Organic polymerizable composition, polymerized product and optical article formed therefrom, and method of reducing opacity

Abstract

The present disclosure relates to an organic polymerizable composition, and polymerized products and optical articles prepared therefrom. The composition comprises (a) an isocyanate-functional prepolymer and (b) an aromatic diamine having at least one primary amino group. The prepolymer (a) is prepared from a reaction mixture comprising: (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) a 4, 4 '-methylene bis (cyclohexyl isocyanate); and (ii) a polyol component. The composition further includes a photochromic compound, which may be present in the reaction mixture that forms the prepolymer. A method of reducing opacity of an optical article is also provided.

Description

Technical Field

[0001] This disclosure provides an organic polymerizable composition, a polymeric product formed from the organic polymerizable composition, and an optical article formed from the polymeric product. This disclosure also provides a method for reducing the opacity of the optical article. Background Technology

[0002] The use of various thermosetting organic polymer compositions in the production of polymeric products and molded polymer articles is known in the art. When such molded polymer articles include polymeric optical articles, the composition must provide optical articles with acceptable optical quality while maintaining durability and impact resistance. Examples of such molded polymeric optical articles may include windshields, sunglasses lenses, fashion lenses, over-the-counter and prescription lenses, sports masks, protective face shields, components for augmented reality, virtual reality, mixed reality, or smart glasses, and goggles.

[0003] Many organic polymer materials, such as plastics, have been developed as alternatives to glass in applications such as optical lenses, optical fibers, windows, and transparent films for automotive, marine, and aerospace applications. These polymer materials offer advantages over glass, including shatter resistance, lighter weight for a given application, ease of molding and demolding, and ease of dyeing or imparting color or hue. However, molding polymer products can result in haze and increased opacity, especially when incompatible components (i.e., components that do not form a homogeneous mixture) are used together in the reaction mixture. Haze can be defined as the percentage of incident light scattered by a glass or plastic sample at a degree greater than 2.5. In the art, haze is typically measured at 550 nm using instruments such as the Haze Gard Plus available from BYK-Gardner, according to ASTM D-1003 (published in 2003). Alternatively, inhomogeneities due to component incompatibility may manifest as a milky appearance (opaqueness), particularly in colored or dark-colored articles. In this context, measuring opacity (usually reported as a percentage) at high thicknesses (such as 8 mm or 12 mm) can be used as a way to measure optical phenomena in quantitative articles.

[0004] There is a need in the art to develop a polymerizable composition that does not produce opacity during casting and polymerization while maintaining other desired optical properties, resulting in an article of acceptable optical quality. Summary of the Invention

[0005] This disclosure relates to an organic polymerizable composition and polymeric products and optical articles prepared therefrom. The composition comprises: (a) an isocyanate-functionalized prepolymer and (b) an aromatic diamine having at least one primary amino group. The prepolymer (a) is prepared from a reaction mixture comprising: (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate); and (ii) a polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent. The composition further comprises a photochromic compound as a third component (c) in the reaction mixture used to prepare the prepolymer (a) and / or in the organic polymerizable composition.

[0006] Methods for reducing the opacity of optical articles are also provided. An exemplary method includes (a) preparing an isocyanate-functionalized prepolymer by reacting a reaction mixture together, the reaction mixture comprising: (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the isocyanate functional group in the aliphatic polyisocyanate (1) reacts with the 4,4'-methylenebis(cyclohexyl isocyanate). (2) The isocyanate functional groups in the form of an equivalent ratio of 1:8 to 5:1 or 1:7.5 to 4.75:1; and (ii) a polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent; (b) reacting the prepolymer formed in (a) with an aromatic diamine in the presence of a photochromic compound to form a polymer; and (c) forming an optical article from the polymer. Compared to optical articles not prepared by this method, the opacity is reduced; for example, by not using a polyisocyanate component in the reaction mixture, the polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; or by not using (2) 4,4'-methylenebis(cyclohexyl isocyanate) in the reaction mixture; or wherein the isocyanate functional group in the aliphatic polyisocyanate (1) is related to the 4,4'-methylenebis(cyclohexyl isocyanate). (2) The isocyanate functional group equivalent ratio is not 1:8 to 5:1; or by not using (ii) the polyol component in the reaction mixture, which comprises a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent; or by reacting the prepolymer formed in (a) with an aromatic diamine to form a polymer product in the presence of a photochromic compound, not in (b).

[0007] Alternatively, at least one photochromic compound containing a functional group that reacts with the polyisocyanate component (i) may be included in the reaction mixture used to prepare the isocyanate functional prepolymer. Detailed Implementation

[0008] Note that, as used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural indicators unless explicitly and precisely limited to one indicator.

[0009] For the purposes of this specification, unless otherwise indicated, all figures used in the specification and claims to represent quantities of ingredients, reaction conditions, or other parameters should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that can vary depending on the desired properties to be obtained from the disclosed compositions. At least, and not in an attempt to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0010] All numerical ranges in this document include all values ​​within the listed ranges and all numerical ranges. Although the numerical ranges and parameters that illustrate the broad scope of this disclosure are approximations, the values ​​described in specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that must be caused by the standard deviation found in its corresponding test measurement.

[0011] Each of the various examples presented herein is to be understood as not limiting the scope of this disclosure.

[0012] As previously mentioned, the present invention relates to an organic polymerizable composition and polymeric products and optical articles prepared therefrom. The term "optical quality" (as used, for example, in conjunction with polymeric materials such as "optical quality resin" or "optical quality organic polymeric material") means that the indicated material (e.g., polymeric material, resin, or resin composition) is or forms a substrate, layer, film, or coating that can be used as or combined with optical articles (such as lenses).

[0013] The term "optical article" means that the specified article exhibits a transmittance value (transmitted incident light) of at least 4%, such as at least 50%, or at least 70%, or at least 85%. As used herein, an optical article may exhibit at least 70% transmittance (% transmittance, as defined in Equation 1 below, where I is the light transmitted through the article and Io is the incident light) when measured at 550 nm using, for example, a Hunter UltraScan PRO (Hunter Associates Laboratory, Inc.) with a D65 light source.

