METHOD FOR PREPARING LOW TURBIDITY POLYMER COMPOSITIONS FOR USE IN HIGH REFRACTIVE INDEX OPTICAL MATERIALS.

Abstract

A method is provided for preparing a polyurethane or polythiourethane with a high refractive index and low bubbling and yellowing. A method is also provided for evaluating an aromatic polyiso(thio)cyanate material, such as an aromatic diisocyanate, for example, m-xylylene diisocyanate. The method assesses the transmittance of a sample of the isocyanate to determine whether the aromatic polyiso(thio)cyanate material will produce unacceptable bubbling or yellowing in a polymer composition with a high refractive index or high Abbe number.

Description

METHOD FOR PREPARING LOW TURBIDITY POLYMER COMPOSITIONS FOR USE IN HIGH REFRACTIVE INDEX OPTICAL MATERIALS CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority over U.S. Provisional Application No. 63 / 001,643, filed on March 30, 2020, the disclosure of which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION

[0002] A method is provided for preparing polyurethanes and polythiourethanes together with polyurethane and polythiourethane compositions and a method for evaluating the quality of isocyanate monomers for use in the manufacture of high refractive index optical products.

[0003] Isocyanates, such as aromatic polyisocyanates (e.g., m-xylylene diisocyanate (mXDI)) or polyisothiocyanates (collectively, polyiso(thio)cyanates), can be used in the manufacture of high-refractive-index optical products, such as lenses. For example, among others, isocyanates, such as diisocyanates, can be polymerized with diols or polyols to produce polyurethanes, and with di-thiols or poly-thiols to produce polythiourethanes (poly(thio)urethanes, collectively referred to as polyurethanes and polythiourethanes). Certain isocyanates, such as m-xylylene diisocyanates, are very labile and sensitive to very small amounts of water, resulting in polymer products with unacceptable properties, such as bubbling, cloudiness, and yellowing.

[0004] Optical articles, such as lenses, are analyzed after polymerization as part of a quality control process, where bubbles, turbidity, and yellowing can be determined by visual inspection, or absorbance can be determined at a specific wavelength, but this process is inefficient in terms of manufacturing time and costs and can produce significant delays in bringing a product to market.

[0005] A method is convenient for determining whether an isocyanate, such as a polyiso(thio)cyanate or an aromatic diisocyanate, an example of which is m-xylylene diisocyanate, will produce bubbling or discoloration, e.g., yellowing, in a final lens product. ^77. ίη / ΖΖΠΖ / Ε / ΥΙΛΙ BRIEF DESCRIPTION OF THE INVENTION

[0006] According to one aspect of the disclosure, a method for preparing a polymer composition is provided. The method comprises polymerizing a polymerizable composition comprising a mixture of an aromatic polyiso(thio)cyanate material and at least one polyol or polythiol, wherein the percent transmittance (%T) of the aromatic polyiso(thio)cyanate material used to prepare the polymerizable composition is measured at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate material added to the mixture has at least 35 percent transmittance (%T) at a wavelength of 310 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T of 100%.

[0007] In another aspect, a polymerizable composition is provided for use in the preparation of a polymer composition. The polymerizable composition comprises a mixture of an aromatic polyiso(thio)cyanate composition and a polyol compound or a polythiol, wherein the transmittance of the polyiso(thio)cyanate composition used to prepare the mixture is determined at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate composition added to the polymerizable composition has at least 35 percent transmittance (%T) at a wavelength of 310 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T of 100%.

[0008] In yet another aspect, a method is provided for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol. The method comprises illuminating a liquid sample of the lot of the aromatic polyiso(thio)cyanate material with a light source that produces light at 310 nm ± 2 nm; obtaining transmittance or absorbance values ​​of the light passing through the aromatic polyiso(thio)cyanate material;and determining from the transmittance or absorbance values ​​whether the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%, wherein, when the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%, it produces an optical article with a high refractive index and a low bubble and / or yellowing index when polymerized into a polymerizable composition with a polyol or a polythiol.

[0009] In a further aspect, a method for manufacturing a molded article is provided, which **77 Vf\l77(\7iaiWrA comprises preparing a polymerizable composition; introducing the polymerizable composition into a mold; and curing, at least partially, the polymerizable composition within the mold. The polymerizable composition comprises a mixture of an aromatic polyiso(thio)cyanate composition and a polyol compound or a polythiol, wherein the transmittance of the polyiso(thio)cyanate composition used to prepare the mixture is determined at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate composition added to the polymerizable composition has at least 35 percent transmittance (%T), at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit %T of 100%. [OO1O] Other aspects are provided as follows.

[0011] According to a first aspect, a method is provided for preparing a polymer composition, comprising polymerizing a polymerizable composition comprising a mixture of an aromatic polyiso(thio)cyanate material and at least one polyol or polythiol, wherein the percent transmittance (% T) of the aromatic polyiso(thio)cyanate material used to prepare the polymerizable composition is measured at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate material added to the mixture has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0012] According to a second aspect, a method is provided for preparing a polymer composition according to the first aspect, wherein the aromatic polyiso(thio)cyanate is an aromatic diisocyanate.

[0013] According to a third aspect, a method is provided for preparing a polymer composition according to the second aspect, wherein the aromatic polyiso(thio)cyanate is 7-xylylene diisocyanate.

[0014] According to a fourth aspect, a method is provided for preparing a polymer composition according to any of the first to third aspects, wherein the polyol or polythiol is selected from 4-mercaptomethyl-3,6-dithial,8-octandithiool, 1,5-dimercapto-3-thiapentane, 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-1-ol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, or mixtures of two or more of these.

