TWI285651B - Sulfur-containing polyurethane/polyurea resin-based optical polymerizate - Google Patents

Abstract

The present invention is directed to a novel method of preparing a polymerizate, which includes the step of polymerizing a two-component composition, which includes: a first component containing at least one polycyanate reactant having at least two functional groups selected from isocyanate, isothiocyanate and combinations thereof, the polycyanate reactant being the reaction product of: a polythiol monomer having at least two thiol groups; and a polycyanate monomer having at least two functional groups selected from isocyanate, isothiocyanate and combinations thereof; and a second component containing at least one polyamine reactant having at least two functional groups selected from primary amine, secondary amine and combinations thereof. The molar equivalent ratio of (NCO + NCS) groups from the first component to (-NH2 + -NH-) groups from the second component is from 0.5 to 100. The present invention is also directed to polymerizates prepared according to the method of the present invention. The present invention is further directed to photochromic articles that may be prepared from the polymerizates of the present invention.

Description

1285651 A7 V. INSTRUCTIONS (7 (I) ff c-r2

HS--Ri>-Q

ο-CH—CH2 〇-C-R2—SH The center and each of each of them are selected from the group consisting of an alkyl group of a straight chain or a branched chain, a cyclic alkyl group, a phenyl group, and an alkyl group substituted with Ci_C9. Phenyl. Examples of alkyl groups which may be selected from the center and the straight or branched chain of 112 include methyl, ethyl, 1,3-propyl, 1,2, propyl, 1,4, butyl. , hydrazine, butyl, phenyl, hexyl, heptyl, octyl, decyl, decyl, octadecyl and eicosyl, but not limited thereto . Examples of the cycloalkyl group which may be selected as each of Ri and I include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodextyl group, and an alkyl-substituted derivative thereof, but are not limited thereto. The divalent bonding core and heart may also be selected from a phenyl group and an alkyl substituted phenyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a fluorenyl group. In a preferred embodiment of the invention, each of the heart and the heart may be a methyl or ethyl group. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, prints a polythiol represented by Formula I, which can be derived from 3-mercapto-i,2-propanediol in the presence of a strong acid catalyst (eg, methanesulfonic acid) (Chemical Summary Service) (CAS) Registration No. 96-27-5) and esterification or transesterification of a thiol-functional carboxylic acid or a carboxylic acid ester while simultaneously removing water or alcohol from the reaction mixture. More particularly, it is preferred that the polythiol monosystem is related to the core of Formula 1 and that each of the methyl groups is 112. When used herein, a polythiol monomer (for example, 'thioglycerol bis(2-mercaptoacetate)), which is described and named with reference to the formula j, also includes the national standard for the country to which the residual paper size is applied ( CNS)A4 ^21G χ诺公发) 1285651 A7

V. INSTRUCTIONS (8) Any of the related co-product oligomer species and polythiol monomer compositions. For example, when the reaction mixture formed by the esterification reaction of 3-Myl-12-propanediol and the functional group tarenic acid (example, acetic acid) is washed with an excess of a base (for example, aqueous ammonia), the thiol group Oxidative coupling may occur. This oxidative coupling may result in the formation of oligomeric polythiol species with disulfide bonding (i.e., _s_s_bonding). The polythiol monomer used to prepare the polycyanate reactant may be a disulfide-bonded polythiol oligomer which can be self-contained in the presence of a basic catalyst to a polythiol group. The reaction of a thiol monomer with sulfur is obtained. The ratio of the polythiol monomer to the thiol molar g is m to (m-1), wherein m is an integer from 2 to 21. The polythiol monomer may be selected from the foregoing examples herein, for example, 2,5-dimercaptomethyl-1,4-dithiane. The sulfur used may be, for example, in the form of crystals, colloids, powders and sublimed sulfur, and has a purity of at least 98% and preferably at least 99%. The co-product 5^ species may comprise an oligomer of the formula I, which may be described by the formula la: la > loading -------- order --------- (please read the back first) Note on this page.) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 11 1285651 A7 B7

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

Wherein Ri and I are as described above, and n and m are each an integer from 〇 to 21, and n+m is at least 1. It is shown that 1a confirms that the oligomerization reaction can be produced via a disulfide bond between any of the thiol groups in the general structure I. Although all possibilities are not shown, Formula Ia is intended to mean all oligomers which may form from the general structure I. The alkaline catalyst used to prepare the disulfide-bonded polythiol polymer can be selected from the group consisting of ammonia, amines, and mixtures thereof. Examples of the amine include an alkylamine (for example, ethylamine and n-butylamine), a diamine amine (for example, diethylamine), a trialkylamine (for example, triethylamine), morpholine, and Substituted morpholine, piperidine and substituted piperidine, but are not limited thereto. The basic catalyst is typically present in an amount of from 0.001 to 1.0 mol% (e.g., from 0 01 to 0 mol%, based on the number of moles of the polythiol monomer present at the beginning of the reaction). The alkali catalyst may be injected into the reaction vessel together with the polythiol monomer and sulfur, or may be added to the reaction vessel after the addition of the polythiol monomer and sulfur. The synthesis of a disulfide-bonded polythiol oligomer can be carried out in a solvent (for example, a halogenated hydrocarbon (such as chloroform) 'aliphatic hydrocarbon (such as hexane), an aromatic hydrocarbon (such as toluene), and an ether ( It is carried out in the presence of, for example, tetrahydrofuran. The polythiol oligomer can be prepared at a temperature ranging from room temperature to the boiling point of the solvent (for example, room temperature to 120 C.) It can be used in the disulfide-bonded polysulfide of the present invention. The preparation of the alcohol oligomers is described in more detail in U.S. Patent No. 5,961,889, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety The alcohol oligomer may be selected from those represented by the following formula II: (Please read the note on the back and then fill out this page) _Shang--------Book---- The paper size of the curtain is applicable to the Chinese country. Standard (CNS) A4 specification (210 X 297 mm) 12 1285651 A7 B7 V. Description of invention (l〇) (Π)

The Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives, print the integers of the η series 1 to 21. The polythiol condensate represented by the general formula II can be produced by reacting 2,5-dibenzylmethyl-1,4-dithiane with sulfur in the presence of a basic catalyst (such as the foregoing) Got it. The polycyanate monomer (a)(ii) used to prepare the polycyanate reactant of the first component (a) may be selected from polyisocyanates having at least a diisocyanate group, and having at least an 'isothio group The acid S is an isothiocarbamic acid 6 and a polycyanate having an oleic acid vinegar and an isothiocyanate group. Optionally, the polyisocyanate of the polycyanate monomer (a) (ii) includes, but is not limited to, an aliphatic polyisocyanate; an ethylenically unsaturated polyisocyanate; an alicyclic polyisocyanate; wherein the isocyanate group An aromatic polyisocyanate not directly bonded to an aromatic ring (for example, α 5 α xylene diisocyanate); wherein the isocyanate group is directly bonded to the aromatic polyisocyanate of the aromatic group (for example, phenyl diisocyanate) An aliphatic polyisocyanate containing a sulfide bond; an aromatic polyisocyanate containing a sulfide or a disulfide bond; an aromatic polyisocyanate containing a ruthenium bond; a polyisocyanate of a sulfonate type (for example) , 4-methyl-3-isocyanatobenzene sulfonyl 4'-isocyanato-phenol ester; aromatic isocyanuric acid type polyisocyanate, sulfur-containing heterocyclic polyisocyanate (for example, α plug Benzene-2,5-diisocyanate); halogenated, burnt, burnt, oxidized, carbodiimide modified, urea modified and biuret modified by these types of polyisocyanates And polyisocyanates belonging to these classes The product of the second polymerization and the third polymerization. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public). (Please read the phonetic on the back? Please fill out this page again) _dress ------ --Book --------- 13 1285651 A7

NCO V. INSTRUCTION DESCRIPTION (11) It is particularly preferred to have a sulfide-bonded aliphatic polycyanate monomer and other polycyanate mono-systems having one or more sulfur atoms in the monomer backbone. Particularly good 2 sulfur-containing polycyanate single system of one of the general formula (III): 1 (III)

OCN wherein R10 and R" each are individually (^ to ^^). Examples of aliphatic polyisocyanates which can be selected as monomers of polycyanate include ethylidene diisocyanate and trimethylene Diisocyanate, tetramethylammonium diisocyanate, hexamethylene diisocyanate, octamethyl methyl diisocyanate, hexamethylene diisocyanate, 2,2, dimethylpentane diisocyanate, 2,2,4- Trimethyl hexane diisocyanate, decylmethyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, i,6,u-undecane triisocyanate, 1,3,6-six Methyl triisocyanate, hydrazine, diisocyanate _4 isocyanatomethyl)octane, 2,5,7-trimethyl-i,8-diisocyanato _5 isocyanate Methyl)octane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 2-isocyanatopropyl-2,6-diisocyanato Acid vinegar, lysine diisocyanate methyl ester and lysine triisocyanate methyl ester, but are not limited thereto. Examples of ethyl saturated polyisocyanate include butyl diisocyanate and 1, 3 · Butadiene-1,4_diisocyanate, but not limited to it. The alicyclic group which can be selected as the polycyanate monomer (a) (ii) contains isophorone diisocyanate酉 、, cyclohexene diisocyanate, methylcyclohexene diisocyanate, double (isocyanate paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----------.-^ ^Shang--------Book---------CPlease read the phonetic transcription on the back? Please fill out this page again} Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7