[0014]

[0015] The term "optical article" further refers to an article exhibiting a haze value of less than 5%, for example less than 1% or less than 0.5%, when measured at 550 nm using an instrument such as the Haze Gard Plus available from BYK-Gardner. Optical articles include, but are not limited to, lenses, optical layers such as optical resin layers, optical films and optical coatings, and optical substrates with light-affecting properties. As mentioned above, inhomogeneities due to component incompatibility can themselves manifest as a milky appearance ("opacity"), especially in colored or dark-colored articles (e.g., sunglass lenses, polarized lenses, etc.), and become more pronounced with increasing article thickness. In such cases, measuring opacity at a constant thickness using an opacity smoke meter or spectrophotometer can be used as a way to quantify this phenomenon. Opacity is typically determined by one or more measurements of the reflectance of visible light transmitted through the article. For example, opacity can be calculated based on the ratio of diffuse reflectance measurements of an article with a black backing to those of an article with a white backing. When the opacity value is measured at an article thickness of 8 mm, for example using an EEL 12M opacity meter available from Smithers or an Ultra Scan PRO spectrophotometer available from HunterLab, the optical articles of this disclosure typically exhibit an opacity value of less than 28%, for example less than 27%; or when the opacity value is measured at an article thickness of 12 mm, for example using an EEL 12M opacity meter available from Smithers or an Ultra Scan VIS spectrophotometer available from HunterLab, the optical articles of this disclosure typically exhibit an opacity value of less than 51%, for example less than 50%.

[0016] The organic polymerizable compositions disclosed herein comprise (a) an isocyanate-functionalized prepolymer. The prepolymer (a) is prepared from a reaction mixture comprising: (i) a polyisocyanate component; and (ii) a polyol component. The polyisocyanate component (i) comprises: (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate). It has been found that the asymmetric aliphatic polyisocyanate (1) having at least one secondary isocyanate functional group, when combined with the following 4,4'-methylenebis(cyclohexyl isocyanate) (2) in a specific equivalence ratio, unexpectedly and significantly contributes to reducing the opacity of the polymerized product, particularly when including additive components (such as colorants or dyes, including photochromic dyes, thermochromic dyes, electrochromic dyes, etc.) that may present compatibility difficulties.

[0017] Suitable aliphatic polyisocyanates (1) having at least one primary isocyanate functional group and at least one secondary isocyanate functional group include isophorone diisocyanate. Other such aliphatic polyisocyanates having at least one primary isocyanate functional group and at least one secondary isocyanate functional group are also suitable. As used herein, the term "aliphatic and alicyclic polyisocyanate" refers to a straight-chain or cyclized compound having 6 to 100 carbon atoms and having two or more isocyanate reactive groups.

[0018] Based on the total weight of aliphatic polyisocyanate (1) and 4,4'-methylenebis(cyclohexylisocyanate) (2), aliphatic polyisocyanate (1) is typically present in the polyisocyanate component (i) in an amount of at least 10% by weight, or at least 20% by weight, or at least 30% by weight, or at least 40% by weight and at most 80% by weight, or at most 70% by weight, or at most 60% by weight. For example, based on the total weight of aliphatic polyisocyanate (1) and 4,4'-methylenebis(cyclohexylisocyanate) (2), aliphatic polyisocyanate (1) may be present in the polyisocyanate component (i) in an amount of 10 wt% to 80 wt%, or 20 wt% to 80 wt%, or 30 wt% to 80 wt%, or 40 wt% to 80 wt%, or 10 wt% to 70 wt%, or 20 wt% to 70 wt%, or 30 wt% to 70 wt%, or 40 wt% to 70 wt%, or 10 wt% to 60 wt%, or 20 wt% to 60 wt%, or 30 wt% to 60 wt%, or 40 wt% to 60 wt%.

[0019] The polyisocyanate component (i) further comprises (2) 4,4'-methylenebis(cyclohexyl isocyanate), also known as dicyclohexylmethane-4,4'-diisocyanate, 4,4'-diisocyanate-methylenedicyclohexane, 4,4'-HMDI, or bis(4-isocyanate-cyclohexyl)methane. 4,4'-methylenebis(cyclohexyl isocyanate) (2) typically comprises a mixture of its isomers. As used herein and in the claims, the term "mixture of isomers" refers to a mixture of at least two of the cis-cis isomers, trans-trans isomers, and cis-trans isomers of the polyisocyanate. Non-limiting examples of mixtures of isomers may include the trans-trans isomer of 4,4'-methylenebis(cyclohexyl isocyanate) (hereinafter referred to as "PICM" (p-isocyanocyclohexylmethane)), as well as one or both of the cis-trans isomer and the cis-cis isomer of PICM.

[0020] Non-limiting examples of suitable commercial sources include VESTANAT® H12MDI (available from Evonik) and DESMODUR® W (available from Covestro).

[0021] The equivalence ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in 4,4'-methylenebis(cyclohexyl isocyanate) (2) is typically in the range of 1:8 to 5:1, such as 1:7.5 to 4.75:1. In specific examples, when the aliphatic polyisocyanate (1) is an isophorone diisocyanate, the weight ratio of isophorone diisocyanate to 4,4'-methylenebis(cyclohexyl isocyanate) (2) can be in the range of 10:90, or 20:80, or 30:70 or 40:60 to 80:20, or 75:25 or 70:30. For example, the weight ratio of isophorone diisocyanate to 4,4'-methylenebis(cyclohexyl isocyanate) (2) can be in the range of 10:90 to 80:20 (i.e., 10 to 80 parts by weight of isophorone diisocyanate: 90 to 20 parts by weight of 4,4'-methylenebis(cyclohexyl isocyanate) (2)), or 20:80 to 80:20, or 30:70 to 80:20, or 40:60 to 80:20, or 10:90 to 75:25, or 20:80 to 75:25, or 30:70 to 75:25, or 40:60 to 75:25, or 10:90 to 70:30, or 20:80 to 70:30, or 30:70 to 70:30, or 40:60 to 70:30.

[0022] The equivalent ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) can be in the range of 1:8, or 1:6, or 1:4, or 1:1 to 5:1, or 4:1, or 3:1. For example, the equivalent ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) can be in the range of 1:8 to 5:1 (i.e., 1 to 5 equivalents of polyisocyanate (1): 8 to 1 equivalent of 4,4'-methylenebis(cyclohexylisocyanate) (2)), or 1:6 to 5:1, or 1:4 to 5:1, or 1:1 to 5:1, or 1:8 to 4:1, or 1:6 to 4:1, or 1:4 to 4:1, or 1:1 to 4:1, or 1:8 to 3:1, or 1:6 to 3:1, or 1:4 to 3:1, or 1:1 to 3:1.

[0023] The polyisocyanate component (i) may further comprise one or more additional polyisocyanates different from (1) and (2). Other diisocyanates that may be used include hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate, m-xylene diisocyanate (“MXDI”), and m-tetramethylxylene diisocyanate (1,3-bis(1-isocyanato-1-methylethyl)-benzene), which may be commercially available from Cytec Industries Inc. under the trade name TMXDI® (m) aliphatic isocyanate.