[0015] According to a fifth aspect, a method is provided for preparing a polymer composition according to any of the first to fourth aspects, further comprising, prior to polymerizing the polymerizable composition, injecting the polymerizable composition into a mold to form an optical article.

[0016] Pursuant to a sixth aspect, a method is provided for preparing a polymer composition according to the fifth aspect, wherein the optical article is an ophthalmic article.

[0017] Pursuant to a seventh aspect, a method is provided for preparing a polymer composition according to the sixth aspect, wherein the ophthalmic article is a lens.

[0018] In accordance with an eighth aspect, a method is provided for preparing a polymer composition according to the seventh aspect, wherein the ophthalmic article is a spectacle lens.

[0019] According to a ninth aspect, a method is provided for preparing a polymer composition according to any of the first to eighth aspects, further comprising, prior to polymerizing the polymerizable composition, determining the percent transmittance of one or more batches of the polyiso(thio)cyanate material at 310 nm ± 2 nm; selecting a batch of the aromatic polyiso(thio)cyanate material having at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%; and combining the aromatic polyiso(thio)cyanate material from the selected batch with the polythiol to produce the polymerizable composition.

[0020] In accordance with a tenth aspect, a method is provided for preparing a polymer composition according to the ninth aspect, wherein determining the percent transmittance of one or more lots of the polyiso(thiocyanate material is carried out by illuminating a liquid sample of a lot of the aromatic polyiso(thiocyanate) material with a light source, including light at a wavelength of 310 nm ± 2 nm; and measuring the % T at 310 nm ± 2 nm.

[0021] According to an eleventh aspect, a method is provided for preparing a polymer composition according to any of the first to tenth aspects, wherein the aromatic polyiso(thio)cyanate material has at least 40 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0022] According to a twelfth aspect, a method is provided for preparing a polymer composition according to any of the first to tenth aspects, wherein the aromatic polyiso(thiocyanate) material has at least 50 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0023] According to a thirteenth aspect, a method is provided for preparing a polymer composition according to any of the first to eleventh aspects, wherein the aromatic polyiso(thio)cyanate material has at least 60 percent transmittance (% T) at a wavelength of 320 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit T % of 100% and measured at a wavelength of 320 nm ± 2 nm.

[0024] According to a fourteenth aspect, a polymerizable composition is provided for use in the preparation of a polymer composition comprising a mixture of an aromatic polyiso(thio)cyanate composition and a polyol compound or a polythiol, wherein the transmittance of the polyiso(thio)cyanate composition used to prepare the mixture is determined at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate composition added to the polymerizable composition has at least 35 percent transmittance (% T), at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0025] In accordance with a fifteenth aspect, a polymerizable composition is provided in accordance with the fourteenth aspect, wherein the aromatic polyiso(thio)cyanate is an aromatic diisocyanate.

[0026] According to a sixteenth aspect, a polymerizable composition is provided according to the fourteenth aspect, wherein the aromatic polyiso(thio)cyanate is a 77-xylylene diisocyanate.

[0027] According to a seventeenth aspect, a polymerizable composition is provided according to any of the fourteenth to sixteenth aspects, wherein the polyol or polythiol is 4-mercaptomethyl-3,6-dithia-1,8-octandithiool; 1,5-dimercapto-3-thiapentane; 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-1-ol; or a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl1,11-dimercapto-3,6,9-trithiaundecane.

[0028] According to an eighteenth aspect, a polymerizable composition is provided according to any of the fourteenth to seventeenth aspects, wherein the polyiso(thio)cyanate added to the polymerizable composition has at least 40 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0029] According to a nineteenth aspect, a polymerizable composition is provided according to any of the fourteenth to seventeenth aspects, wherein the polyiso(thio)cyanate added to the polymerizable composition has at least 50 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0030] According to a twentieth aspect, a polymerizable composition is provided according to any of the fourteenth to nineteenth aspects, wherein the ^77. ίη / 77P7 / E / YILI polüso(thio)cyanate added to the polymerizable composition has at least 60 percent transmittance (% T) at a wavelength of 320 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0031] According to a twenty-first aspect, a polymerizable composition is provided according to any of the fourteenth to twentieth aspects, wherein determining the percent transmittance of one or more lots of the aromatic polyiso(thio)cyanate material is carried out by illuminating a liquid sample of a lot of the aromatic iso(thio)cyanate material with a light source, including light at a wavelength of 310 nm ± 2 nm; and measuring the % T at 310 nm ± 2 nm.

[0032] Pursuant to a twenty-second aspect, a method is provided for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol, comprising illuminating a liquid sample of the lot of the aromatic polyiso(thio)cyanate material with a light source that produces light at 310 nm ± 2 nm; obtaining transmittance or absorbance values ​​of the light passing through the aromatic polyiso(thio)cyanate material;and determining from the transmittance or absorbance values ​​whether the aromatic iso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%, wherein, when the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%, it produces an optical article with a high refractive index and a low bubble and / or yellowing index when polymerized into a polymerizable composition with a polyol or a polythiol.

[0033] Pursuant to a twenty-third aspect, a method is provided for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol according to the twenty-second aspect, further comprising classifying the lot of the aromatic polyiso(thio)cyanate material according to its ability to produce an acceptable or unacceptable low bubble and / or yellowness index in a high refractive index optical article prepared from a copolymer produced by copolymerizing the aromatic polyiso(thio)cyanate material with a polyol or a polythiol,wherein the batch of aromatic polyiso(thio)cyanate material produces an acceptably low index of bubbles and / or yellowing when the composition of the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0034] In accordance with a twenty-fourth aspect, a method is provided for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol in accordance with the twenty-second or twenty-third aspect, wherein the lot of the aromatic polyiso(thio)cyanate compound produces an acceptably low bubble and / or yellowness index when the composition of the aromatic polyiso(thio)cyanate material also has 60 percent transmittance (% T) at a wavelength of 320 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0035] In accordance with a twenty-fifth aspect, a method is provided for identifying a lot of an aromatic polyiso(thiocyanate) material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol in accordance with the twenty-second through twenty-fourth aspects, wherein the optical article is a lens.