1285651 V. INSTRUCTIONS (l2) acid methyl) cyclohexane, bis(isocyanatocyclohexyl)methane, bis(isocyanatocyclohexyl)_2,2-propane, bis(isocyanato) Hexylethane, 2-isocyanatomethyl-3-(3.isocyanatopropyl)_5-isocyanatomethyl-bis[2.2.1]·heptane, 2-isocyanato _3-(3-Isocyanatopropyl)-6-isocyanatomethyl_; ι_bicycloheptane, 2-isocyanatomethyl-2-(3-isocyanate) -5 -Isocyanatomethyl-bicyclo[2.2.1]heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanate Base-diacid [2·2·1]-heptane, 2-isocyanatomethyl_3_(3-isocyanatopropyl)-6-(2-isocyanatoethyl)·bicyclic [2 2"]_heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)_5-(2-isoxanthateethyl)-bicyclo[2.2.1]_ Geng Shao and 2-isocyanatomethyl-2(3_isoxanthionate propyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]·g-burning 'but not limited to this The isocyanate group is not directly bonded to the aromatic ring Examples of the polyisocyanate include bis(isocyanatoethyl)benzene, α,_tetramethyltoluene diisocyanate, 1,3_bis(1-isocyanato-1-methylethyl) Benzo, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)anthracene An acid ester, a triisocyanate, and a 2,5-di(isocyanatomethyl)furan, but is not limited thereto. The polycyanate monomer (a) (ii) can be directly bonded to the monomer selected therefrom. Examples of the aromatic polyisocyanate of the isocyanate group of the aromatic ring include phenyl diisocyanate, ethyl phenyl diisocyanate, isopropyl phenyl diisophthalic acid vinegar, and dimethyl phenyl diisocyanate. , diethyl phenyl diisoxic acid S, diisopropyl phenyl diisocyanate, trimethyl benzene triisocyanate paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 PCT) I —*—装--------定--------- (please read the note on the back? Please fill out this page again) Printed by the Intellectual Property Office of the Ministry of Economic Affairs15 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1256651 A7 ^_ R7__ V. Description of invention (l3) Ester, benzene triisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, bisphenyl diisocyanate, o-toluidine II Isocyanate, o-tolyl diisocyanate, o-tolyl diisocyanate, 4,4,-diphenylmethane diisocyanate, bis(3-methyl-4-isocyanatophenyl)methane, bis ( Isocyanatophenyl)ethylene, 3,3'-dimethoxy-bisphenyl-4,4,-diisocyanate, triphenylmethane triisocyanate, polymerized 4,4,_diphenylmethane Isocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4,-triisocyanate, 4-methyldiphenylmethane_3,5_2,4,6,5 pentaisocyanate, diphenyl ether diisocyanate, Bis(isocyanatophenyl ether) ethylene glycol, bis(isocyanatophenyl ether)-1,3-propanediol, benzophenone diisocyanate, carbachol diisocyanate, ethyl carboazole diisocyanate Dichlorocarbazol diisocyanate, but is not limited thereto. The sulfide-bonded aliphatic polyisocyanate which may be selected from the polycyanate monomer (a) (ii) comprises thiodiethyl diisocyanate, thiodipropyl diisocyanate, disulfide II Hexyl diisocyanate, dimethyl hydrazine diisocyanate, dithio dimethyl diisocyanate, dithiodiethyl diisocyanate 6, dithiodipropyl diisocyanate g and dicyclohexyl sulfide _4,4'-diisocyanate, but is not limited thereto. Examples of the aromatic or polysulfide-bonded spheroidal poly(isosuccinic acid) include diphenyl sulfide-2,4'-diiso-acidic acid, diphenyl sulfide-4,4'-di Isocyanate, 3,3'-dimethoxy-4,4,diisocyanatodiphenylsulfanylthio, bis(4-isocyanatomethylbenzene)-sulfide, diphenyl Sulfide-4,4,-diisocyanate, 2,2,-dimethyldiphenyl disulfide_5,5,diisocyanate, 3,3'-dimethyldiphenyldisulfide-5 , 5'-diisocyanate, 3,3,-dimethyldiphenyl disulfide 6,6, · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 16 (Read first Note on the back of the page. _#襄定---- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1256651 A7 ______ B7 ___ V. Description of Invention (14) Diisocyanate, 4,4'-dimethyl Diphenyl disulfide _5,5,_diiso sulphuric acid, 3,3'-dimethoxydiphenyl disulfide _4,4,-diisocyanate and 4,4,_ dimethoxy Diphenyl disulfide 3,3,-diisocyanate, but not limited to It is selected as the polycyanate monomer (a) (ii), which contains a ruthenium-bonded fluorene polyisomer. The Ss system contains a base _4,4'-diisocyanate, diphenyl money 3.3' -diisocyanate, benzidine maple _4,4'-diisocyanate, diphenylmethyl sulfonium-4,4'-diisocyanate, 4-methyldiphenylmethane oxime-2,4,-diiso-acid Vinegar, 4,4,-dimethoxydiphenylphosphonium-3,3,-diisocyanate, 3 3,_J, 丨_methoxy-4,4'-diisocyanatodiphenyl Base, 4,4,-dimethyldiphenylphosphonium-3,3, diisocyanate, 4,4,2-di-t-butyl-diphenyl maple-3,3, diisocyanate and 4,4 '-Dihydrodiphenylphosphonium 3,3,-diisocyanate, but is not limited thereto. An example of an aromatic isocyanide type polyisocyanate which can be used to prepare a polycyanate reactant comprises 4-methyl-3-isocyanato-benzene-sulfonylaniline-3'-methyl-4 '_Isocyanate, diphenylsulfonyl-ethylenediamine·4,4, diisocyanate, 4,4′-methoxybenzenesulfonyl-ethylenediamine_3,3,-diisocyanate and 4 Methyl-3-isocyanato-benzene-sulfonylaniline_4_ethyl_3,-isocyanate, but is not limited thereto. The polyisothiocyanate type from which the polycyanate monomer (a) (ii) can be selected includes: an aliphatic polyisothiocyanate; an alicyclic polyisothiocyanate (for example) 'Cyclohexane diisothiocyanate); an aromatic polyisothiocyanate in which an isothiocyanate group is not directly bonded to an aromatic ring (for example, a phenyldiisothiocyanate) Acid ester); wherein the isothiocyanate group is directly applied to the paper size of the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 17 [.«裳订--------- ( Please read the precautions on the back and fill out this page.) 1285651 A7 B7 V. INSTRUCTIONS (15) (Please read the note on the back and fill out this page). The aromatic polyisothiocyanate of the aromatic ring. (for example, phenyl diisothiocyanate); heterocyclic polyisothiocyanate (for example, 2,4,6-triisothiocyanate, 1,3,5-triazine and Thiophene-2,5-diisothiocyanate); carbonyl polyisothiocyanate; sulfide-bonded aliphatic polyisothiocyanate (for example, thiobis(3-isosulfur) Base cyanide propane); containing isothiocyanate base Polyisothiocyanates of sulfur atoms outside; halogenated, alkylated, alkoxylated, nitrated, modified carbodiimide, urea modified and bisected by these types of polyisothiocyanates a urea-modified derivative; and a product of dimerization and tri-polymerization of such polyisothiocyanates, but is not limited thereto. The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, can be selected as a poly Examples of the aliphatic polyisothiocyanate of the cyanate ester monomer (a) (ii) include 1,2-diisothiocyanate ethane, l,3-diisothiocyanate propane , 1,4-diisothiocyanate butane and 1,6-diisothiocyanate hexane, but are not limited thereto, and have an isothiocyanate group directly bonded to an aromatic alkane. Examples of the aromatic polyisothiocyanate include 1,2·diisothiocyanate benzene, 1,3-diisothiocyanate benzene, and 1,4-diisothiocyanate Benzene, 2,4-diisothiocyanate toluene, 2,5-diisothiocyanate-m-xylene, 4,4,-diisothiocyanate _1,1 Benzene, 1, Γ-extension methyl bis(4-isothiocyanate ), ι,ι,_methyl bis(4-isothiocyanate-2-methylbenzene), 1,1'-methyl bis(4-isothiocyanate-3-methyl Benzo), hydrazine, -(ι,2-ethane-diyl)bis(4-isothiocyanate benzene), 4.4'-diisothiocyanate benzophenone, phenyltoluamide _ 3,4, diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate and diphenylamine-4,4'-diisothiocyanate g, but This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 18 1285651 A7 —_______B7 V. Invention Description (I6) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