[0024] The polyol component (ii) used to prepare the prepolymer (a) comprises a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent. The hydroxyl equivalent weight may be derived from a calculated or measured molecular weight. Number-average molecular weight (Mi) n The number-average molecular weight of a compound can be determined by nuclear magnetic resonance (NMR) spectroscopy, as is well known to those skilled in the art. NMR spectroscopy for terminal group analysis has long been established as a viable analytical technique for determining the number-average molecular weight of a compound.

[0025] The polyol component (ii) used to prepare the prepolymer (a) typically comprises a polyester polyol. Such polyols can be prepared in a known manner by condensation of a polyol and a polycarboxylic acid. Exemplary polyols include, but are not limited to, ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, and pentaerythritol. Suitable polycarboxylic acids may include succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and trimellitic acid. In addition to the polycarboxylic acids mentioned above, functional equivalents of acids (such as acid anhydrides) or lower alkyl esters of acids (such as methyl esters) may also be used, where present.

[0026] In some instances, polyol component (ii) comprises at least one polyester polyol derived from an autolactone, such as α-acetyllactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. In particular instances, polyol component (ii) may comprise at least one polyester polyol derived from an autolactone, such as a mixture of up to four different polyester polyols derived from autolactones. Particularly suitable polyester polyols include the reaction product of ε-caprolactone with one or more polyols (typically diols) that typically contain 2 to 16, 2 to 10, or 2 to 6 carbon atoms. Non-limiting examples of diols and other such polyols may include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 1,3-pentanediol, 2,4-pentanediol and 1,5-pentanediol, 2, 5-Hexanediol and 1,6-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, 1,2-bis(hydroxyethyl)cyclohexane, glycerol, trimethylolethane and trimethylolpropane; and their isomers. Polyester polyols can be prepared by condensing caprolactone in the presence of a bifunctional active hydrogen compound (such as water or at least one of the diols listed above). For example, polyester polyols used to prepare prepolymer (a) can be prepared using known esterification or transesterification procedures, as described, for example, in the article DM Young, F. Hostettler et al., “Polyesters from Lactone”, Union Carbide F-40, page 147. Specific examples of polyester polyols derived from autolactones include polyester diols available from Ingevity as CAPA® 2047 and CAPA® 2077. When using more than one polyester polyol derived from an autolactone, typically at least one polyol has a number-average molecular weight greater than 500 g / mol, as determined by gel permeation chromatography using polystyrene as a standard.

[0027] The polyol component (ii) used to prepare the prepolymer (a) may contain additional polyols other than one or more polyester polyols. Such additional polyols may include one or more of those listed above; in particular, trimethylolpropane.

[0028] The equivalent ratio of isocyanate functional groups in the polyisocyanate component (i) to hydroxyl functional groups in the polyol component (ii) can be in the range of 3.5:1 to 2:1, such as 3.2:1 to 2:1; or 2.8:1 to 2:1. Typically, the resulting isocyanate-functionalized prepolymer (a) has an isocyanate equivalent weight range of 300 to 700 g / equivalent, such as 300 to 500 g / equivalent.

[0029] The organic polymerizable composition further comprises (b) an aromatic diamine having at least one primary amino group. Non-limiting examples of suitable aromatic diamines include phenylenediamine and toluenediamine, such as o-phenylenediamine and p-toluenediamine. Polynuclear aromatic diamines such as 4,4'-biphenylenediamine, 4,4'-methylenediphenylamine, and monochloro- and dichloro-derived forms of 4,4'-methylenediphenylamine are also suitable.

[0030] Suitable diamines may include, but are not limited to, materials having the following chemical formulas:

[0031]

[0032] R1 and R2 can each be independently selected from methyl, ethyl, propyl, and isopropyl, and R3 can be selected from hydrogen and chlorine. Non-limiting examples of such diamines include the following compounds manufactured by Lonza Ltd. (Basel, Switzerland):

[0033] LONZACURE® M-DIPA: R1=C3H7; R2=C3H7; R3=H

[0034] LONZACURE® M-DMA: R1=CH3; R2=CH3; R3=H

[0035] LONZACURE® M-MEA: R1=CH3; R2=C2 H5; R3=H

[0036] LONZACURE® M-DEA: R1=C2H5; R2=C2H5; R3=H

[0037] LONZACURE® M-MIPA: R1=CH3; R2=C3H7; R3=H

[0038] LONZACURE® M-CDEA: R1=C2H5; R2=C2H5; R3=Cl

[0039] R1, R2, and R3 correspond to the above chemical formulas.

[0040] Diamines may include compounds such as 4,4'-methylenebis(3-chloro-2,6-diethylaniline) (Lonzacure® M-CDEA), which is available in the United States from Air Products and Chemical, Inc. (Lonzacure, Pennsylvania); 2,4-diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene, and mixtures thereof (collectively, "diethyltoluene diamine" or "DETDA"), which is commercially available from Ketjen Corporation under the trade name Ethacure® 100; dimethylthiotoluene diamine (DMTDA), which is commercially available from Albemarle Corporation under the trade name Ethacure® 300; and 4,4'-methylenebis(2-chloroaniline), which is commercially available from Kingyorker Chemicals under the trade name MOCA. A color-stabilized version of Ethacure® 100, which can be obtained under the name Ethacure® 100S (i.e., formulations containing additives that reduce yellowing), can be used in organic polymerizable compositions.

[0041] Other examples of aromatic diamines may include one or more isomers of C1-C3 dialkyltoluenediamines, such as, but not limited to, 3,5-dimethyl-2,4-toluenediamine, 3,5-dimethyl-2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, 3,5-diisopropyl-2,4-toluenediamine, 3,5-diisopropyl-2,6-toluenediamine, and mixtures thereof. Methylene diphenylamine and trimethylenediol di(p-aminobenzoate) are also suitable.

[0042] The equivalence ratio of the isocyanate functional group in the prepolymer to the primary amino group in the aromatic diamine can be in the range of 0.75:1 to 1:0.75.

[0043] The organic polymerizable compositions disclosed herein may further comprise a carbamate catalyst and / or other additional components. Non-limiting examples of suitable catalysts may be selected from Lewis bases, Lewis acids, and insertion catalysts, as described in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1992, Vol. A21, pp. 673-674. The catalyst may be a stannous salt of an organic acid, such as, but not limited to, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiol, dibutyltin dimaleate, dimethyltin diacetate, dibutyltin dichloride, and mixtures thereof. Alternatively, the catalyst may be zinc octoate, bismuth, or iron acetylacetonate.

