0.01 equiv) was added. After stirring this solution for 1 minute, 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 minutes (more than 100 drops in total). This solution was stirred for an additional 15 minutes, where CaH 2It was dried and distilled butyl methacrylate (10.49 mL, 0.0653 mmol, 18 equivalents) was injected into the stirred solution. Finally, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (51 μL, 0.1456 mmol, 0.04 equivalents) was added. M n = 2,940 Da, PDI = 1.07.

[0131] Example 4. Synthesis of Brush Block Copolymer (BBCP)

Chemical Structure

[0132] BBCP1: In a vial containing isobutyl methacrylate macromonomer (200 equivalents) and a stir bar, CH 2 Cl 2 was added to obtain a 0.05 M solution. The polymerization was initiated by the addition of Grubbs third-generation catalyst (1.0 equivalent). After stirring at room temperature for 1 hour, a solution of CH 2 Cl 2 and pyridine (1.0 mM, 5.0 equivalents) was added. In another vial, a solution of the second block was prepared by adding styrene macromonomer (200 equivalents) to CH 2 Cl 2 (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 hours. The reaction was quenched by the addition of excess ethyl vinyl ether and the block copolymer was isolated by precipitation into methanol at -78 °C.

Chemical Structure

[0133] BBCP2 (see J. Am. Chem. Soc. 2017, 139, 17683): In a 30 mL brown vial containing PLA-MM (1173 mg, 0.325 mmol, M n = 3608 Da) and a stir bar, CH in d,x-DME 2 Cl2 A solution (68.32 mg, 0.325 mmol, 0.05 M in 6.5 mL) was added. The copolymerization was carried out with PLA 170 -r-DME 170 targeted by the third-generation Grubbs catalyst ((H 2 IMes)-(pyr) 2 (Cl) 2 RuCHPh, 1.91 μmol). After stirring at room temperature for 75 minutes, an aliquot was extracted for analysis and a CH 2 Cl 2 solution of pyridine was added (3.8 mL, 1.0 mM). In a separate vial, the solution of the second block was prepared by dissolving PS-MM (1138 mg, 0.325 mmol, M n = 3500 Da) in a CH 2 Cl 2 solution of d,x-DiPE (86.56 mg, 0.325 mmol, 0.05 M in 6.5 mL). Then, using a 12 mL 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 12 hours. The reaction was stopped 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] Certain embodiments have been described above with reference to the disclosed embodiments and examples, but such embodiments are merely illustrative and do not limit the scope of the invention. In a broader aspect defined by the following claims, changes and modifications can be made by those skilled in the art without departing from the invention.

[0135] All publications, patents, and patent documents are hereby incorporated by reference as if individually incorporated by reference. Restrictions that conflict with the present disclosure should not 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 present invention. The various aspects or embodiments that may be included in the present invention are summarized as follows. [1]. A photonic crystal composition comprising a pigment and a brush block copolymer (BBCP) of formula IA or formula IB, [Chemical formula 1] JPEG0007689075000018.jpg66133 wherein, R x is -(C 2 -C 6 )alkyl-OC(=O)G 1 where G 1 includes 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 includes polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate or polylactic acid, R 1 is unbranched alkyl, R 2 is branched alkyl, J 1 and G are each independently 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 from 0 to about 1000, x and y are each independently from 1 to about 1000, where the blocks a, b, x and y are in any order, and 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, a photonic crystal composition. [2]. The composition according to item 1 above, 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, a fluorescent whitening agent, 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]. The composition according to item 1 above, wherein the pigment is acridine, bromothymol, carmin, eosin Y, guaiac azulene, perylene, or a combination thereof. [4]. The composition according to item 1 above, 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]. The composition according to item 1 above, wherein the ratio of x:a is from about 1:0.5 to about 1:1. [6]. The composition according to item 1 above, wherein the ratio of y:b is from about 1:0.5 to about 1:1. [7]. The composition according to item 1 above, wherein the weight percentage of BBCP is from about 25% to about 99.9%, and the weight percentage of the pigment is from about 0.1% to about 10%. [8]. The composition according to item 1 above, further comprising a metal oxide, a linear polymer additive, or a combination thereof. [9]. The composition according to item 1 above, further comprising zirconium dioxide nanocrystals.