[0036] In accordance with a twenty-sixth aspect, a method is provided for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol in accordance with the twenty-second through twenty-fifth aspects, wherein the polyiso(thio)cyanate is 77-xylylene diisocyanate.

[0037] In accordance with a twenty-seventh aspect, a method is provided for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol in accordance with the twenty-second through twenty-sixth aspects, wherein the polyol or polythiol is 4-mercaptomethyl-3,6-dithio-8-octandithio-ol; 1,5-dimercapto-3-thiapentane; 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-1-ol; or a mixture of 5,7-dimercaptomethyl-1,1-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,1-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,1-dimercapto-3,6,9-trithiaundecane.

[0038] According to a twenty-eighth aspect, a method for manufacturing a molded article is provided, comprising preparing a polymerizable composition according to any of the fourteenth to twenty-first aspects; introducing the polymerizable composition into a mold; and curing, at least partially, the polymerizable composition within the mold. *>*>77 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1: Graph representing the % visible UV transmittance compared to wavelength for mXDI samples described in the Example.

[0040] Figure 2: Graph representing the yellowness index of the polymers compared to the percentage of transmittance (% T) at 310 nm for mXDI samples described in the Example. DETAILED DESCRIPTION OF THE INVENTION

[0041] As used herein, the articles un, una, el and la include plural referents unless expressly and unequivocally limited to one referent.

[0042] Unless otherwise indicated, all ranges or relationships disclosed herein shall be understood to encompass each and every subrange or subrelationship included therein. For example, a range or relationship indicated as 1 to 10 shall be deemed to include each and every subrange between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges or subrelationships that begin with a minimum value of 1 or more and end with a maximum value of 10 or less, such as, but not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0043] Apart from operational examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, etc., used in the descriptive memorandum and the claims shall be understood as modified in all cases by the expression around.

[0044] The methods provided herein use a transmittance measurement to analyze a sample of an aromatic polyiso(thio)cyanate composition to predict the presence of bubbling or yellowing in an optical article, such as a lens, produced from a copolymer made by polymerizing aromatic polyiso(thio)cyanate, such as mXDI, with a suitable polythiol or polyol, such as a dithiol or diol. Aromatic polyiso(thio)cyanates, such as mXDI, can be highly sensitive to water, and impurities can cause bubbling or yellowing in an optical article prepared from a polymerization product, which is the result of the polymerization reaction of aromatic polyiso(thio)cyanate with a suitable polythiol or polyol.Impurities in an aromatic polyiso(thiocyanate) composition, such as an mXDI composition, may include phenol, dichlorobenzene, (x-chloromethyl)benzene, and / or chloroxylylene isocyanate, among other impurities, such as degradation products, depending on the iso(thiocyanate) monomer compound. The term polyiso(thiocyanate), when referring to compounds or compositions, collectively refers to both polyisocyanate compounds or compositions and polyisothiocyanate compounds or compositions.

[0045] In this respect, a method for preparing a polymer composition is provided. A polymer composition is prepared from precursors, such as monomers and macromers. Any suitable reaction condition, catalyst, cofactor, or crosslinking agent may be used to carry out the polymerization reaction used to prepare a polymer composition.In the polymerization method presented herein, the aromatic polyiso(thiocyanate) material is analyzed before carrying out the polymerization reaction and, generally, before adding the aromatic polyiso(thiocyanate) material to the polymerization reaction mixture (polymerizable composition) to determine whether the batch of aromatic polyiso(thiocyanate) material to be used in the polymerization reaction mixture is of sufficient quality to prevent the formation of yellowing and / or bubbles in the polymerization product (reaction product of the polymerization reaction). A batch is defined as any volume of a composition and refers to a complete batch of a composition, e.g., as received, or any portion thereof.

[0046] The transmittance of a batch can be evaluated once or multiple times, for example, immediately during manufacturing, shipping, at regular intervals, or immediately before use. Any suitable spectrophotometric method can be used to determine the percent transmittance. Likewise, properties related to percent transmittance, such as absorbance values, can be converted to percent transmittance to determine if a sample meets the requirements, for example, of at least 35 percent transmittance (%T), measured at a wavelength of 310 nm with an optical path length of one centimeter using a quartz cuvette calibrated in water having a unit %T of 100%. For example, among others, Beer-Lambert's law and suitable equations can be used to interconvert transmittance and absorbance values.

[0047] As a measure of the quality of the batch of aromatic polyiso(thio)cyanate material, the batch shall have a transmittance of at least 35 percent transmittance (%T), at least 40% T, or at least 50% T, at a wavelength of 310 nm, in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T of 100%. The aromatic polyiso(thio)cyanate material as measured may be pure, without any additional solvents. Alternatively, the material may include solvents and / or other ingredients, provided that such other ingredients do not interfere with the ability to determine the quality of the aromatic polyiso(thio)cyanate material, as described herein.

[0048] Transmittance can be measured at 310 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit T percentage of 100%. Alternatively, transmittance can be measured at any suitable wavelength, e.g., 310 nm ± 77 nm, and in any suitable cuvette or spectrophotometric system, with any standard or calibration method suitable for obtaining a measurement at a wavelength of 310 nm, in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit T percentage of 100%.