The carbonyl polyisocyanate which can be used to prepare the first component of the two component composition of the polycyanate reactant comprises hexane-dicarbonyldiisothiocyanate vinegar, octanedicarbonyldiisothiocyanate Ester, diisothiocyanate, 1,3-p-mono-diisothiocyanate, iota, 4-phenylenediyldiisothiocyanate and (2,2,-di Pyridine)-4,4,-dicarbonyldiisothiocyanate, but is not limited thereto. In addition to the isothiocyanate groups, examples of the aromatic polyisothiocyanates containing sulfur atoms which can be used in the present invention include 丨-isothiocyanate-4-[(2- Isothiocyanate)sulfonyl]benzene, thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanate benzene), sulfinyl bis ( 4-isothiocyanate benzene), dithio bis(4-isothiocyanate benzene), 'isothiocyanate isocyanatocyanatophenyl sulfonate> 2 Oxybenzene, 4-methyl-3-isothiocyanate benzene-continuous sulfonyl-4, _isothiocyanate phenyl ester and 4-methyl-3-isothiocyanate benzene - sulfophenylaniline 3, methyl 4'-isothiocyanate, but is not limited thereto. The polycyanate monomer (a) (ii) used to prepare the first component of the two component composition of the polycyanate reactant may also be selected from the group consisting of isocyanate and isothiocyanate groups. The acid ester monomer may be, for example, an aliphatic, alicyclic, aromatic, heterocyclic or sulfur atom other than the isothiocyanate group. Examples of such compounds include 1-isocyanato-3-isothiocyanate propane, 1-isocyanato-5-isothiocyanate pentane, and isocyanato -6. Thiocyanate hexane, isocyanatocarbonyl carbonyl isothiocyanate, isocyanato-4-isothiocyanate hexane, hydrazine-isocyanate _4•isothiocyanate Acid benzene, 4-methyl-3-isocyanato _; u isothiocyanate benzene, 2-isocyanato-4,6-diisothiocyanate _l53,5-three Izine, (please read the note on the back and then fill out this page) I installed — — — — — —

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1285651 A7 I iiiini - ...... B7 _ V. Invention description (Π ) ' "" 4_Isocyanate -4'-isothiocyanate-diphenyl sulfide and]•iso-acido-2'-isothiocarbazide diethyldisulfide' but not limited to the composition of the two components The first component of the polycyanate reactant can be selectively prepared from the reactive hydrogen material (a) (iii), which can be selected from the group consisting of polyols having at least dihydroxy groups, having hydroxyl groups and thiols. a mixture of materials and the like. When used herein, a reactive hydrogen material means a material having a reactive hydrogen group capable of forming a covalent bond with an isocyanate and an isothiocyanate group. The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, prints the types of polyols that can be selected as selective reactive hydrogen materials (a) (iii). Polyols of linear or branched chain (for example, 12- Ethane diol, 1,3-propane diol, iota, 2-propane diol, iota, 4-butane diol, 13 · butyl diol, glycerin, neopentyl diol, trimethyl alcohol B Alkane, trimethylolpropane, di-trimethylolpropane, erythritol, pentaerythritol and dipentaerythritol); polyalkylene glycol (for example, diethylene glycol, dipropylene glycol) 'and more south polyalkylene glycol (such as, for example, 2 to 2 g / mol) of the number average molecular weight of the polyethylene glycol); naphthenic polyol (for example , cyclopentanediol, cyclohexanediol, cyclohexanetriol, cyclohexanedimethanol, propylidene hexanol, and j-hexanol diethanol); aromatic polyols (eg, di-based benzene, benzene) Triol, hydroxyphenylhydrinol and dihydroxytoluene); bisphenol (for example, 4,4'-isopropylidene diphenol); 4,4,_oxybisphenol, 4,4'-dihydroxybenzo Benzene S, 4, 4'_ Thiobisphenol, phenolphthalein, bis(4-hydroxyphenyl)methane, 4,4'-(1,2-ethanediyl)bisphenol, and 4,4,-sulfonylbisphenol); Phenol (for example, 4,4,-isopropylidene bis(2,6-dibromophenol), 4,4,-isopropylidene bis(2,6·dichlorophenol) and 4,4, isopropyl Forked bis(2,3,5,6-tetrachlorophenol)); alkoxylated bisphenol (eg 20 paper grades for Chinese National Standard (CNS) A4 size (210 X 297 mm) 1285651 A7 B7 5. Description of the invention (I8), alkoxylation of 4 to 70 alkoxy groups (for example, ethoxy, propoxy, butoxy and /5-butoxy) 4,4,-iso Propyldiphenol); and dicyclohexanol obtainable by hydrogenating the corresponding bisphenol (for example, 4,4,-isopropylidene-dicyclohexanol, 4,4,-oxodicyclohexanol) 4,4,-thiodicyclohexanol and bis(4-hydroxycyclohexanol)methane, but are not limited thereto. In one embodiment of the invention, a selective reactive hydrogen material (a) may be selected. The polyol of (iii) is a polyurethane prepolymer having two or more hydroxyl groups. The hydroxy functional polyurethane prepreg used in the present invention The material may be prepared from any of the polyols listed above and a suitable polyisocyanate. The ratio of the hydroxyl group to the molar equivalent of the isocyanate group is selected such that the hydroxy-functional polyurethane having no free isocyanate group is pre-prepared. Polymers are produced. Examples of polyisocyanates suitable for the preparation of hydroxy-functional polyurethane prepolymers are included herein as described above. Selective reactive hydrogen materials can be selected therefrom. The transfunctional polyurethane prepolymer of (a) (iii) typically has less than 50,000 (preferably less than 2 Torr, more preferably less than 1 Torr, 〇〇〇) The average molecular weight (??) of grams per mole is determined by gel permeation chromatography using polystyrene standards. Examples of materials having a thiol group and a thiol group which can be selected as the selective reactive hydrogen material (aXiii) include 2-mercaptoethanol, succinyl-1, propylene glycol, and glycerin (2-mercaptoacetate), glycerol bis(3-mercaptopropionate), b. base_4_weiki% hexane, 2,4-one basophilic age, 2-sulfohydrogen , 4_ylphenol, 1,3-dimercapto-2·propanol, 2,3-dimercapto-1-propanol, indole, diindolyl-1,3-butanediol, trimethylol Propane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), pentaerythritol mono(2-mercaptoacetate), (please read the back note first and then fill out this page) I--------Book---------. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 21 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1256651 A7 ------ ---B7___ V. Description of the invention (20) The substance may also be selected from one or more isomers of the dialkyl toluenediamine of Ci_C3, such as 3,5-dimethyl-2,4. -toluenediamine, 3,5-dimethyl-2,6.toluenediamine, 3,5-diethyl-2, 'toluenediamine, 3,5-diethyl-2,6-A A mixture of phenylenediamine, 3,5-diisopropyl-2,4-tolyldiamine, 3,5-diisopropyl-2,6-toluenediamine, and the like. Further examples of the polyamine which can be selected as the polyamine reactant include, but are not limited to, methyl diphenylamine and trimethyl glycol bis(p-aminobenzoate). In one embodiment of the invention, the polyamine reactant can generally be described as having one of the following general structures (IV-VI): (IV)

(Please read the phonetic on the back first? Then fill out this page) (V) (VI)

A particularly preferred structure comprises the following general structure νπ·χχ or a plurality of diamines, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) 23 - ------ --Book --------- Line Qin 1856651 A7 B7 V. Invention Description (21)

(V

(V

X)

R4R5R4R5

(X Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed

(X

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 24 ~ Pack-------- Order--------- (Please read the notes on the back first) Fill in this page) 1285651 A7 _B7 V. Description of Invention (22) (XII)

(X

I (X

(X

R4 R5 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

(XV

(Please read the notes on the back and fill out this page.) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 25 1285651

V. Description of invention (23 (XVII)

Nh2 (XVIII)

(XIX)

(XX) Ministry of Economic Affairs, Intellectual Property, Bureau of Staff, Consumers, and Consumers

Wherein each of Han 3 and R 4 is individually a CrC 3 alkyl group, and R 5 is selected from the group consisting of hydrogen and halogen (for example, gas and bromine). The diamine represented by the formula VII can be generally described as 4,4, methyl-bis(dialkylaniline). Specific examples of the diamine represented by the formula VII include 4,4,_methyl-bis(2,6-dimethylaniline), 4,4 stretch paper size applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) 26 ---------,------------------------- τ (Please read the phonetic on the back? Fill in this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1256651 A7 --------B7___ V. Description of Invention (24 ) Methyl·bis(2,6-diethylaniline), 4,4 , _ methyl, bis(2·ethyl-6-methylaniline), 4,4, methyl-bis(2,6-diisopropylaniline), 4,4,-methyl- Bis(2-isopropyl-6-methylaniline) and 4,4,-extended methyl-bis(2,6-diethyl-3-isoaniline), but are not limited thereto. Preferred diamines of the formula Vii are 4,4\methyl-bis(2,6-diethyl-3-aniline). In another embodiment of the present invention, the polyamine reactant is generally a 2,6-diaminotoluene 3,5 dialkyl sulfide of the formula XXI (XXI)

Wherein R6 and R7 are linear, branched or cyclic q to c2G alkyl groups. Preferred compounds of the formula XXI are 2,6-diaminotoluene 3,5-dimethyl sulfide and 2,6-diaminotoluene 3,5 diethyl sulfide. Polymerizing the two component composition in accordance with the process of the present invention can be accomplished by mixing the first and second components together using, for example, an impeller or an extruder: selectively degassing the combined mixture; The mixture is added to the mold; the mold and other mixtures are then heated for a period of time. The heat curing cycle used will vary depending on, for example, the reactivity of the components used and the molar ratio and the presence of any catalyst. Typically, the heat curing cycle comprises heating the combined mixture of the two component components from room temperature to up to 200X during 5 hours to 72 hours (preferably 〇 5 to 16 hours): (preferably 1 〇) 〇°c to 140〇C) 〇r *·装--------Book---------^_«wi (Please read the notes on the back and fill out this page)