[0044] Further non-limiting examples of suitable catalysts may include tin compounds (such as dibutyltin oxide), phosphine (such as trioctylphosphine), ammonium salts and tertiary amines (such as, but not limited to, triethylamine, triisopropylamine, dimethylcyclohexylamine, 1,4-diazabicyclo[2.2.2]octane, N,N-dimethylbenzylamine and mixtures thereof).

[0045] When used, catalyst levels can vary and can depend on a variety of factors, such as the type and amount of reactive compounds used, as well as reaction conditions, reaction rate, and the desired degree of reaction. Typically, organotin catalysts are present in amounts of less than 300 ppm, often less than 250 ppm, and tertiary amine catalysts are present in amounts of less than 1000 ppm, typically less than 800 ppm, often about 720 ppm, each based on the total weight of the prepolymer (a) and component (b).

[0046] If desired, the composition may contain other commonly used solvents and / or additives. Suitable solvents may include any organic solvents known to those skilled in the art, provided they do not react with the isocyanate functional groups. Examples of solvents are ketones, furans, ethers, aromatic solvents, and chlorinated solvents. Suitable solvents may include, but are not limited to, acetone, amyl propionate, anisole, benzene, butyl acetate, cyclohexane, and ethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether and its derivatives (as CELLOSOLVE). ® Industrial solvents for sale include diethylene glycol dibenzoate, dimethyl sulfoxide, dimethylformamide, dimethoxybenzene, ethyl acetate, methylcyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, methyl propionate, propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethyl ether, 3-propanediol methyl ether, dichloromethane, and mixtures thereof. Suitable additives may include, but are not limited to, light stabilizers, heat stabilizers, release agents, antioxidants, UV absorbers, colorants, and toughening additives.

[0047] Organic polymerizable compositions include photochromic compounds. As used herein, the term "photochromic" and similar terms such as "photochromic compound" mean having an absorption spectrum of at least visible radiation that changes in response to the absorption of at least photochemical radiation.

[0048] As used herein, the term “photochemical radiation” means electromagnetic radiation that can induce a response in a material, such as, but not limited to, changing a photochromic compound from one form or state to another, as discussed in further detail herein.

[0049] As used herein, the term "photochromic compound" includes thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound / material" means a compound / material capable of transitioning from a first state (such as a "transparent state") to a second state (such as a "colored state") in response to photochemical radiation and returning to the first state in response to thermal energy.

[0050] As used herein, the terms "first" and "second" are not intended to refer to any particular order or chronology, but rather to two different conditions or properties, in order to modify the term "state". For non-limiting illustrative purposes, the first and second states of a photochromic compound may differ in at least one optical property, such as, but not limited to, absorption of visible light and / or UV radiation. Thus, according to the disclosure herein, a photochromic compound used in conjunction with this disclosure may have different absorption spectra in each of the first and second states. For example, while not limiting herein, a photochromic compound used in conjunction with this disclosure may be transparent in the first state and colored in the second state. Alternatively, a photochromic compound used in conjunction with this disclosure may have a first color in the first state and a second color in the second state.

[0051] Suitable photochromic compounds may include any known in the art, including chromenes such as naphthopyran, benzopyran, inden-fused naphthopyran, phenanthrenepyran, or mixtures thereof; spiropyrans such as spiro(benzoindoline)naphthopyran, spiro(indoline)benzopyran, spiro(indoline)naphthopyran, spiro(indoline)quinopyran, and spiro(indoline)pyran; oxazines such as spiro(indoline)naphthooxazine, spiro(indoline)pyridobenzooxazine, spiro(benzoindoline)pyridobenzooxazine, spiro(benzoindoline)naphthooxazine, and spiro(indoline)benzooxazine; metal dithiohydrazone salts; succinic anhydrides; succinic imides; and mixtures thereof. Photochromic compounds may contain functional groups that react with the polyol or polyisocyanate component. In this case, the functional groups can chemically bond the compound to the prepolymer and / or the final polymer, thereby inhibiting the migration of the compound. Functional groups that react with the polyisocyanate component include, for example, active hydrogen groups such as hydroxyl, primary or secondary amino, thio, carboxyl (-C(O)OH), etc. In cases where the photochromic compound contains functional groups that react with the polyol or polyisocyanate component, the photochromic compound may be included as a third component (iii) in the reaction mixture used to prepare the prepolymer. Such photochromic compounds containing functional groups that react with the isocyanate-functionalized prepolymer (a) may additionally or alternatively exist as a separate third component (c) in the organic polymerizable composition. A combination of two or more photochromic compounds can be used to produce the desired color. Two or more different photochromic compounds may be present in the reaction mixture used to prepare the prepolymer, and two or more different photochromic compounds may be present in the organic polymerizable composition. When photochromic compounds are present simultaneously in the reaction mixture and the bulk organic polymerizable composition, they may be the same or different from each other. Based on the total weight of solids in the organic polymerizable composition, the photochromic compound is typically present in the organic polymerizable composition in amounts ranging from 0.10% to 10.0%, such as 0.2% to 7.0%, or 0.2% to 5.0%. The solids (i.e., non-volatile) content can be determined using ASTM D1353-13 (2021). When used in the reaction mixture to prepare a prepolymer, the photochromic compound is typically present in the reaction mixture in amounts ranging from 0.12% to 12.0%, such as 0.24% to 8.5%, or 0.24% to 6.0%, based on the total weight of reactants in the reaction mixture.

[0052] In some instances, in addition to the prepolymer (a), component (b), and any other components mentioned above, the organic polymerizable composition may further comprise a monomeric polyisocyanate, such as isophorone diisocyanate. When used, the monomeric polyisocyanate is typically present in the organic polymerizable composition in an amount of 0.05% to 20% based on the total weight of solids in the organic polymerizable composition.

[0053] In certain instances of organic polymerizable compositions, at least one component (such as, but not limited to, any of, polyisocyanates, polyols, or solvents) may be prepared from a bio-based carbon source. For example, aliphatic polyisocyanates (1), particularly isophorone diisocyanates, may be prepared from a bio-based carbon source (“biomass”). In a particular instance, isophorone diisocyanate may be prepared from acetone, a byproduct of hemicellulose fermentation. Hemicellulose is a matrix polysaccharide present in the cell walls of terrestrial plants along with cellulose. Based on the total carbon content of the organic polymerizable composition, the organic polymerizable composition may contain at least 20%, or at least 30%, or at least 40%, or at least 50% bio-based carbon. Using components derived from bio-based carbon sources improves the sustainability of the final product.

[0054] The reactive components of the organic polymerizable compositions described above can react together to produce polymeric products, as further illustrated in the following examples.