[0049] In addition to or as an alternative to measuring the transmittance at 310 nm ± 2 nm, the transmittance of the batch of aromatic polyiso(thio)cyanate composition may also be measured at a second wavelength, such as 320 nm ± 2 nm. For use in a polymerization reaction, the batch may have a transmittance of at least 60 percent transmittance (%T) at a wavelength of 320 nm, in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T of 100%. As with the measurement of transmittance at 310 nm, any suitable measurement method may be used to determine if the lot meets the requirements of having a transmittance of at least 60 percent transmittance (% T) at a wavelength of 320 nm, in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

[0050] In the methods and compositions provided herein, the polymerizable composition includes an aromatic polyiso(thiocyanate) material that was evaluated and verified, confirmed, or certified at least once prior to preparation and prior to polymerization to meet the stated transmittance requirement. This verification, confirmation, or certification may be performed at any time prior to the use of the composition in a polymerization reaction.

[0051] In some respects, a method is also provided herein for identifying a batch of aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low cloud and / or yellowness index free of bubbles (e.g., ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol. The method may comprise illuminating a liquid sample of the batch of aromatic polyiso(thio)cyanate material (e.g., aromatic polyiso(thio)cyanate monomer composition) with a light source that produces light at 310 nm ± 2 nm. The transmittance or absorbance values ​​of the light passing through the aromatic polyiso(thio)cyanate material can then be obtained.Based on transmittance or absorbance values, it can be determined whether the iso(thio)cyanate material has at least 35 percent transmittance (%T) at a wavelength of 310 nm in a quartz cuvette with a one-centimeter optical path, calibrated in water with a unit %T of 100%. When the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (%T) at a wavelength of 310 nm in a quartz cuvette with a one-centimeter optical path, calibrated in water with a unit %T of 100%, the aromatic polyiso(thio)cyanate material can produce an optical article with a high refractive index and a low yellowness index with few bubbles when polymerized in a polymerizable composition with a polyol or a polythiol.

[0052] As used herein, the term isocyanate, and related terms, refers to a compound that includes at least one isocyanate group (-NCO). A polyisocyanate includes at least two isocyanate groups (-NCO). An aromatic isocyanate refers to isocyanates comprising an aromatic group where at least one isocyanate group (-NCO) is attached to the aromatic group directly or indirectly, such as by one or more methylene groups. Aromatic diisocyanate refers to isocyanates, such as mXDI, comprising two isocyanate groups (-NCO) and one aromatic group, and aromatic polyisocyanate refers to isocyanates, such as mXDI, comprising at least two isocyanate groups (-NCO) and one aromatic group.

[0053] As used herein, the term isothiocyanate, and related terms, refers to a compound comprising at least one isothiocyanate (-NCS) group. A polyisothiocyanate comprises at least two isothiocyanate (-NCS) groups. An aromatic isothiocyanate refers to isothiocyanates comprising an aromatic group where at least one isothiocyanate (-NCS) group is attached to the aromatic group directly or indirectly, such as by one or more methylene groups. An aromatic diisothiocyanate refers to isothiocyanates comprising two isothiocyanate (-NCS) groups and one aromatic group, and an aromatic polyisothiocyanate refers to isothiocyanates comprising at least two isothiocyanate (-NCS) groups and one aromatic group.

[0054] The classes of aromatic polyiso(thio)cyanates that can be evaluated by or used in the methods of the present invention include, among others, aromatic polyiso(thio)cyanate compounds; aromatic polyiso(thio)cyanate compounds that include one or more thioether linkages; aromatic polyiso(thio)cyanate compounds that include one or more disulfide bridges; and aromatic polyiso(thio)cyanate compounds that include at least one isothiocyanate group and at least one isocyanate group.

[0055] Examples of aromatic polyisocyanate compounds from which the aromatic polyiso(thio)cyanate compound can be selected include, but are not limited to, 1,2-benzene diisocyanate, 1,3-benzene diisocyanate, 1,4-benzene diisocyanate, tolylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylenebis(2-methylphenyl isocyanate), bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, bis(isocyanatomethyl)benzene, xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, α,α,α',α'tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethylphenyl)ether,bis(isocyanatoethyl)phthalate, 2,5-di(isocyanatomethyl)furan and combinations of two or more of these. *>*>77 ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ

[0056] A non-limiting example of an aromatic polyisocyanate compound from which the aromatic polyiso(thio)cyanate compound can be selected is 77-xylylene diisocyanate (mXDI).

[0057] Examples of aromatic polyisothiocyanate compounds, from which the aromatic polyiso(thiocyanate) compound can be selected, include, among others, benzene 1,2-diisothiocyanate, benzene 1,3-diisothiocyanate, benzene 1,4-diisothiocyanate, toluene 2,4-diisothiocyanate, m-xylene 2,5-diisothiocyanate, 4,4'-methylenebis(phenyl isothiocyanate), 4,4'-methylenebis(2-methylphenyl isothiocyanate), 4,4-methylenebis(3-methylphenyl isothiocyanate), benzophenone 4,4'-diisothiocyanate, benzophenone 4,4'-diisothiocyanate-3,3'-dimethylbenzophenone, or bis(4-isothiocyanatophenyl) ether and combinations of two or more of these.

[0058] Examples of aromatic polyisocyanate compounds that include one or more sulfide bridges, from which the aromatic polyiso(thio)cyanate compound can be selected, include, among others, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis(4-isocyanatophenyl)sulfide, bis(4-isocyanatomethylphenyl)sulfide, and combinations thereof.

[0059] Examples of aromatic polyisocyanate compounds that include one or more disulfide bridges, from which the aromatic polyiso(thiocyanate) compound can be selected, include, among others, bis(4-isocyanatophenyl)disulfide, bis(2-methyl-5-isocyanatophenyl)disulfide, bis(3-methyl-5-isocyanatophenyl)disulfide, bis(3-methyl-6-isocyanatophenyl)disulfide, bis(4-methyl-5-isocyanatophenyl)disulfide, bis(4-methoxy-3-isocyanatophenyl)disulfide, and combinations of two or more of these.