1285651 A7 B7 V. INSTRUCTIONS (25) Catalysts which can be used with the two component composition, for example, tertiary amines (for example, triethylamine, triisopropylamine and decyldimethylbenzylamine) And organometallic compounds (for example, dibutyltin dilaurate, dibutyltin diacetate, and tin octoate). A further example of a tertiary amine is shown in column 10, lines 6 to 38 of U.S. Patent No. 5,693,738. The disclosures of which are incorporated herein by reference. Incorporation is for reference. If used, the catalyst is typically incorporated into the second component prior to the combination of the first and second components of the two component composition. The amount of catalyst is typically less than 5% by weight (more Preferably, it is less than 3% by weight, and more preferably less than 丨% by weight, based on the total weight of the first and second components combined. The first and second components of the two component composition are typically polymerized in an amount sufficient to provide a molar basis of (NC 2 + NCS) groups of from 0.5 to up to 100 or more. Together. Acceptable (Nc〇+ Ncs), the ratio of (_ NH2+ -NH-) ranges from 〇5 to 5〇, 〇5 to 1〇, 〇5 to 5, 〇·5 to 3·0 ' 〇·5 to 1.5, or (^ to 丨 2). The correct ratio will depend on the true nature of the final polymer. A preferred method of polymerizing the two component composition is reaction injection molding (RIM). 'Two or more liquids in the RIM process (which are fast anti-illusion to form a solid polymer. The liquid system is individually metered into the molding machine via a mixing head during which a solid polymer is formed. As part of the present invention An example of a surface machine is described in U.S. Patent No. 4,189, the disclosure of which is incorporated herein by reference. 1285651 A7 V. INSTRUCTIONS (26) A preferred device for completing the RIM method of the present invention is a component structure machine that can be accurately metered and fully mixed over a wide range of stoichiometric ratios. The machine includes several storage containers for use. Each of the plurality of reactant metering cylinders is individually connected to one of the liquid storage containers. Each cylinder contains a reciprocable piston. Power is supplied & All of the cylindrical pistons reciprocate together. One end of the rod arm is connected to the piston of the first metering cylinder. The rod arm shaft is grooved at a point spaced from the piston connected to the first metering cylinder The method is connected to the movable lever fulcrum. The lever arm also connects the piston of the other measuring cylinder in a groove connection manner. Each measuring cylinder is sequentially connected to the mixing head through an appropriate passage, and the reactive mixture is injected into the molding machine from the same. The continuous proportional control of the reactants is provided by controlling the change in position of the movable lever fulcrum of the lever arm of one of the metering cylinders. Various conventional additives can be incorporated into the two component organic composition polymerized by the method of the present invention. Additives may include light stabilizers, heat stabilizers, antioxidants, UV absorbers, mold release agents, static (non-photochromic) dyes, colorants, and flexible additives, such as alkoxylated phenolic benzoates and poly( Stretching mono-alcohol) dibenzoate. The preferred release agent is ketone to C16 alkyl phosphate, E"dup〇ntdeNem〇urs and Cc) mpany,

Wilmington, sold by Deieware). Anti-yellowing additives, for example, 3 methyl-2-butenol, organic pyrocarbonate, and triphenylphosphite (cas registration number 101-02-0) may also be added to the two-component organic composition. To promote anti-K effect. Such additives are typically present in a total amount of less than 1% by weight (preferably less than 5% by weight, and more preferably less than 3% by weight, based on the Chinese National Standard (CNS). A4 size (21G x 297 public hair 29

Amendment 丨1285651 Application for the period of 7 〇, 卜" Case. No. category ^ Qo > Β χ. (The above are filled by this Council) A4 C4 Ministry of Economic Affairs Zhichong is the hook Xiaogong ^ fee cooperative printing patent $ brother The invention of the first book, said Chinese sulphur-containing polyamine phthalate / polyurea resin as the base of the optical polymer English SULFUR-CONTAINING POLYURETHANE / POLYUREA RESIN-BASED OPTICAL POLYMERIZATE Name (1) Michael 0 · Occoro (2) Robert A. Smith (3) Lifet Tabakovy (4) Marvin J. Graham (5) Robert D. Hirod Nationality (1) (2) (4) (5) United States (3) Bosnian invention - '面面,居所0) 274 Jefferson Street, Exeter, Pennsylvania, USA (2) 3517, Murraysville, McIlroy Road, Pennsylvania, USA (3) 1287, Troyx Avenue, Michigan, USA Apartment 51 (4) 1400 Baymont Avenue, Monroville, PA 204 (5) 218 Monroville Lane, Liss, Pennsylvania, USA Name (name) US Business · Piece Hard Ohio Industrial Company Nationality US III, Applicant Residence, Residence (Company) Ohio, USA No. 3800, 143 West Street, Lanzhou, Xi Li, the name of the representative Lita Bergstrom, a book paper ft scale applicable to Chinese national standards (C: NS) A4 specifications (2丨0 X 297 mm) Patent application I28565f 089124386 Prosecution Amendment Page A7

V. INSTRUCTIONS q _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a polymer from a two-component organic composition, which is a polymer system. Having a refractive index of at least 1.6, at least Abbe niimber, and at least 1 Barc 〇 1 hardness. More particularly, the present invention relates to polymerizing certain two-component organic compositions, including a polycyanate reactant having at least one at least diisocyanate and/or an isothiocyanate group, and a polyamine having at least two primary and/or secondary amine groups. The present invention is also related to polymers and Photochromic articles. Incorporating technology into applications such as optical lenses, fiber optics, windows and transparencies for automotive, marine and aircraft applications, several organic polymeric materials (eg, plastics) have been developed as alternatives to glass. And alternatives. ,,, here when used in glass "refers to a speech-based Silica * of inorganic glass. These polymeric materials offer glass-related advantages, including resistance to comminution, lighter weight for specific applications, lighter than molding, and lighter dyeing. Representative examples of such polymeric materials include poly(methyl methacrylate), thermoplastic polycarbonate, and poly[diethylidene bis (dihydrohexyl carbonate). Many polymeric materials generally have a lower refractive index than glass. For example, the refractive index of 'poly[diethylethylene bis(allyl carbonate)] is about the paper scale applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) I -II i 1 I · -- ---------Φ ! (Please read the notes on the back and fill out this page) Order the Economic and Industrial Cooperatives to print the Intellectual Property Office 4 - 2 1285653⁄4❶89124386 Patent Application Manual ϋ — Α7 Β7 V. DESCRIPTION OF THE INVENTION (1,50, compared to high index glass, the range may be, for example, u❶ to (4). When preparing a lens for bridging a specified degree of visual loss (for example, correction of myopia), Materials with high refractive index (for example, high-index glass), use a polymer material with a lower refractive index to be thicker than 2 lenses. If the required degree of correction is large, such as in severe myopia, self-low-index polymer Lenses made from materials may need to be very thick. Very thick lenses may offset the benefits of using lower density lens materials in relation to the correctness obtained from lenses with higher refractive indices. In addition, thicker optical lenses are not. It is expected that a polymer material having a refractive index greater than 1.50 can be prepared from an aromatic monomer and a monomer containing a _ and/or a sulfur atom. A lens (especially an optical lens) can be prepared. The materials may be classified by their refractive index. As is known to those skilled in the art, the low index typically contains less than the refractive index: the medium index contains a refractive index of 1.54 to 1.57; and the high index generally contains a refractive index of 1.58 and greater. Index. Lenses made from polymeric materials with high refractive index typically also have a lower number of shells (also known as nu value). The lower Abbe number indicates increased color dispersion. Typically, it is shown by the light distortion at the edge of the lens or at its entrance. U.S. Patent No. 5,961,889 (Jiang et al.) discloses an optical polymer for use in a lens which is self-containing a polythiol group. The component, the polyisocyanate-containing component, and/or the polyfunctional vinyl-containing component are prepared. The disclosed polymer typically has a refractive index of less than 1.69 and an Abbe number of less than 35. Patent No. 5,932,681 (Herold et al.) An optical polymer as a lens material, which is based on the isocyanate or isothiocyanate paper size. It is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public sauce) ---------·丨丨 (Please read the notes on the back and fill out this page) - Order the Economic and Industrial Cooperatives to print the Intellectual Property Bureau-5