[0055] Any of the above-described organic polymerizable compositions are particularly useful for producing molded optical articles formed from polymeric products, such as transparent films, glass, colored or colorless lenses, windshields, sunglass lenses, fashion lenses, plano lenses and prescription lenses, sports masks, protective masks and goggles. The above-described organic polymerizable compositions can also be used to produce components for augmented reality, virtual reality, mixed reality, or smart glasses.

[0056] The aforementioned organic polymerizable composition can be introduced into a mold of any desired shape at a certain temperature and time to form a polymeric product, such as a thermosetting polymer. The reaction mixture can undergo an exothermic reaction and, after mixing, is typically introduced into the mold by injection, and in the case of lenses, typically into a glass mold. The temperature of the reaction mixture can be up to 130°C, typically up to 120°C, when it is introduced into the mold. The reaction mixture is held in the mold at a temperature and time sufficient to substantially cure the reaction mixture and form a molded optical article. The mold can have any shape desired for the final product. It is typically a lens mold; typically a mold for ophthalmic lenses. The molded article can then be demolded from the mold. Alternatively, the reaction mixture, optionally degassed, can be typically introduced into the mold by injection, and the mold can be heated using various conventional techniques known in the art (i.e., using a thermosetting cycle). The thermosetting cycle can vary depending on the reactivity and molar ratio of the reactants and the presence of one or more catalysts. The thermosetting cycle can include heating the mixture from room temperature to a temperature of 200°C over a period of 0.5 hours to 120 hours; or from 80°C to 150°C over a period of 5 hours to 72 hours.

[0057] The 8 mm thick optical articles of this disclosure typically exhibit an opacity value of less than 28% or less than 27%, as measured using a HunterLab Ultra Scan PRO spectrophotometer according to the manufacturer's instructions. The 12 mm thick optical articles of this disclosure typically exhibit an opacity value of less than 51% or less than 50%, as measured using a HunterLab UltraScan VIS spectrophotometer according to the manufacturer's instructions. Therefore, this disclosure also provides a method for reducing the opacity of an optical article, the method comprising:

[0058] (a) To prepare isocyanate-functionalized prepolymers by reacting together the following:

[0059] (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the equivalent ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2) is 1:8 to 5:1 or 1:7.5 to 4.75:1; and

[0060] (ii) A polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent.

[0061] (b) In the presence of a photochromic compound, reacting the prepolymer formed in (a) with an aromatic diamine having at least one primary amino group to form a polymer; and

[0062] (c) Optical articles are formed from polymer products.

[0063] Alternatively, the photochromic compound may be included as a third component in the reaction mixture used to prepare the prepolymer, particularly when the photochromic compound contains functional groups that react with the polyol or polyisocyanate component. The prepolymer can be prepared using polymerization techniques known in the art, as illustrated in the following examples.

[0064] Each component used in this method may be any of those disclosed above, and the optical article may be formed as disclosed above.

[0065] This disclosure also relates to the following aspects:

[0066] 1. An organic polymerizable composition comprising:

[0067] (a) An isocyanate-functionalized prepolymer prepared from a reaction mixture, the reaction mixture comprising:

[0068] (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the equivalence ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2) is from 1:8 to 5:1; and

[0069] (ii) A polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent.

[0070] (b) an aromatic diamine having at least one primary amino group; and

[0071] (c) Photochromic compounds.

[0072] 2. The organic polymerizable composition according to aspect 1, wherein the equivalent ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2) is 1:7.5 to 4.75:1.

[0073] 3. The organic polymerizable composition according to any of the foregoing aspects, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2500 g / equivalent.

[0074] 4. The organic polymerizable composition according to any of the foregoing aspects, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 150 to 2000 g / equivalent.

[0075] 5. The organic polymerizable composition according to any of the foregoing aspects, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2000 g / equivalent.

[0076] 6. An organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 10% by weight and at most 80% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0077] 7. An organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 20% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0078] 8. An organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 30% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0079] 9. An organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 40% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0080] 10. An organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of up to 70% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0081] 11. An organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of up to 60% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0082] 12. The organic polymerizable composition according to any of the foregoing aspects, wherein the aliphatic polyisocyanate (1) comprises isophorone diisocyanate.

[0083] 13. The organic polymerizable composition according to aspect 12, wherein at least one component is prepared from a bio-based carbon source.

[0084] 14. The organic polymerizable composition according to aspect 13 or 14, wherein the isophorone diisocyanate is prepared from acetone, which is a byproduct of hemicellulose fermentation.

[0085] 15. The organic polymerizable composition according to any of the foregoing aspects, wherein the polyol component (ii) comprises at least one polyester polyol.

[0086] 16. The organic polymerizable composition according to aspect 15, wherein the polyester polyol is derived from an autolactone or is a mixture of polyester polyols containing up to four different autolactones.

[0087] 17. The organic polymerizable composition according to any of the foregoing aspects, wherein the polyol component (ii) further comprises trimethylolpropane.

[0088] 18. The organic polymerizable composition according to any of the foregoing aspects, wherein the aromatic diamine (b) comprises diethyltoluene diamine.

[0089] 19. The organic polymerizable composition according to any of the foregoing aspects, wherein the reaction mixture further comprises (iii) a photochromic compound containing a functional group that reacts with the polyisocyanate component (i).

[0090] 20. The organic polymerizable composition according to any of the foregoing aspects, wherein the photochromic compound (c) comprises a functional group that reacts with the isocyanate functional prepolymer (a).

[0091] 21. The organic polymerizable composition according to aspect 19 or 20, wherein the functional group comprises a hydroxyl group, a primary amino group, a secondary amino group, a carboxylic acid group, and / or a thio group.

[0092] 22. The organic polymerizable composition according to any one of aspects 19 to 21, wherein the photochromic compound (iii) is the same as or different from the photochromic compound (c).

[0093] 23. The organic polymerizable composition according to any of the foregoing aspects, further comprising (d) isophorone diisocyanate.

[0094] 24. The organic polymerizable composition according to any of the foregoing aspects, wherein the photochromic compound (c) comprises two or more different photochromic compounds.

[0095] 25. A polymeric product formed from an organic polymerizable composition according to any of the foregoing aspects.

[0096] 26. An optical article formed from the polymer product according to aspect 25.

[0097] 27. The optical article according to aspect 26, wherein the optical article includes transparent film; glass; colored or colorless lens; plano lens or prescription lens; sports mask; protective mask; component for augmented reality, virtual reality, mixed reality or smart glasses; or goggles.

[0098] 28. An organic polymerizable composition comprising:

[0099] (a) An isocyanate-functionalized prepolymer prepared from a reaction mixture, the reaction mixture comprising:

[0100] (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the equivalence ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2) is 1:8 to 5:1;

[0101] (ii) a polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent; and

[0102] (iii) A photochromic compound containing a functional group that reacts with the polyisocyanate component (i); and

[0103] (b) An aromatic diamine having at least one primary amino group.