[0060] As used herein, references to linear or branched groups, such as linear or branched alkyl, are understood to include a methylene group or a methyl group; groups that are linear, such as linear C2-C10 alkyl groups; and groups that are suitably branched, such as branched C3-C10 alkyl groups.

[0061] Polyols or polythiols can be bonded or polymerized in a polymerizable composition to the aromatic polyiso(thiocyanate) described herein to produce copolymers, such as polyurethane and polythiourethane polymers.Examples of suitable polyols include, but are not limited to, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-propylene glycol, triethylene glycol, tripropylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol and neopentyl glycol, hydrogenated bisphenol A; cyclohexanediol; propanediols including 1,2-propanediol, 1,3-propanediol, butyl ethyl propanediol, 2-methyl-1,3-propanediol and 2-ethyl-2-butyl-1,3-propanediol; butanediols including 1,4-butanediol, 1,3-butanediol and 2-ethyl-1,4-butanediol; pentanediols including trimethylpentanediol and 2-methylpentanediol; 2,2,4-trimethyl-3-pentanediol, cyclohexanediol; hexanediols including 1,6-hexanediol; 2-ethyl-1,3-hexanediol, caprolactondiol (e.g., the reaction product of epsilon-caprolactone and ethylene glycol); hydroxyalkylated bisphenols; 77 glycols.Ln / Zznz / E / YIAI polyether, for example, poly(oxytetramethylene) glycol; trimethylol propane, di-trimethylol propane, pentaerythritol, di-pentaerythritol, trimethylol ethane, trimethylol butane, dimethylol cyclohexane, glycerol, tris(2-hydroxyethyl) isocyanurate and the like.

[0062] Suitable polythiol compositions include a polythiol compound (A) comprising at least two thiol groups. In some embodiments, the polythiol compound (A) comprises at least three thiol groups. In some further embodiments, the polythiol compound (A) comprises from 2 to 10 thiol groups, from 2 to 8 thiol groups, from 2 to 6 thiol groups, or from 2 to 5 thiol groups, including the numbers indicated. In some further embodiments, the polythiol compound (A) comprises 2, 3, 4, 5, or 6 thiol groups. In some embodiments, the polythiol compound (A) optionally comprises at least one hydroxyl group, such as, but not limited to, 0, 1, 2, or 3 hydroxyl groups.

[0063] With some embodiments, the polythiol compound (A) is represented by the following Formula (A-II), ^77. ίη / ΖΖΠΖ / Ε / ΥΙΛΙ

[0064] With some additional embodiments, the polythiol compound (A) is represented by the following Formula (A-III), ch2sh s-ch2ch2^—^s—chch2 (A-III) ch2oh s—chch2-^— z CH2OH s—ch2ch^--S-CH2CH2—SH z'JP

[0065] With reference to Formula (A-III): p is from 0 to 4; yx, t, t', zyz' are each independently from 0 to 4 for each p. With some forms of embodiment, and with further reference to Formula (A-III): p is from 0 to 3; yx, t, t', zyz' are each independently from 0 to 3 for each p.

[0066] Examples of polythiols from which the polythiol compound (A) can be selected include, but are not limited to, 1,2-ethandthiol, 1,2-propandthiol, 1,3-propandthiol, 1,2,3-propantrithiol, tetrakis(mercaptomethyl)methane, trimethylolpropan tris(2-mercaptoacetate), trimethylolpropan tris(3-mercaptopropionate), trimethylolethan tris(2-mercaptoacetate), trimethylolethan tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), l,2,3-tris(mercaptomethylthio)propane, l,2,3-tris(2-mercaptoethylthio)propane, l,2,3-tris(3mercaptopropylthio)propane, l,5-dimercapto-3-thiapentane, 4-mercaptomethyl-l,8-dimercapto-3,6dithiaoctane, 5,7-dimercaptomethyl,ll,ll-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-l,lldimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl,ll-dimercapto-3,6,9-trithiaundecane, 7(mercaptomethyl)-3,6,9,12-tetrathiatetradecan-l,14-dithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane,tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane and combinations of two or more of these.

[0067] Examples of polythiol (A) compounds that include a hydroxyl group include, but are not limited to, 2,3-dimercapto-l-propanol; l,3-dimercaptopropan-2-ol; 2,3-bis((2-mercaptoethyl)thio)propan-l; l,3-bis((2-mercaptoethyl)thio)propan-2-ol; 3-mercapto-2-((2-mercaptoethyl)thio)propan-l-ol; 2-((2-mercaptoethyl)thio)-3-((2-((2-mercaptoethyl)thio)ethyl)thio)propan-l-ol; 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-l-ol; glycerin bis(2-mercaptoacetate); glycerin bis(3mercaptopropionate); l,3-dimercapto-2-propanol; trimethylolpropane bis(2-mercaptoacetate); trimethylolpropane bis(3-mercaptopropionate); pentaerythritol bis(2-mercaptoacetate); pentaerythritol tris(2-mercaptoacetate); pentaerythritol bis(3-mercaptopropionate); and pentaerythritol tris(3mercaptopropionate).

[0068] With some embodiments, the polythiol compound (A) is selected from at least one of the following polythiol compounds represented by Formulas (A-3) to (A-8): *>*>77 ίη / 77Π7 / E / YΙΛΙ SH(A.4) *>*>77 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ and combinations of two or more of these.