[10] . The BBCP of formula IA is a BBCP of formula IC or formula II, [Chemical formula 2] JPEG0007689075000019.jpg101128 wherein R 3 and R 4 are each independently H or unbranched or branched -(C 1 -C 6 ) alkyl, m and n are each independently from 1 to about 100, the composition according to item 1 above.

[11] . The composition according to item 10 above, wherein m and n are each independently from 10 to about 50.

[12] . The BBCP of formula IA is a BBCP of formula III, [Chemical formula 3] JPEG0007689075000020.jpg7598 wherein R 5 is H or unbranched or branched -(C 1 -C 6 ) alkyl, q and t are each independently from 1 to about 100, the composition according to item 1 above.

[13] . A method of adjusting the electromagnetic radiation reflectivity, absorbance, and transmittance profiles of a substrate, comprising coating the substrate with a film of the photonic crystal composition according to item 1 above, wherein the pigment in the photonic crystal composition adjusts the reflectivity, absorbance, and transmittance profiles of the substrate, and the electromagnetic radiation reflected by the coated substrate is increased by at least 5% compared to the corresponding uncoated substrate.

[14] . The method according to item 13 above, wherein the film has an optical thickness f ratio of from about 0.25 to about 0.55.

[15] . The reflectivity, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation at a wavelength of from about 280 nanometers to about 400 nanometers, or The reflectivity, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation at a wavelength of from about 400 nanometers to about 700 nanometers, or The reflectivity, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation at a wavelength of from about 700 nanometers to about 1600 nanometers, the method according to item 13 above.

[16] . A method for forming a photonic coating, 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, [Chemical formula 4] JPEG0007689075000021.jpg31114 wherein R x is -(C 2 -C 6 ) alkyl-OC(=O)G 1 where G 1 includes 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, and G 3 includes polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid, R 1 is unbranched alkyl, R 2 is branched alkyl, a and b are each independently from 0 to about 1000, x and y are each independently from 1 to about 1000, where 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, step b) applying a layer of the mixture to a substrate, and c) drying the layer to form a film, wherein the film forms the photonic coating on the substrate, method.

[17] . The method according to item 16 above, wherein the pigment is an acid dye, a basic dye, an azo dye, an acridine dye, a perylene dye, a sulfur dye, a pH indicator, a food dye, a fluorescent whitening agent, 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 according to item 16 above, wherein the mixture contains the pigment at about 0.1 wt% to about 3 wt%.

[19] . The method according to item 16 above, wherein the weight percentage of BBCP in the mixture is about 2.5% to about 50%.

[20] . The method according to item 16 above, wherein BBCP has a number average molecular weight of about 500 kDa to about 4000 kDa.

[21] . The method according to item 16 above, wherein step a) further includes adding a metal oxide, a linear polymer additive, or a combination thereof to the mixture.

[22] . The method according to item 16 above, wherein the application of the layer of the mixture to the substrate includes spray deposition, drawdown coating, slot die coating, screen printing, spray deposition, or paint brush / roller of the mixture onto the substrate.

Claims

1. A photonic crystal composition comprising a pigment and a brush block copolymer (BBCP) of formula IA or formula IB, 【Chemical 1】 wherein, R ｘ is -(C ２ -C ６ )alkyl - OC(=O)G １ where G １ includes 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, and G ３ includes 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 CH ２ or C=O, and Each J ２ is independently CH ２ or C=O, and each Q is independently alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, a and b are each independently 0 to 1000, x and y are each independently 1 to 1000, where the blocks a, b, x and y are in any order, the ratio of x:a is 1:0 to 1:3, and the ratio of y:b is 1:0 to 1:3, the pigment is an azo dye, an acridine dye, a perylene dye, a sulfur dye, a pH indicator, a food dye, a fluorescent 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 perylenediimide dye, a rhodamine dye, or a combination thereof, a photonic crystal composition.