[0104] 29. The organic polymerizable composition according to aspect 28, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2500 g / equivalent.

[0105] 30. The organic polymerizable composition according to aspect 28 or 29, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 150 to 2000 g / equivalent.

[0106] 31. The organic polymerizable composition according to any one of aspects 28 to 30, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2000 g / equivalent.

[0107] 32. The organic polymerizable composition according to any one of aspects 28 to 31, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 10% by weight and at most 80% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0108] 33. The organic polymerizable composition according to any one of aspects 28 to 32, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 20% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0109] 34. The organic polymerizable composition according to any one of aspects 28 to 33, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 30% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0110] 35. The organic polymerizable composition according to any one of aspects 28 to 34, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 40% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0111] 36. The organic polymerizable composition according to any one of aspects 28 to 35, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of up to 70% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0112] 37. The organic polymerizable composition according to any one of aspects 28 to 36, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of up to 60% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0113] 38. The organic polymerizable composition according to any one of aspects 28 to 37, wherein the equivalent ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2) is 1:7.5 to 4.75:1.

[0114] 39. The organic polymerizable composition according to any one of aspects 28 to 38, wherein the aliphatic polyisocyanate (1) comprises isophorone diisocyanate.

[0115] 40. The organic polymerizable composition according to aspect 39, wherein at least one component is prepared from a bio-based carbon source.

[0116] 41. The organic polymerizable composition according to aspect 40, wherein the isophorone diisocyanate is prepared from acetone, which is a byproduct of hemicellulose fermentation.

[0117] 42. The organic polymerizable composition according to any one of aspects 28 to 41, wherein the polyol component (ii) comprises at least one polyester polyol.

[0118] 43. The organic polymerizable composition according to aspect 42, wherein the polyester polyol is derived from an autolactone or is a mixture of polyester polyols containing up to four different autolactones.

[0119] 44. The organic polymerizable composition according to any one of aspects 28 to 43, wherein the polyol component (ii) further comprises trimethylolpropane.

[0120] 45. The organic polymerizable composition according to any one of aspects 28 to 44, wherein the aromatic diamine comprises diethyltoluene diamine.

[0121] 46. ​​The organic polymerizable composition according to any one of aspects 28 to 45, wherein the photochromic compound (iii) comprises two or more different photochromic compounds.

[0122] 47. The organic polymerizable composition according to any one of aspects 28 to 46, further comprising (c) isophorone diisocyanate.

[0123] 48. A polymeric product formed from an organic polymerizable composition according to any one of aspects 28 to 47.

[0124] 49. An optical article formed from the polymer product according to aspect 48.

[0125] 50. The optical article according to aspect 49, wherein the optical article includes transparent film; glass; colored or colorless lens; plano lens or prescription lens; sports mask; protective mask; component for augmented reality, virtual reality, mixed reality or smart glasses; or goggles.

[0126] 51. A method for reducing the opacity of an optical article, the method comprising:

[0127] (a) To prepare isocyanate-functionalized prepolymers by reacting together the following:

[0128] (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the isocyanate functional group in the aliphatic polyisocyanate (1) is in an equivalent ratio of 1:8 to 5:1 to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2); and

[0129] (ii) A polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent.

[0130] (b) In the presence of a photochromic compound, reacting the prepolymer formed in (a) with an aromatic diamine having at least one primary amino group to form a polymer; and

[0131] (c) Optical articles are formed from polymer products.

[0132] 52. The method according to aspect 51, wherein the equivalence ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexylisocyanate) (2) is 1:7.5 to 4.75:1.

[0133] 53. The method according to aspect 51 or 52, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2500 g / equivalent.

[0134] 54. The method according to any one of aspects 51 to 53, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 150 to 2000 g / equivalent.

[0135] 55. The method according to any one of aspects 51 to 54, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2000 g / equivalent.

[0136] 56. The method according to any one of aspects 51 to 55, wherein the photochromic compound comprises a functional group that reacts with the isocyanate functional prepolymer.

[0137] 57. The method according to any one of aspects 51 to 56, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 10% by weight and at most 80% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0138] 58. The method according to any one of aspects 51 to 57, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 20% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0139] 59. The method according to any one of aspects 51 to 58, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 30% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0140] 60. The method according to any one of aspects 51 to 59, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 40% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0141] 61. The method according to any one of aspects 51 to 60, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of up to 70% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0142] 62. The method according to any one of aspects 51 to 61, wherein the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of up to 60% by weight, based on the total weight of the aliphatic polyisocyanate (1) and the 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0143] 63. The method according to any one of aspects 51 to 62, wherein the aliphatic polyisocyanate (1) comprises isophorone diisocyanate.

[0144] 64. The method according to any one of aspects 51 to 63, wherein the polyol component (ii) comprises at least one polyester polyol.

[0145] 65. The method according to aspect 64, wherein the polyester polyol is derived from an autolactone or is a mixture of polyester polyols containing up to four different autolactones.

[0146] 66. The method according to any one of aspects 51 to 65, wherein the polyol component (ii) further comprises trimethylolpropane.

[0147] 67. The method according to any one of aspects 51 to 66, wherein the aromatic diamine comprises diethyltoluene diamine.

[0148] 68. A method for reducing the opacity of an optical article, the method comprising:

[0149] (a) To prepare isocyanate-functionalized prepolymers by reacting together the following:

[0150] (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the equivalence ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2) is from 1:8 to 5:1;

[0151] (ii) a polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent; and

[0152] (iii) A photochromic compound containing a functional group that reacts with the polyisocyanate component (i);

[0153] (b) reacting the prepolymer formed in (a) with an aromatic diamine having at least one primary amino group; and

[0154] (c) Optical articles are formed from polymer products.

[0155] 69. The method according to aspect 68, wherein the equivalence ratio of the isocyanate functional group in the aliphatic polyisocyanate (1) to the isocyanate functional group in the 4,4'-methylenebis(cyclohexylisocyanate) (2) is 1:7.5 to 4.75:1.

[0156] 70. The method according to aspect 68 or 69, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2500 g / equivalent.

[0157] 71. The method according to any one of aspects 68 to 70, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 150 to 2000 g / equivalent.

[0158] 72. The method according to any one of aspects 68 to 70, wherein the difunctional polyol and / or trifunctional polyol has a calculated hydroxyl equivalent weight of 200 to 2000 g / equivalent.