[0069] In some embodiments, the methods for preparing the polythiol compound (A) may involve the use of acids and / or bases during the isolation of the polythiol compound (A). Therefore, in some embodiments, the polythiol compound (A) may have an acidic or basic pH. For non-limiting illustrative purposes, if an excess of acid, such as HCl, is used, the isolated polythiol compound (A) may have an acidic pH. For further non-limiting illustrative purposes, if an excess of base, such as NaOH, is used, the resulting polythiol compound (A) may have a basic pH.

[0070] Also provided herein is a polymerizable composition comprising (i) an aromatic polyiso(thiocyanate) material described above herein and (ii) a mixing tank comprising one or more impellers; continuous mixing, such as in a static mixer and / or extruder; impact mixing, such as within a mixing chamber of a molding injection head; and combinations of such mixing methods.

[0077] Once the mixture is formed, the polymerizable composition can be introduced into a mold by any suitable method. The polymerizable composition can be introduced into a mold by methods including, but not limited to, pouring, such as from a beaker or other container, and / or injection, such as from a molding injection head. In some embodiments, the mold is a multi-piece mold, such as a two-piece mold that includes at least one injection port and, optionally, one or more gaskets.

[0078] After the introduction of the mold, the polymerizable composition can be cured within the mold. The term "cured" is as defined above herein. The polymerizable composition can be cured within the mold at room temperature, such as about 25°C; elevated temperature, such as 90°C to 204°C, 100°C to 177°C, or 110°C to 140°C, for a period of 20 to 240 minutes; or any combination thereof. With some embodiments, the polymerizable composition is substantially fully cured within the mold.

[0079] In some embodiments, after the curing of the polymerizable composition within the mold, the resulting polymerization product is generally removed from the mold. The polymerization product may be subjected to one or more additional stages such as, but not limited to, milling; surface cleaning; surface treatment, such as etching and / or plasma treatments; the formation of one or more coatings on at least one surface of the polymerization product, such as, but not limited to, protective coatings, tinted coatings, and / or antireflective coatings; and combinations thereof.

[0080] In the examples presented herein, the percentage of light transmittance within the wavelength range of 300 nm to 325 nm, or at a single wavelength of 310 nm, is used to predict the suitability of the sample for preparing polymerization products with a low bubbling index and yellowness. Beyond theory, it is believed that insignificant impurities, undetectable by other standard methods, exhibit small differences in refractive index compared to the bulk sample, resulting in a reduced percentage of transmittance in a selected portion of the ultraviolet spectrum. The %T can be quantified in several ways. In one example, a different optical system can be used.The choice of wavelength used to obtain a transmittance value may vary to some extent to effectively distinguish aromatic polyiso(thio)cyanate material, which, when polymerized as described herein, can produce polyurethane and polythiourethane polymer compositions and optical articles with a low bubbling and yellowing index. A sample of aromatic polyiso(thio)cyanate material having at least 35 percent transmittance (%T), measured at a wavelength of 310 nm with an optical path length of one centimeter using a water-calibrated quartz cuvette having a unit %T of 100%, can be identified with any equivalent transmittance or absorbance measurement.

[0081] Due to the nature of the impurities found in degraded aromatic polyiso(thio)cyanates and the physics of transmittance and absorbance, non-mXDI aromatic polyiso(thio)cyanates are expected to alter transmittance at approximately the same wavelength range as mXDI. Non-limiting examples of impurities may include urea and biuret products formed when polyiso(thio)cyanates are exposed to moisture.

[0082] For the methods herein, the percent transmittance (%T), or any other optical property that can be used to measure spectral properties such as absorbance of light, may be measured at any wavelength from 300 nm to 325 nm, such as 310 nm, 311 nm, 312 nm, 313 nm, 314 nm, or 315 nm, or for any range within the range of 300 nm to 325 nm, such as 300 nm to 400 nm, 300 nm to 375 nm, 300 nm to 350 nm, 300 nm to 325 nm, or 305 nm to 315 nm, or for a subrange of any of the foregoing, such as, for example, but not limited to, 305 nm to 320 nm or 306 nm to 318 nm, to effectively distinguish the aromatic polyiso(thiocyanate) materials that produce polyurethane and polythiourethane polymer compositions and optical articles with high refractive index (e.g., η > 1).6) and low bubble and / or yellowness index of aromatic polyiso(thiocyanate) materials that can be polymerized to produce polyurethane and polythiourethane polymer compositions and optical articles with high refractive index and unacceptably high bubble and / or yellowness index.

[0083] A light source emits light in any specified spectrum and may be coherent (e.g., a laser) or incoherent (e.g., a lamp). For the purposes of this document, the light source emits within the ultraviolet (UV) range of 300 nm to 325 nm, but it may produce a broader or narrower spectrum. A broad-spectrum light source, covering, for example, a large portion of the visible light range along with UV emissions suitable for the methods described herein, may be used. A typical spectrophotometer may be used to measure the transmission or absorbance spectra for the methods described herein, and it may be configured to measure at a single wavelength or over a range of wavelengths.