Patent Application No. I28565fG89124386, J Dongzhengbai A7 B7 V. Inventive Note (3) and Polythiol. The disclosed polymer has a refractive index of at least 1.57 and an Abbe number of at least 33. U.S. Patent No. 5,679,756 (Zhu et al.) discloses an optical polymer disclosed by a thermoplastic thiourethane-urethane copolymer which is formed by the reaction of an aliphatic diisocyanate with a dithiol to form a thio group. A carbamate, acid vinegar prepolymer is then prepared by reacting with a diisocyanate and a polyol. The polymer disclosed typically has a refractive index between 1.57 and 1.60 and an Abbe index between 35 and 38. Although the above optical polymer has an appropriate refractive index and color dispersibility, it does not have the impact resistance required for daily wearing of lenses for glasses. Accordingly, it would be desirable to be able to formulate new polymeric materials (e.g., polymers) that can be used to prepare a combination of a refractive index and a suitably high Abbe number and possess a polymer material at least equal to the lower index. And preferably a transparent polymer, especially an optical lens, which is better than its physical properties (especially impact resistance). SUMMARY OF THE INVENTION The present invention is directed to a method of preparing a polymer comprising the step of polymerizing a two component composition comprising: (a) a first component comprising at least one difunctional The polycyanate-branched reactant 'the functional group is selected from the group consisting of isocyanic acid vinegar, isothiocyanate vinegar and the like, and the polycyanate reactant is the following reaction product: (1) There are at least two a thiol group-containing polythiol monomer; and (11) a polycyanate monomer having at least two functional groups selected from the group consisting of isocyanates, isothiocyanates, and the like; Turn (CNS) one ^ (21GX297 public Li) ---------9 ! (Please read the notes on the back and fill out this page) Order the Economic and Consumer Consortium to print the Intellectual Property Office

V. DESCRIPTION OF THE INVENTION (4) 1285651 and (b) a second component comprising at least one polyamine reactant having at least two functional groups selected from the group consisting of a primary amine, a primary amine, and the like; wherein the first component The molar equivalent ratio of the (NCO + NCS) group to the (-Nh2 + -ΝΗ·) group of the second component is 0.5 to 100. The invention is also directed to polymers made in accordance with the process of the invention. The invention further relates to photochromic articles made from the polymers of the invention. DETAILED DESCRIPTION OF THE INVENTION The number or representation of all relevant components, reaction conditions, etc. used herein, unless otherwise indicated, is to be understood in all instances. The present invention relates to a method of preparing a polymer comprising the steps of polymerizing a composition of two components, the composition comprising: (a) a first component comprising at least one polycyanide having at least a difunctional group a vinegar reactant, the functional group is selected from the group consisting of isocyanates, isothiocyanates, and the like, and the polycyanate reactants are the following reaction products: (0) polysulfide having at least a dithiol group An alcohol monomer; (Π) a polycyanate monomer having at least two functional groups selected from the group consisting of isocyanates, isothiocyanates, and the like; and (iii) optionally having at least two reactive hydrogen groups a reactive hydrogen material selected from the group consisting of a polyol, a material having a hydroxyl group and a thiol group, and the like, and the reaction amounts of (i), (ii) and (iii) are selected such that The molar equivalent ratio of (NCO + NCS) / (SH + OH) is greater than 1.0; and the paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ---------- -------I--book---- (please read the note on the back? Please fill out this page again) Debate. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Apparel Economy, Industrial and Consumer Cooperatives, Printing and Intellectual Property Bureau, 1285653⁄4089124386 Patent Application Manual Amendment ^Gong--一-一一------------------------ -^ Α7丨释正if 转?f康秦丨|Page! B7 ' ! V. Description of the invention (5) (b) The second component, which contains at least one at least two selected from the group consisting of primary amines and secondary amines a polyamine reactant of a mixed functional group thereof. The first component and the second component are selected such that when they are polymerized, they are provided with from about 1.57 to about 1.80 (preferably a refractive index of from 1.60 to about 1.75); an Abbe number of at least about 30 (preferably at least about 33) and a polymer having an initial Barco hardness of at least 1. The refractive index is based on the American Standard Test Method ( ASTM) No. D 542-95. The Abbe number or value is determined using a suitable instrument (eg, Bausch & ABBE-3L refractometer). Initial Barco hardness (also commonly referred to as zero second Barco hardness) It is determined according to ASTM No. D 2583-95. The first component of the two-component composition has at least two selected from the group consisting of isocyanate (-NCO), isothiocyanate (-NCS) and isocyanate. base a functional group of a mixed isothiocyanate group. As used herein, the term "cyanate ester" refers to an isocyanate and an isothiocyanate group which are not blocked (or capped), And it is capable of forming a covalent bond with a reactive hydrogen group (for example, a thiol, a hydroxyl group or an amine group). The polycyanate reactant is a polythiol, a polycyanate monomer, and a selective reactivity. a reaction product of a material such as a polyol or a material having a hydroxyl group and a thiol group. When preparing a polycyanoester reactant, a polythiol monomer, a polycyanate monomer, and a selective reactive hydrogen The material is selected such that the molar equivalent ratio of (NC〇+ NCS)/(SH + OH ) is greater than 1.0, for example, 1·2: ΐ·〇 to 4·0:1·〇, or 2·〇:ΐ ·〇 to 3 〇: 1〇. The first component of the two components of the composition consists of a urethane linkage (-NH-C(O)-O-), a thiocarbamate linkage G NH -C(O)-S-), thiocarbamate linkage (-NH-C(S)-O-), disulfide-----:------ (please read the back first) Note on this page), 11

1285653⁄4089124386^ Patent application manual revision page one... _ A7 Participation date: _ January τ B7 ^~ one ~ one ~ one _ five, invention description ς) 0 generation urethane bonding (-JVH-C ( The backbone bonding of S)-S·) and its mixtures. The molecular weight of the polycyanate reactant can vary widely, for example, having a number average molecular weight (Mn) of from 5 to 15,000 (or from 500 to 5,000) by gel coat chromatography using polystyrene standards. The decision was made. The polythiol monomer which can be used to prepare the polycyanate S-reactant has at least a dithiol group and can be selected from the group consisting of aliphatic polythiols, cycloaliphatic polythiols, aromatic polythiols, and the like. mixture. Further, the polythiol monomer may also be selected from the group consisting of ether bonding (-0-), sulfide bonding (-S-), polysulfide bonding (_sx_, wherein 1 is at least 2, for example, 2 to 4 And a combination of these bonding bonds. As used herein, "thiol", "thiol group,", "mercapto, or, thiol," refers to a -SH group which is capable of forming a thiocarbamic acid with a isocyanate group. Binding (ie, _Njj_C(O)-S-) or forming a dithiocarbamate linkage with an isothiocyanate group. Economic, Completion Consumption Cooperation, Printed Intellectual Property Bureau (please read the note on the back and fill out this page) Examples of polythiol monomers that can be used to prepare polycyanate reactants include 2,5_ Di-sulphide-yl-1,4-dioxin, 2,2'-thiodi- thiol, pentaerythritol tetrakis(3- mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), trimethylglycol Propane tris(3-mercaptopropionate), trimethylolpropane tris(2- mercaptoacetate), 4-nonylmethyl-3,6·dithia-1,8-octane disulfide Alcohol, 't-butyl-1,2-benzenedithiol, 4,4'-thiodiphenylthiol, phenyldithiol, B'-yield'-(2-sodium acetate), B Glycol bis(3-propionyl vinegar), poly(ethylene glycol) bis(2-mercaptoacetate), and poly(ethylene glycol) bis(3·mercaptopropionate), but are not limited thereto . Mixtures of polythiol monomers can also be used to prepare the polycyanate reactant. The polythiol monomer may also be selected from the group consisting of polythiol represented by the following formula I. This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210X297 mm) _ 9 _ Μ Workers' Cooperatives Printed Intellectual Property Bureau Ι28565Ϊ089124386 Patent Application Specification Amendment Page~~ One, One A7 Master Period: _Thin) Five, Invention Description (19) Pentaerythritol bis(2-mercaptoacetate) 'Pentaerythritol III (2_ Mercaptoacetate), pentaerythritol mono(3- mercaptopropionate), pentaerythritol bis(3- mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), hydroxymethyl·tris(decylethyl sulfide) Methyl)methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-M-based diphenylanthracene, dihydroxyethyl sulfide mono(3-mercaptopropionic acid Ester) and hydroxyethylthiomethyl-tris(decylethylthio)methane, but are not limited thereto. The reaction of the polythiol monomer (a) (i), the polycyanate monomer (... ((1) and the selective reactive hydrogen material (a) (iii) can be carried out in the presence of a suitable catalyst. A tertiary amine (for example, triethylamine) and an organometallic compound (for example, dibutyltin dilaurate). Further examples of catalysts which can be used to prepare the polycyanate reactant are shown below. In the preparation of the polyoxic acid S-reactant, which is typically present in an amount of less than 5% by weight (less than 3% by weight of the cargo, and more preferably less than i by weight of 0/〇), Based on the total weight of (4) (1), (a) (ii) and (a) (iii), the second component of the two-component composition may be selected from the group consisting of aliphatic polyamines, cycloaliphatic groups. a polyamine, an aromatic polyamine, and mixtures thereof, etc. The polyamine reactant has at least two functional groups selected from the group consisting of monoamines (-NIIj, secondary amines, and the like. Preferred, polyamine reactant systems Having at least two primary amine groups. The polyamine reactant may be selected from any of the group of vinylamines, for example, ethylenediamine (EDA), diethylidene (DETA), tri-ethyltetramine (TETA), tetraethylamamine (ΤΕΡΑ), pentaethylhexamine (PEHA), piperidine (ie, diethylenediamine (DEDA)) and 2-Amino-1-ethylpiperazine. Polyamine reaction This paper scale applies to Chinese National Standard (cNS) A4 specification (2丨0><297 mm) (please read the notes on the back) The amount of _ 22 - , 27 I089124386 patent application specification A7 B7 5, the invention description α - and the total weight of the second component is based on the amount of the second component is present. Conventional additives may be added to the first or second component of the composition' which is typically incorporated into the second component of the composition to render the isocyanate (four) or the different component of the first component The potential is minimal. The polymer produced by the process of the present invention may be solid, and preferably transparent, suitable for optical or ophthalmic applications. The polymers of the present invention also have from about 1.57 to about 1.80 (more a refractive index of from about L6〇 to about 1β75); an Abbe number of at least about 30 (preferably at least about 33); and a zero-second Barco hardness of at least i, and Good impact resistance. The reactants and compounds comprising the first and second components of the two component composition are selected and combined in such a way that the polymer produced therefrom possesses a non-characteristic property. The solid objects produced include optical lenses (such as flat and ophthalmic lenses), sunglasses, έι, brake transparent materials (for example, window shielding, side lights and backlights), and aircraft transparency, but are not limited to When used to prepare a photochromic article (eg, a lens), the polymer can be part of the electromagnetic spectrum of the photochromic substance that is activated into the substrate (ie, producing a colored or open form of light) The ultraviolet (UV) wavelength of the color-changing substance and the portion of the visible light spectrum of the maximum wavelength of absorption of the photochromic material contained in its UV-activated pattern (i.e., open form) are transparent. Photochromic materials which can be used with the polymers of the present invention are organic photochromic compounds or materials which can be incorporated (e.g., dissolved, dispersed or diffused) into such polymers. The first type of paper that is considered to form the photochromic article of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (210 X 29 < 7 mm) (please read the note on the back and fill out this page) Set the economy, the production of the Bayer Consumers' Society, and the Intellectual Property Office 30 -