[0159] The following working examples are intended to further describe and demonstrate the compositions, polymers, articles, and methods described herein. It should be understood that this disclosure is not necessarily limited to the examples described in this section. Components mentioned elsewhere in the specification as suitable alternatives but not shown in the working examples below are expected to provide results comparable to their shown counterparts. Unless otherwise stated, all parts are by weight.

[0160] Example

[0161] The reactants used in the example are as follows:

[0162]

[0163] Example 1

[0164] An isocyanate-functionalized prepolymer was prepared in a weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) of 10:90 and an equivalent ratio of 1:7.59. 4,4-dicyclohexylmethane diisocyanate (507 g, 3.87 equivalents), isophorone diisocyanate (56.3 g, 0.51 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and trimethylolpropane (TMP) (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction was continued until the indicated isocyanate content of 12% (approximately 350 g / eq isocyanate equivalent) was achieved by titration. The isocyanate content of the isocyanate-functionalized prepolymer prepared in each example was determined by reacting it with excess dibutylamine (DBA), followed by titration of unreacted DBA with HCl according to ASTM-2572-97 to form the corresponding urea. The titration was performed using a Metrohm 809 Titrando automated titrator unit equipped with 800 Dosino dosing units.

[0165] Example 2

[0166] An isocyanate-functionalized prepolymer was prepared in a weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) of 20:80 and an equivalent ratio of 1:3.37. 4,4-dicyclohexylmethane diisocyanate (438.6 g, 3.34 equivalents), isophorone diisocyanate (109.7 g, 0.99 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and trimethylolpropane (TMP) (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction was continued until the indicated isocyanate content of 12% (approximately 350 g / eq isocyanate equivalent) was achieved by titration. The isocyanate content of the isocyanate-functionalized prepolymer prepared in each example was determined by reacting it with excess dibutylamine (DBA), followed by titration of unreacted DBA with HCl according to ASTM-2572-97 to form the corresponding urea. The titration was performed using a Metrohm 809 Titrando automated titrator unit equipped with 800 Dosino dosing units.

[0167] Example 3

[0168] An isocyanate-functionalized prepolymer was prepared in a weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) of 30:70 and an equivalent ratio of 1:1.98. 4,4-dicyclohexylmethane diisocyanate (373.8 g, 2.85 equivalents), isophorone diisocyanate (160.2 g, 1.44 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and trimethylolpropane (TMP) (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction continues until the indicated isocyanate content of 12% (approximately 350 g / eq) is achieved by titration.

[0169] Example 4

[0170] An isocyanate-functionalized prepolymer was prepared in a weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) of 40:60 and an equivalent ratio of 1:1.27. 4,4-dicyclohexylmethane diisocyanate (312.3 g, 2.38 equivalents), isophorone diisocyanate (208.2 g, 1.87 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and trimethylolpropane (TMP) (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction continues until the indicated isocyanate content of 12% (approximately 350 g / eq) is achieved by titration.

[0171] Example 5

[0172] An isocyanate-functionalized prepolymer was prepared in which the weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) was 50:50 and the equivalent ratio was 1.18:1. 4,4-dicyclohexylmethane diisocyanate (253.8 g, 1.93 equivalents), isophorone diisocyanate (253.8 g, 2.28 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and TMP (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction continues until the indicated isocyanate content of 12% (approximately 350 g / eq) is achieved by titration.

[0173] Example 6

[0174] An isocyanate-functionalized prepolymer was prepared in a weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) of 60:40 and an equivalent ratio of 1.77:1. 4,4-dicyclohexylmethane diisocyanate (198.1 g, 1.51 equivalents), isophorone diisocyanate (297.2 g, 2.67 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and trimethylolpropane (TMP) (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction continues until the indicated isocyanate content of 12% (approximately 350 g / eq) is achieved by titration.

[0175] Example 7

[0176] An isocyanate-functionalized prepolymer was prepared in a weight ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2) of 70:30 and an equivalent ratio of 2.75:1. 4,4-dicyclohexylmethane diisocyanate (145.1 g, 1.11 equivalents), isophorone diisocyanate (338.5 g, 3.05 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077A (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and TMP (4.3 g, 0.1 equivalents) were added to a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was then heated to maintain an internal temperature of 80°C. The reaction continues until the indicated isocyanate content of 12% (approximately 350 g / eq) is achieved by titration.

[0177] Example 8 (Comparison)

[0178] Isocyanate-functionalized prepolymers were prepared without the use of polyisocyanates (1). 4,4-Dicyclohexylmethane diisocyanate (579.3 g, 4.42 equivalents), CAPA 2047A (260.1 g, 1.3 equivalents), CAPA 2077 (70.1 g, 0.19 equivalents), CAPA 2403D (81.3 g, 0.04 equivalents), and TMP (4.3 g, 0.1 equivalents) were charged into a reactor. The contents were stirred at approximately 600 rpm under a continuous nitrogen atmosphere. The reactor was heated to maintain an internal temperature of 100 °C. The reaction was continued until the indicated isocyanate content of 12% (approximately 350 g / eq isocyanate equivalent) was achieved by titration.

[0179] 8 mm prepolymer casting

[0180] 37 g (0.105 equivalents) of the prepolymers of Examples 2, 5, 7, and Comparative Example 8 were warmed and mixed with a blend of 0.7 g of a hydroxy-functionalized indene-fused naphthylpyran photochromic compound and 0.3 g of MoldWiz® INT 1681 (a release agent available from AxelPlastics Research Laboratories, Inc.). The resulting mixtures were degassed at 70°C to 90°C for 4 hours. In separate containers, 8.7 g (0.098 equivalents) of PRIMACURE® DETDA 80 (DETDA) was maintained under reduced pressure until degassed. Each prepolymer mixture and DETDA were then combined and subjected to a 15-second mixing cycle using a Speedmixer DAC 400 high-speed mixer available from Hauschild Engineering. 35 g of the resulting mixture was poured into a 75 mm diameter glass mold. The mold is heated in an oven set to 125°C for 16 hours, then allowed to cool to below 85°C and demolded to obtain an 8 mm thick polymer disc.

[0181] According to the manufacturer's instructions, an HunterLab Ultra Scan PRO spectrophotometer was used to collect opacity data on the resulting polymer disks. Opacity is affected by and proportional to the sample thickness. An 8 mm thick disk magnifies the effect to provide measurable differences in opacity between samples.