[0084] The present invention is described more particularly in the following examples, which are intended to be illustrative only, since numerous modifications and variations will be evident to persons of average skill. Unless otherwise specified, all parts and all percentages are by weight. *>*>77 ίΠ / ΖΖηΖ / Ε / ΥΙΛΙ Examples Measurement of the percentage of transmittance (% of T) of mXDI

[0085] Samples of m-xylylene diisocyanate (mXDI) were evaluated for percent transmittance at 310 nm and 320 nm according to the following procedure. Initial corrected percent transmittance measurements were made using a Cary 300 UV-Vis spectrophotometer. Ultraviolet-visible (UV-Vis) percent transmittance values ​​were obtained in the wavelength range of 800–200 nm with a wavelength accuracy of ±0.2 nm. The separation between data points on the spectral bandwidth and wavelength axes was set at 2.0 nm and 1.0 nm, respectively. For the analysis, a pair of UV-grade quartz cuvettes with a path length of 1 cm were used. One cuvette was filled with isocyanate monomer and placed in the sample beam position, and the second was filled with deionized water and placed in the instrument's reference beam position.The percentage transmittance of each sample was recorded at 310 nm and 320 nm, as shown in Table 1. *>*>77 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ Table 1: % transmittance of mXDI samples mXDI % of T at 310 nm % of T at 320 nm Sample A 55.6 78.2 Sample B 54.1 78.7 Sample C 36.7 63.0 Sample D 27.8 58.7 Sample E 26.3 55.9 Sample F 15.1 41.6

[0086] Figure 1 provides a graph showing the relationship between the % T of each of the evaluated mXDI lots with respect to wavelength. This graph illustrates that the % T at 310 nm or between 305 and 320 nm, such as at 311 nm, 312 nm, 313 nm, 314 nm, 315 nm, 316 nm, 317 nm, 318 nm, 319 nm, or 320 nm, can be used to differentiate lots of aromatic polyiso(thiocyanates), such as mXDI, capable of producing an acceptable yellowness index and bubbling. Casting process

[0087] Each of the samples A to F was formulated in 5 kg batches according to the following general casting procedure to obtain cast articles of Examples 1 to 6. Table 2. Cast Example mXDI Sample Example 1 Sample A Example 2 Sample B Example 3 Sample C Example 4 Sample D Example 5 Sample E Example 6 Sample F bb77 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ

[0088] First, according to Table 2, the indicated m-xylylene diisocyanate (mXDI, 52 wt parts), dimethyltin dichloride (110 ppm total batch), and ZELEC® UN (a mold release agent available through Stepan Company; 1200 ppm total batch) were loaded into a 10 L reactor set at 18°C. The contents were mixed for 30 min under vacuum (<15 torr). The vacuum was released, 2,3-bis((2-mercaptoethyl)thio)-1-propanthiool (42 wt parts, with a water content of 650 ± 100 ppm) was introduced, and the resulting homogeneous solution was mixed at 140 rpm under vacuum (<15 torr) for 1 h. The vacuum was released, and nitrogen was introduced. Mixing continued at 40 rpm for 2.5 h. The resulting solution was filtered through a 5-micron Polycap™HD filtration capsule and injected into a tape-secured glass mold. The glass mold was configured to produce a base-5 lens with a diameter of 85 mm and a thickness of 8 mm at the center.The mold was placed in an oven and gradually heated from 15°C to 120°C over a period of approximately 16 hours; it was then held at 120°C for a sufficient time to complete the polymerization reaction, typically at least four hours. Once polymerization was complete, the mold was removed from the oven, and the molten lens was released from the mold. A total of 55 lenses were molded for each of Examples 1 to 6. Results

[0089] A random sample of 10 lenses from each example composition was measured to determine the Yellowness Index (YI) using a Hunter UltraScan® Pro instrument, purchased from Hunter Associates Laboratory, Inc. The Yellowness Index was obtained using EasyMatchQC software. The measurements were confirmed using the following equation: Yl £313 = 100(CxY -CzZJ / Y Where Cx is a standard coefficient of 1.3013 for D65 / 10°C and Cz is a standard coefficient of 1.1498 for D65 / 10°C. X, Y, and Z were the production values ​​for each sample. The results, as an average of 10 representative samples, are shown in Table 3.

[0090] The 55 cast lenses for each cast composition were visually inspected for bubbles. Any bubbles present and visible to the naked eye on the lens were then measured from the outer edge of the lens. Any bubbles within 3 mm of the outer edge of the lens were considered acceptable; any bubbles beyond 3 mm on the lens, measured from the outer edge, were considered center bubbles and failed the inspection. A lens with no visible bubbles beyond the 3 mm edge area was considered PASS, even if bubbles were present along the 3 mm edge. The results of the center bubble test are shown in Table 3. Table 3: Evaluation of molten compositions using the yellowness index and bubbles. ^77. ίη / ΖΖΠΖ / Ε / ΥΙΛΙ mXDI samples with % of variable T YI of the lens (E313) % of central bubbles APPROVED Example 1 1.78 100 Example 2 1.73 100 Example 3 1.88 100 Example 4 1.85 100 Example 5 1.96 7 Example 6 2.09 0

[0091] Figure 2 provides a graph showing the relationship between the yellowness index and % T of the evaluated mXDI lots, illustrating that increasing the % T of the mXDI (e.g., at least 35% T at 310 nm and / or at least 60% T at 320 nm) correlates with an acceptable yellowness index.

[0092] All documents, including but not limited to patents and patent applications issued and referenced herein, unless otherwise stated, shall be deemed to be incorporated by reference in their entirety.

[0093] The forms of implementation were described with reference to various examples. Other people may notice modifications and alterations after reading and understanding the examples above. Accordingly, the examples above should not be interpreted as limiting disclosure.

Claims

1. A method for preparing a polymer composition, comprising polymerizing a polymerizable composition comprising a mixture of an aromatic polyiso(thio)cyanate material and at least one polyol or polythiol, wherein the percent transmittance (%T) of the aromatic polyiso(thio)cyanate material used to prepare the polymerizable composition is measured at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate material added to the mixture has at least 35 percent transmittance (%T), at least 40% T, or at least 50% T at a wavelength of 310 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T of 100%, and optionally at least 60% T at a wavelength of 320 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water which has a unit T % of 100%, and measured at a wavelength of 320 nm ± 2 nm.