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printing Clothing 1,285,651. 5. Invention (28) The organic photochromic material has an activation absorption maximum value in the visible light range of more than 590 nm, for example, greater than 59 〇 s7 〇〇 Between nm. When the UV light is exposed to a suitable > troche or substrate, the materials typically exhibit blue, green or blue-violet color. Examples of such materials which can be used in the present invention include, but are not limited to, snail (naphthoquinone) naphthoazine and snail (ton) benzoxazine. These and other types of photochromic materials are described in the open literature. No. 3,562,172; See also, for example, Japanese Patent Publication No. 62/1953 83; and textbooks, Chemical Technology, Book III, 'Photochromism Theory', Chapter 3, Glenn H. Brown, Editor, John Wiley & Sons, Inc. New York, 1971. Considering that the second type of organic photochromic material used to form the photochromic article of the present invention has at least one absorption maximum and preferably two absorption maximums, which is 400 and less. In the visible range between 500 nm. These materials typically exhibit a yellow light color when exposed to ultraviolet light in a suitable solvent or substrate. These compounds contain certain chromenes, ie, benzo rings. South and naphthalene A number of such chromenes are described in the open literature, for example, U.S. Patent Nos. 3,567,605; 4,826,977; 5,066,81 8; 4,826,977; 5,066,818; 5,466,398; 5,384,077; 5,238,93 1; and 5,274,132. The third type of organic photochromic material to form the photochromic article of the present invention has an absorption maximum in the visible range between 400 and 500 nm and another absorption maximum in the visible range between 500 and 700 nm. When exposed to ultraviolet light in an appropriate solvent or substrate, such sheet dimensions suitable for the present Chinese National Standard (CNS) A4 size (210 X 297 mm)

31 1285651 月日修 (more) is replacing trade btL------------- V. Invention description (29) (Please read the note on the back and then fill out this page) The material is typically yellow. / brown to purple / gray. Examples of such materials include certain phenanthro-pyran compounds having a substituent at the 2-position of the pyran ring and a substituted or unsubstituted heterocyclic ring, such as a fused to benzopyrene Benzothiophene is either stupid or stupid. More than. These materials are the subject of U.S. Patent No. 5,429,774. Other photochromic materials to be considered are photochromic organometallic-sigma sulphate salts 'i' (aryl azo)-thio decanoic acid aryl sulfonium salts, for example, mercury dithiazole salts, which are described For example, U.S. Patent No. 3,361,706. The fulgide and the physicochemicals (for example, 3···················································· Line 5 to 21, line 38. The disclosure of the photochromic materials in the various patents is hereby incorporated by reference. The photochromic article of the present invention may contain a photochromic material or a mixture of photochromic materials, depending on the intended one. Mixtures of photochromic materials can be used to achieve certain activating colors, such as near neutral gray or brown. The Ministry of Economic Affairs, the Intellectual Property Office, the Staff Consumer Cooperative, which prints each of the photochromic materials described herein, may be such that a mixture of the compounds is applied or the polymer incorporated therein exhibits the desired color (for example, when filtering sunlight) Substantially neutral colors upon activation, such as 'grey or shaded shades', are used in amounts and ratios that are as close as possible to the neutral color of the particular color of the activated photochromic material. The relative amounts of the aforementioned photochromic materials used will vary and will depend in part on the relative strength of the color of the activated species of such compounds and the final desired color. The photochromic compounds or materials described herein can be applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) by the paper size specified by the industry. 32 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Ί 285651 μ / Yuexiu repair (2) is replacing 鸾 _ ...... B7 ......... 丨丨丨 - 5. Various methods of application (3 〇) are applied or incorporated into the polymer. Such methods include dissolving or dispersing such materials in a polymer, for example, by dipping a polymer into a hot solution of a photochromic material or by thermal transfer to cause the photochromic material to be drawn into the polymer; Providing the photochromic material in an individual layer between adjacent polymer layers', for example, as part of a polymer film; and applying the light to a portion of the coating or coating placed on the surface of the polymer Color changing materials. The term "intake" is used to mean and include the infiltration of photochromic material into the polymer. The solvent assists in the transfer of the photochromic material into the porous polymer, vapor phase transfer and other such transfer mechanisms. An example of an inhalation method comprises the steps of coating the photochromic article with a photochromic material; heating the surface of the photochromic article; thereafter removing residual coating from the surface of the photochromic article. The amount of the photochromic material or composition containing the polymer applied or incorporated is not critical as long as a sufficient amount is utilized to produce a photoreceptive effect that is discernible to the naked eye upon activation. Generally, this amount can be described by the amount of photochromism. The particular amount used will generally depend on the color intensity desired for the radiation and the method of combining or applying the photochromic material. Typically, the more photochromic material is applied or incorporated, the greater the color intensity. Generally, the total amount of photochromic material incorporated or applied to the photochromic optical polymer ranges from 015 to 0.35 mg per square centimeter of the surface of the photochromic material incorporated or applied. It is also contemplated that the photochromic material can be added to the two component organic composition prior to polymerization (e.g., prior to curing the μ匕 composition. However, when this is the case, it is preferred that the photochromic material is The paper size of the isocyanate, isothiocyanate and amine groups of the initiators and/or the first and second components which may be present is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - -------IT--------- (Please read the notes on the back and fill out this page) 33 1285651 Doing the F month repair (more) is replacing ij