2. The composition according to claim 1, wherein the pigment is acridine, bromothymol, carmine, eosin Y, guaiacazulene, perylene, or a combination thereof.

3. The composition according to claim 1, wherein a and b are each independently 1 to 300, or x and y are each independently 1 to 300.

4. The composition according to claim 1, wherein the ratio of x:a is 1:0.5 to 1:

1.

5. The composition according to claim 1, wherein the ratio of y:b is 1:0.5 to 1:

1.

6. The composition according to claim 1, wherein the weight percentage of BBCP is 25% to 99.9%, and the weight percentage of the pigment is 0.1% to 10%.

7. The composition according to claim 1, further comprising a metal oxide, a linear polymer additive, or a combination thereof.

8. The composition according to claim 1, further comprising zirconium dioxide nanocrystals.

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

10. The composition according to claim 9, wherein m and n are each independently 10 to 50.

11. The BBCP of formula IA is a BBCP of formula III, [Chemical Formula 3] wherein, R ５ is H or unbranched or branched -(C １ -C ６ )alkyl, The composition according to claim 1, wherein q and t are each independently 1 to 100.

12. A method for adjusting the electromagnetic radiation reflectivity, absorbance, and transmittance profiles of a substrate, comprising coating the substrate with a film of the photonic crystal composition according to claim 1, wherein the pigment in the photonic crystal composition adjusts the reflectivity, absorbance, and transmittance profiles of the substrate, and the electromagnetic radiation reflected by the coated substrate is at least 5% more than that of the corresponding uncoated substrate.

13. The method according to claim 12, wherein the film has an optical thickness f ratio of 0.25 to 0.

55.

14. The reflectivity, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation at a wavelength of 280 nanometers to 400 nanometers, or The reflectivity, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation at a wavelength of 400 nanometers to 700 nanometers, or The reflectivity, absorbance, and transmittance profiles of the substrate include reflected electromagnetic radiation at a wavelength of 700 nanometers to 1600 nanometers, according to the method of claim 12.

15. 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, 【Chemical Formula 4】 wherein, R ｘ is -(C ２ -C ６ )alkyl-OC(=O)G １ where G １ includes polyacrylate, polymethacrylate or polylactic acid, R ｙ is -(C １ -C ８ )alkyl-G ２ -G ３ wherein G ２ is -C(=O)O- or a nitrogen heterocycle, and G ３ includes 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 1000, x and y are each independently 1 to 1000, where the ratio of x:a is 1:0 to 1:3, and the ratio of y:b is 1:0 to 1:3, the pigment being an azo dye, an acridine dye, a perylene dye, a sulfur dye, a pH indicator, a food dye, a fluorescent 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 perylenediimide dye, a rhodamine dye, or a combination thereof, in the step b) applying a layer of the mixture to a substrate, and c) drying the layer to form a film, wherein the film forms the photonic coating on the substrate.

16. The method according to claim 15, wherein the mixture contains the pigment in an amount of 0.1% to 3% by weight.

17. The method according to claim 15, wherein the weight percentage of BBCP in the mixture is 2.5% to 50%.

18. The method according to claim 15, wherein BBCP has a number average molecular weight of 500 kDa to 4000 kDa.

19. The method according to claim 15, wherein step a) further comprises adding a metal oxide, a linear polymer additive, or a combination thereof to the mixture.

20. The method according to claim 15, wherein the application of the mixture layer to the substrate comprises spray deposition, drawdown coating, slot die coating, screen printing, spray deposition, or paint brush / roller of the mixture onto the substrate.

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