2. The method according to claim 1, wherein the aromatic polyiso(thiocyanate) is an aromatic diisocyanate.

3. The method according to claim 2, wherein the aromatic polyiso(thiocyanate) is 77-xylylene diisocyanate.

4. The method according to any of claims 1-3, wherein the polyol or polythiol is selected from 4-mercaptomethyl-3,6-dithia-1,8-octandithiol, 1,5-dimercapto-3-thiapentane, 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-1-ol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, or mixtures of two or more of these.

5. The method according to any of claims 1-4, further comprising, prior to polymerizing the polymerizable composition, injecting the polymerizable composition into a mold to form an optical article.

6. The method according to claim 5, wherein the optical article is an ophthalmic article.

7. The method according to claim 6, wherein the ophthalmic article is a lens.

8. The method according to claim 6, wherein the ophthalmic article is a spectacle lens.

9. The method according to any of claims 1-8, further comprising, prior to polymerizing the polymerizable composition: ^77. Determining the percent transmittance of one or more batches of the polyiso(thio)cyanate material at 310 nm ± 2 nm; selecting a batch of the aromatic polyiso(thio)cyanate material having at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%; and combining the aromatic polyiso(thio)cyanate material from the selected batch with the polythiol to produce the polymerizable composition.

10. The method according to claim 9, wherein determining the percentage transmittance of one or more batches of the polyiso(thio)cyanate material is carried out by: illuminating a liquid sample of a batch of the aromatic polyiso(thio)cyanate material with a light source, including light at a wavelength of 310 nm ± 2 nm; and measuring the %T at 310 nm ± 2 nm.

11. A polymerizable composition for use in preparing a polymer composition comprising a mixture of an aromatic polyiso(thio)cyanate composition and a polyol or polythiol compound, wherein the transmittance of the polyiso(thio)cyanate composition used to prepare the mixture is determined at a wavelength of 310 nm ± 2 nm, and the aromatic polyiso(thio)cyanate composition added to the polymerizable composition has at least 35 percent transmittance (%T), at least 40% T, or at least 50% T at a wavelength of 310 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T of 100%, and optionally at least 60% T at a wavelength of 320 nm in a quartz cuvette with an optical path length of one centimeter, calibrated in water having a unit %T. of 100%, and measured at a wavelength of 320 nm ± 2 nm.

12. The polymerizable composition according to claim 11, wherein the aromatic polyiso(thiocyanate) is an aromatic diisocyanate.

13. The polymerizable composition according to claim 11, wherein the aromatic polyiso(thiocyanate) is xylylene diisocyanate.

14. The polymerizable composition according to any of claims 11-13, wherein the polyol or polythiol is: 4-mercaptomethyl-3,6-dithia-1,8-octandithiool; 1,5-dimercapto-3-thiaptane; 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-1-ol; or a mixture of 5,7-dimercaptomet¡ll,ll-dimercapto-3,6,9-tr¡t¡aundecane, 4,7d¡mercaptomet¡ll,ll-dimercapto-3,6,9-tr¡t¡aundecane and 4,8-d¡mercaptomet¡ll,ll-dimercapto-3,6,9 *>*>77 ίη / ΖΖΠΖ / Ε / ΥΙΛΙ tritiaundecane.

15. The polymerizable composition according to any of claims 11-14, wherein determining the percentage transmittance of one or more batches of the aromatic polyiso(thio)cyanate material is carried out by: illuminating a liquid sample of a batch of the aromatic polyiso(thio)cyanate material with a light source, including light at a wavelength of 310 nm ± 2 nm; and measuring the % T at 310 nm ± 2 nm.

16. A method for identifying a lot of an aromatic polyiso(thio)cyanate material that produces an optical article with a high refractive index and a low bubble and / or yellowness index (ASTM E313 method), when polymerized into a polymerizable composition with a polyol or a polythiol, comprising: illuminating a liquid sample of the lot of the aromatic polyiso(thio)cyanate material with a light source that produces light at 310 nm ± 2 nm; obtaining transmittance or absorbance values ​​of the light passing through the aromatic polyiso(thio)cyanate material;and determining from the transmittance or absorbance values ​​whether the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%, wherein, when the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%, it produces an optical article with a high refractive index and a low bubble and / or yellowing index when polymerized into a polymerizable composition with a polyol or a polythiol.

17. The method according to claim 16, further comprising classifying the batch of aromatic polyiso(thio)cyanate material according to its ability to produce an acceptable or unacceptable low bubble index and / or yellowness in a high refractive index optical article prepared from a copolymer produced by copolymerizing the aromatic polyiso(thio)cyanate material with a polyol or a polythiol, wherein the batch of aromatic polyiso(thio)cyanate material produces an acceptably low bubble index and / or yellowness when the composition of the aromatic polyiso(thio)cyanate material has at least 35 percent transmittance (% T) at a wavelength of 310 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

18. The method according to claim 16 or 17, wherein the batch of aromatic polyiso(thio)cyanate compound produces an acceptably low bubble index and / or yellowness when the aromatic polyiso(thio)cyanate material composition also has 60 percent transmittance (% T) at a wavelength of 320 nm in a quartz cuvette with an optical path of one centimeter, calibrated in water having a unit % T of 100%.

19. The method according to any of claims 16-18, wherein the optical article is a lens.

20. The method according to any of claims 16-19, wherein the polyiso(thio)cyanate is / 7+xylylene diisocyanate.

21. The method according to any of claims 16-20, wherein the polyol or polythiol is: 4-mercaptomethyl-3,6-dithia-1,8-octandithiool; 1,5-dimercapto-3-thiapentane; 2,3-bis((2-((2-mercaptoethyl)thio)ethyl)thio)propan-1-ol; or a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

22. A method for manufacturing a molded article, comprising preparing a polymerizable composition according to any of claims 11-15; introducing the polymerizable composition into a mold; and curing, at least partially, the polymerizable composition within the mold.