[0182] 12 mm prepolymer casting

[0183] 63 g (0.18 equivalent) of each sample of prepolymer was warmed and mixed with a blend of 1.2 g of a hydroxy-functionalized indene-fused naphthylpyran photochromic compound and 0.5 g of MoldWiz® INT 1681 (a release agent available from Axel Plastics Research Laboratories, Inc.). The resulting mixture was degassed at 70°C to 90°C for 4 hours. In separate containers, 15 g (0.17 equivalent) of PRIMACURE® DETDA 80 (DETDA) was maintained under reduced pressure until degassed. Subsequently, each prepolymer mixture and DETDA were combined and subjected to a 10-second mixing cycle using a Speedmixer DAC 400 high-speed mixer available from Hauschild Engineering. The resulting mixture was poured into a circular glass mold (82 mm in diameter) with a 12 mm thick cavity. The mold is heated in an oven set to 125°C for 16 hours, then allowed to cool to below 85°C and demolded to obtain a 12 mm thick polymer disc.

[0184] According to the manufacturer's instructions, an HunterLab Ultra Scan VIS spectrophotometer was used to collect opacity data on the resulting polymer disks. Opacity is affected by and proportional to the sample thickness. A 12 mm thick disk magnified the effect to provide measurable differences in opacity between samples.

[0185] Table 1 summarizes the measured opacity of an 8 mm thick polymer disk:

[0186] Table 1

[0187]

[0188] Each of the 8 mm samples in Examples 2, 5, and 7 exhibited an opacity value of less than 28%, as shown in Table 1. It is believed that the 15-second mixing cycle of the prepolymer mixture and DETDA (opposite to the 10-second mixing cycle used for the 12 mm samples shown in Table 2 below) may have caused gelation affecting the opacity value, resulting in the absence of the expected decreasing trend in opacity value proportional to the ratio of polyisocyanate (1) to 4,4'-methylenebis(cyclohexylisocyanate) (2).

[0189] Table 2 is a summary of the measured opacity of a 12 mm thick polymer disk:

[0190] Table 2

[0191]

[0192] When exposed to ultraviolet (UV) radiation, each disc darkens (corresponding to the "active" state, exhibiting photochromic behavior). After the UV radiation source is removed, each disc returns to the "inactive" or undarkened state.

[0193] Although specific examples of this disclosure have been described above for illustrative purposes, it will be apparent to those skilled in the art that many variations may be made to the details of this disclosure without departing from the scope of the disclosure as defined in the appended claims. While various examples of this disclosure are described in a “comprising” manner, embodiments substantially consisting of or composed of the following are also within the scope of this invention.

Claims

1. An organic polymerizable composition comprising: (a) An isocyanate-functionalized prepolymer prepared from a reaction mixture, said reaction mixture comprising: (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the isocyanate functional group in the aliphatic polyisocyanate (1) is in an equivalent ratio of 1:8 to 5:1 to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2); and (ii) a polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent. (b) An aromatic diamine having at least one primary amino group; as well as (c) Photochromic compounds.

2. The organic polymerizable composition according to claim 1, wherein, based on the total weight of the aliphatic polyisocyanate (1) and the ,4'-methylenebis(cyclohexylisocyanate) (2), the aliphatic polyisocyanate (1) is present in the polyisocyanate component (i) in an amount of at least 10% by weight, or at least 20% by weight, or at least 30% by weight, or at least 40% by weight and at most 80% by weight, or at most 70% by weight, or at most 60% by weight.

3. The organic polymerizable composition according to claim 1 or 2, wherein the isocyanate functional group in the aliphatic polyisocyanate (1) has an equivalent ratio of 1:7.5 to 4.75:1 to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2).

4. The organic polymerizable composition according to any one of claims 1 to 3, wherein the aliphatic polyisocyanate (1) comprises isophorone diisocyanate.

5. The organic polymerizable composition according to claim 4, wherein at least one component is prepared from a bio-based carbon source.

6. The organic polymerizable composition according to claim 4 or 5, wherein the isophorone diisocyanate is prepared from acetone, wherein the acetone is a byproduct of hemicellulose fermentation.

7. The organic polymerizable composition according to any one of claims 1 to 6, wherein the polyol component (ii) comprises at least one polyester polyol.

8. The organic polymerizable composition according to claim 7, wherein the polyester polyol is derived from an autolactone or is a mixture of polyester polyols containing up to four different autolactones.

9. The organic polymerizable composition according to any one of claims 1 to 8, wherein the polyol component (ii) further comprises trimethylolpropane.

10. The organic polymerizable composition according to any one of claims 1 to 9, wherein the aromatic diamine (b) comprises diethyltoluene diamine.

11. The organic polymerizable composition according to any one of claims 1 to 10, wherein the reaction mixture further comprises (iii) a photochromic compound containing a functional group that reacts with the polyisocyanate component (i).

12. The organic polymerizable composition according to any one of claims 1 to 11, wherein the photochromic compound (c) comprises a functional group that reacts with the isocyanate functional prepolymer (a).

13. The organic polymerizable composition according to claim 11 or 12, wherein the functional group comprises a hydroxyl group, a primary amino group, a secondary amino group, a carboxylic acid group, and / or a thio group.

14. The organic polymerizable composition according to claim 11, wherein the photochromic compound (iii) is the same as or different from the photochromic compound (c).

15. The organic polymerizable composition according to any one of claims 1 to 14, further comprising (d) isophorone diisocyanate.

16. The organic polymerizable composition according to any one of claims 1 to 15, wherein the photochromic compound (c) comprises two or more different photochromic compounds.

17. A polymeric product formed from an organic polymerizable composition according to any one of claims 1 to 16.

18. An optical article formed from the polymer product according to claim 17.

19. The optical article of claim 17 or claim 18, wherein the optical article comprises transparent film; glass; colored or colorless lens; plano lens or prescription lens; sports mask; protective mask; component for augmented reality, virtual reality, mixed reality or smart glasses; or goggles.

20. An organic polymerizable composition comprising: (a) An isocyanate-functionalized prepolymer prepared from a reaction mixture, said reaction mixture comprising: (i) a polyisocyanate component comprising (1) an aliphatic polyisocyanate having at least one primary isocyanate functional group and at least one secondary isocyanate functional group; and (2) 4,4'-methylenebis(cyclohexyl isocyanate), wherein the isocyanate functional group in the aliphatic polyisocyanate (1) is in an equivalent ratio of 1:8 to 5:1 or 1:7.5 to 4.75:1 to the isocyanate functional group in the 4,4'-methylenebis(cyclohexyl isocyanate) (2). (ii) a polyol component comprising a difunctional polyol and / or a trifunctional polyol having a calculated hydroxyl equivalent weight of 150 to 2500 g / equivalent, or 200 to 2500 g / equivalent, or 150 to 2000 g / equivalent, or 200 to 2000 g / equivalent. as well as (iii) A photochromic compound containing a functional group that reacts with the polyisocyanate component (i); as well as (b) An aromatic diamine having at least one primary amino group.

Images