V. INSTRUCTIONS INSTRUCTIONS (31) Printed by the Ministry of Economic Affairs' Intellectual Property Bureau employee consumption cooperatives Potentially unfavorable interactions are resistant. These unfavorable interactions can cause photochromic materials to become inactive by trapping them in an open or closed form. The photochromic material may also comprise a photochromic colorant and an organic photochromic material coated in a metal oxide, the latter being described in U.S. Patent Nos. 4,166,043 and 4,367,170. A photochromic material (described in U.S. Patent No. 4,931,22) which is sufficiently coated in an organic polymer substrate can also be incorporated into the two component composition of the present invention prior to curing. If a photochromic material is added to the two component organic composition of the present invention, it is typically incorporated into the second component prior to mixing the first and second components together. EXAMPLE 1 Thioglycerol bis(2-M-based acetate) is a preferred polythiol monomer of the present invention, wherein the reference to the center of the invention and the formation of each of the methyl groups. Thioglycerol bis(2-isophthalic acid g) was prepared from the following components. Component Injection 1 Amount (g) 3-mercapto·1,2-propanediol 1995 2-mercaptoacetic acid 2333 Methanesulfonic acid injection 2 14.2 Aqueous ammonia (a) 4218 (a) A 5 wt% aqueous solution of ammonia The component of Feed 1 was added to a 5 liter round bottom flask (which was equipped with a magnetic stirrer, a thermocouple, and a heating mantle coupled via a temperature feedback control device and a vacuum distillation column). 5 to 10 mm (mm) Hg vacuum is inhaled, and the reaction is mixed ---------tr--------- (please read the notes on the back and fill out this page) -34 I2856fl089124386 Patent Application Specification Revision 1 B7............ V. Description of the Invention ς 2) The compound is heated and kept at 70 ° C for 4 to 5 hours while the water is self-steaming collect. (Please read the notes on the back and fill out this page.) When no more water is observed to be collected from the distillation column, the reaction mixture is cooled to room temperature and transferred to a 6 liter round bottom flask (which is equipped with a motor) Agitating knife, thermocouple and water-cooled casing). Feed 2 was added to the mixture and then stirred for 30 to 45 minutes with an exotherm of 10 ° C to 20 ° C. Upon cooling to room temperature, the reaction mixture was allowed to stand to accumulate an upper ammonia layer which was removed by attraction of a pipette. The remaining lower layers were washed 3 times, each time with 2 liters of deionized water. The water was stripped from the washed layer to produce 1995 grams of thioglycerol bis(2-M-based acetate) in the form of a yellow oil and having a refractive index of 1.5825. Example 2-10 Economic and Industrial Consumption Cooperation 衽 Printing of the Intellectual Property Bureau Polyisoxic acid S is designed to be mixed with polysulfide and in some cases with polyol at 80 ° C for 2 hours to produce a viscous liquid prepolymer. The first group. The first component of the warm prepolymer is rapidly stirred and the second component of the diamine is added. After the mixture was stirred for k seconds, the mixture was immediately injected between the two flat glass molds. The filled mold was heated to 120 ° C and maintained at this temperature for 16 hours to produce a plastic sheet. The polyisocyanate-based α,α,-xylene diisocyanate (XDI), α,α,α',α'-tetramethylxylene diisocyanate (TMXDI) and bis(isocyanato) ring used in these examples Hexyl) methane (H-MDI). Dithiol and polyol are 2,2,-thiodiethanethiol (DMDS) and trimethylolpropane (ΤΜΡ), tone polyol 32Β8 (UC32B8), and Tone polyol 32CB (UC32C8); Tone Polyols were obtained from Union Carbide (Danbury, Connecticut). The second component of polyamine is diethyltoluenediamine. The paper size is applicable to China National Standard (CNS) A4 specification (21〇X: 297 mm) 35 1285651 A7 B7 %年丨η曰More) is replacing page five , invention description (33) (DETDA). The specific molar composition and molar ratio of each component used in each of the examples is summarized in Table 1. The physical properties of each of the sample measurements are summarized in Table 2. Example 11 The first component was prepared by mixing 0.6 equivalents of H-MDI and 1 equivalent of DMDS at 90 ° C for 1 hour. When stirred, 0.6 equivalent of XDI was added to the first component. The mixture was stirred for an additional 1.5 hours to produce a viscous prepolymer. 0.25 equivalents of DETDA were added to the warm prepolymer. After stirring for a few seconds, the resulting mixture was injected between the two flat glass molds. The filled mold was heated to 120 ° C and maintained at this temperature for 16 hours to produce a plastic sheet. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Form 1 Sample No. Record Book Number • NCO Composition -SH + -OH Composition NCO/(SH + OH) nh2/nco 2 8247-118 TMXDI DMDS 1.2 0.95 3 8247-120 TMXDI DMDS 2.6 0.95 4 8247-119 TMXDI DMDS 4.0 0.95 5 8247-125-26 TMXDI DMDS 2.6 0.4 6 8247-111 XDI DMDS 1.2 0.95 7 8247-109 H-MDI DMDS 1.2 0.95 8 8247-112 XDI 75% DMDS 25% UC32B8 1.2 0.95 9 8247-113 XDI 75% DMDS 25% UC32B 1.2 0.95 10 8247-107 H-MDI 85% DMDS 15%TMP 1.2 0.95 11 8247-123 50% XDI 50% H-MDI DMDS 1.2 0.25 --------IT---------· This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 36 Five I2856^ ) 8%24386 patent application description repair ~-- B7 date 汍 麟 厫, invention description ^ 2nd table example number NDiAR1) ND (PLM2) Abbe number (AR1) Abbe number (PLM2) Pakistan Available 934 (0-15 seconds) 2 1.604 1.604 33 32 to 38 41-39 3 1.585 31 to 39 1.578 30 to 39 1.582 33 41-40 6 1·62<η<1·6 3 7 1.577 32 to 42 1.600 30 To 51 1.576 29 to 58 10 1.571 1.570 41 41 to 58 (Please read the notes on the back and fill out this page) 11 1.610 35 37-34 1Measure with B&L Abbe refractometer (AR) 2Measure with polarized light microscope (PLM) These examples demonstrate the excellent high refractive index, high Abbe number and hardness (impact resistance) of the polymers of the present invention. The invention has been described with reference to the preferred embodiments. Obvious improvements and changes can be made by reading and understanding the detailed description. It is intended that the present invention be construed as including all such modifications and changes (which are within the scope of the appended claims) or its equivalents. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297). PCT) 37

Claims (1)

1285651 Sixth, the patent application No. 89124386 patent application application special y xiang map correction +,, - 丨丨 and 1.% more and the Japanese page of the preparation of the polymer method, the package of the composition of the composition, the composition The object comprises: (a) a first component comprising a reactant greater than or equal to a difunctional group, the functional group being selected from the group consisting of isocyanates, isothiocyanates, or the like, The reactant is the following reaction product (1) having a polythiol monomer having greater than or equal to a dithiol group; and (ii) having a function of greater than or equal to two selected from the group consisting of isocyanates, isothiocyanates, or the like. a monomer of the group; and (b) a second component comprising a polyamine reactant greater than or equal to a functional group greater than or equal to two selected from the group consisting of a primary amine, a secondary amine, or the like; The molar equivalent ratio of the (NCO + NCS) group to the (-NH 2 + -NH-) group of the second component is 〇. 5 to 1 〇〇, and the first component and the second component are selected. So that when it is polymerized, the polymer formed has a refractive index greater than or equal to ^^ and greater than or equal to 30 Abbe number. 2. The method of claim 1, wherein the first component further comprises (iii) a reactive hydrogen material having a reactive hydrogen group greater than or equal to 'the reactive hydrogen material is selected from the group consisting of polyols, Hydroxyl and thiol based materials, and mixtures thereof. 38 1285651 VI. Scope of Application Patent 3. The method of claim 1, wherein the relative defects of (1) and (ii) in the first component are selected such that (Nc〇+ NCS)/(SH) The molar equivalent ratio is greater than 1. 4. The method of claim 2, wherein the relative amounts of (1), (ii) and (iii) in the first component are selected such that (Nc〇+ NCS)/(SH +OH) The ear equivalent ratio is greater than 1#〇. 5. The method of claim 1, wherein the first component and the second component are selected such that when they are polymerized, the formed polymer has a refractive index greater than or equal to 1.57 and greater than Or equal to the Abbe number of 3 及 and the initial Barco hardness greater than or equal to 1. 6. The method of claim 2, wherein the relative amounts of (1), (ii) and (iii) are selected such that the molar equivalent ratio of (NCO + NCS) / (SH + OH) is 1.2: 1.0 to 4.0:1.0. 7. The method of claim 1, wherein the polythiol monosystem is selected from the group consisting of 2,5-dimercaptodecyl-1,4-dithiane, 2,2, thiodiethane thiol , pentaerythritol tetrakis(3·mercaptopropionate), pentaerythritol tetrakis(2_mercaptoacetate), trimethylolpropane tris(3-M-propionate), trimethylol propylene (2·2) Weiji acetic acid g), 4-weilkylmethyl-3,6-dithia-1,8-octanedithiol, 4_t-butyl-1,2-benzenedithiol, 4,4, _Thionyl dithiol, phenyldithiol, ethylene glycol bis(2- mercaptoacetate), ethylene glycol mono(3-cyanopropionic acid g), poly (Ethylene), one (2) · thioglycolic acid@) and poly(ethylene glycol) bis(3-mercaptopropionate), a polythiol represented by the following formula 39 1285651 6. Patent application scope J- 8. wherein each of 1^ and R2 is independently selected from the group consisting of a stretch or a branched alkyl group, a cyclic alkyl group, a phenyl group, and an alkyl group substituted with an alkyl group of Cl-c9, and An oligomer of a polythiol; and a mixture of the polythiol monomers. The method of claim 7, wherein the polythiol oligomer is disulfide-bonded and is produced by the reaction of a polythiol precursor with sulfur in the presence of an inert catalyst. The method of claim 7, wherein the polythiol oligomer is represented by the following formula: Wherein π is an integer from 1 to 21. The method of claim 7, wherein the polythiol polymer is represented by the following formula: 40 1285651 6. Patent application scope Its center and! ^ Each is an alkyl group selected from a straight chain or a branched chain, an alkylene group, a cyclic alkyl group, a phenyl group, and an alkyl group, and the η and m groups are each an integer of from 〇 to 21, So that #^ is greater than or equal to 1. U. The method of claim 1, wherein the single system has a polycyanate having a diisocyanate group or greater. 12. The method of claim 1, wherein the single system has a polycyanate having one or more sulfur atoms in its backbone. 13. The method of claim 12, wherein the single system having one or more sulfur atoms in its backbone has one of the following formulas: 〇CN, Rl〆 \nco wherein each of R10 and Rn is individually <^ to (:3 alkyl). The method of claim 2, wherein the single system is selected from the group consisting of α 41 1285651 , α-xylene diisocyanate, α,α,α,,α,·tetramethyl dimethyl diisocyanate, isophorone diisocyanate, bis(isocyanato-hexyl)decane, o-toluidine II Isocyanate, o-tolyl diisocyanate, ortho-tolyl diisocyanate, and 4,4, diphenyl-methane-isophthalic acid vinegar and a mixture of the monomers. The method of claim 1, wherein the second component of the polyamine reactant is selected from the group consisting of vinylamine, CfC: 3 dialkyl toluenediamine Methyldiphenylamine, trimethylglycol di(p-aminobenzoic acid benzoate), diamine represented by the general formula (A): (A) a diamine represented by the formula (B): (B) And a diamine represented by the formula (C): (C) The method of claim 15, wherein the diamine represented by the formula (A) is selected from one or more of the following, and a mixture of the diamines: 42 1285651 43 1285651 44 1285651 45 1285651 VI. Application for patent scope Wherein each of Rs and R4 is independently a CpCs alkyl group, and rs is selected from the group consisting of hydrogen and _. 19. The method of claim 1, wherein the second component of the polyamine reactant is diamine toluene dialkyl sulfide. The method of claim 19, wherein the diamine toluene dialkyl sulfide is a 2,6-diaminotoluene-3,5-dialkyl sulfide of the formula: Wherein Re and R7 are linear, branched or cyclic ^ to ^^ alkyl. 21. 22. 23. 24. The method of claim 1, further comprising the step of adding a catalyst to the two component composition. The method of claim 21, wherein the catalyst is selected from the group consisting of a secondary amine and an organometallic compound. The method of claim 1, further comprising the step of mixing the first component and the second component. The method of claim 1, further comprising 46 1285651 VI. Scope of Application for Patent A set of steps for degassing. 25. The method of claim 1 further comprising the step of degassing the second component. 26. The method of claim 23, further comprising the step of adding the mixture to the mold. 27. The method of claim 26, further comprising the step of heating the mold and the mixture of the first component and the second component therein. 28. The method of claim 27, wherein the heating step further comprises heating the mold and the mixture to a temperature of from 10 ° C to 140 ° C during 5 to 16 hours. The method of claim 1, wherein the first component and the second component are in a molar ratio sufficient to provide a (NCO + NCS) basis pair (_NH2 + 30. • NH-) 〇.5 to 1〇 amount together. The method of claim 2, wherein the first component and the second component are in a molar ratio sufficient to provide a (NCO + NCS) basis pair (-Nh2 + · ΝΗ-). • The amounts of 5 to 5 are aggregated together. 31. The method of claim w, further comprising adding a dye selected from the group consisting of a light stabilizer, a heat stabilizer, an antioxidant, a UV absorber, a mold release agent, a static (non-photochromic) dye, a colorant, and a flexibility The steps of additives and additives for anti-yellowing additives and mixtures of such additives. • The method of claim 31, wherein the additive is present in the two groups in an amount of up to 1% by weight of the composition of the two components 47 1285651 Sixth, the scope of application for patents. 33. The method of claim 31, wherein the release agent is a C16 alkyl phosphate. 34. The method of claim 1, wherein the polymer further comprises a photochromic material. 35. A polymer obtained by polymerizing a composition comprising one of the following components, (a) a first component comprising greater than or equal to a reactant greater than or equal to a difunctional group selected from the group consisting of isocyanates, isothiocyanates, or the like, and the reactants are The reaction product (1) has a polythiol monomer having a dithiol group greater than or equal to; and (单体) a monomer having a functional group greater than or equal to two selected from the group consisting of isocyanates, isothiocyanates, and the like. ; and (b) a second component comprising a polyamine reactant greater than or equal to a functional group greater than or equal to two selected from the group consisting of a primary amine, a secondary amine or the like; wherein the first component (NCO + The ratio of the molar equivalent of the (-NH2 + -NH-) group of the second component to the second component is 〇·5 to, the first component and the second component are selected such that when they are polymerized, The formed polymer has a refractive index greater than or equal to 157 and an Abbe number greater than or equal to 30. 36. The polymer of claim 35, wherein the first component further comprises (Hi) a reactive hydrogen having greater than or equal to two reactive hydrogen groups. 48 1285651 VI. Scope of Patent Application The reactive hydrogen material is selected from the group consisting of polyols, materials having a mercapto group and a thiol group, and mixtures thereof. 37. The polymer of claim 35, wherein the relative amounts of (1) and (ii) in the first component are selected such that the molar equivalent ratio of (NCO + NCS) / (SH) is greater than 1.0. . 38. The polymer of claim 36, wherein the relative amounts of (1), (ii) and (iii) in the first component are selected such that (NCO + NCS) / (SH + OH) The ear equivalent ratio is greater than io. 39. The polymer of claim 35, wherein the first component and the first component are selected such that when they are polymerized, the polymer formed has a refractive index greater than or equal to 1.57, greater than or An Abbe number equal to 30 and an initial Barco hardness greater than or equal to 1. 40. The polymer of claim 38, wherein the relative amounts of (1), (ii) and (iii) are selected such that the molar equivalent ratio of (NCO + NCS) / (SH + OH) is 1.2: 1.0 to 4.0: 1.0. 41. The polymer of claim 35, wherein the polythiol single system is selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane, 2,2,-thiodiethane sulfur Alcohol, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2·mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate) Acid ester), 4-mercaptomethyl-3,6-dithia-1,8-octane dithiol, 4_t-butyl-1,2-benzenedithiol, 4,4,·sulfur Diphenylthiol, phenyldithiol, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), poly(ethylene glycol) bis(2-weirylacetic acid) Ester) and poly(ethylene glycol) bis(3- mercaptopropionate), polysulfide represented by the following formula 49 1285651 6. Patent application range: The center and each of the individual are selected from the group consisting of a stretch or a branched alkyl group, a cyclic alkyl group, a phenyl group and a Ci_C9 alkyl substituted phenyl group, and a polythiol polymer. And a mixture of the polythiol monomers. 42. The polymer of claim 41, wherein the polythiol polymer is disulfide-bonded and is produced by the reaction of a polythiol monomer with sulfur in the presence of an inert catalyst. 43. The polymer of claim 41, wherein the polythiol oligomer is represented by the formula: wherein η is an integer from 1 to 21. 44. The polymer of claim 41, wherein the polythiol oligomer is represented by the following formula: 1285651 VI. Application for patent scope SH f Γ —C〇—〇1.....03⁄4— 〇 • S· Ή its center and each of 112 are individually selected from linear or branched alkyl, cyclic alkyl, phenyl and Cl-c9 alkyl substituted phenyl, and 11 The m series are individually integers from 0 to 21 such that n+m is greater than or equal to one. 45. The polymer of claim 35, wherein the single system has a polycyanate having greater than or equal to a diisocyanate group. 46. The polymer of claim 45, wherein the polycyanate monosystem is selected from the group consisting of α,α,_xylene diisocyanate, α,α,α,α, tetramethyl dimethyl benzene Isocyanate, isophorone diisocyanate, bis(isocyanatocyclohexyl)methane, o-toluidine diisocyanate, o-methylidene diisocyanate, o-tolyl diisocyanate and 4,4'- Styrene methane diisocyanate and a mixture of the monomers. 47 » . ^ • σ The polymer of claim 45, wherein the monomer contains one or more sulfur atoms in its backbone. 48 ^ • If the polymer of the scope of patent application 47, which should be contained in its trunk 51 1285651 VI. Scope of Application Patent The monomer with one or more sulfur atoms has the following formula: And NCO wherein each of R10 and Rn is an alkyl group. The polymer of claim 25, wherein the second component of the polyamine reactant is selected from the group consisting of vinylamine, CfCs dialkyl toluenediamine, methyldiphenylamine, trimethylglycol bis(p-aminobenzoate), diamine represented by the general formula (A): (A) Η Diamine represented by formula (Β): (Β) And a diamine represented by the formula (C): (C) 52 1285651 53 1285651 54 1285651 55 1285651 Sixth, the scope of application for patents Wherein each of I and I is individually a Cl_C3 alkyl group, and R5 is selected from the group consisting of hydrogen and halogen. 53. The polymer of claim 35, wherein the second component of the polyamine reactant is a diaminotoluene dialkyl sulfide. 54. The polymer of claim 53, wherein the diaminotoluene dialkyl sulfide is a 2,6-diaminotoluene-3,5-dialkyl sulfide of the formula: Wherein R6 and R7 are linear, branched or cyclic ClSC2G alkyl 〇 55. The polymer of claim 35, wherein a catalyst is added to the two component composition to promote the polymerization. 56. The polymer of claim 55, wherein the catalyst is selected 56 1285651 VI. Scope of application for patents From tertiary amines and organometallic compounds. 57. The polymer of claim 35, wherein the polymerization method further comprises the step of mixing the first component and the second component. 58. The polymer of claim 35, wherein the polymerization further comprises the step of degassing the first component. 59. The polymer of claim 35, wherein the polymerization further comprises the step of degassing the second component. 60. The polymer of claim 57, wherein the polymerization further comprises the step of adding the mixture to a mold. 61. The polymer of claim 60, wherein the polymerization further comprises the step of heating the mold and the mixture of the first component and the second component therein. 62. The polymer of claim 61, wherein the heating step further comprises heating the mold and the mixture to a temperature of from 100 ° C to 140 ° C over a period of from 0.5 to 16 hours. 63. The polymer of claim 35, wherein the first component and the second component are in a molar equivalent ratio sufficient to provide (NCO + NCS) radicals (·ΝΗ2 + -ΝΗ-) groups Aggregated together in an amount of from 0.5 to 10. 64. The polymer of claim 35, wherein the first component and the second component are in a molar equivalent ratio sufficient to provide a (NCO + NCS) radical (_ΝΗ2 + -ΝΗ-) group. The amounts of 0.5 to 5 are aggregated together. 65. The polymer of claim 35, further comprising a light stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorber, a mold release agent, a static (non-photochromic) dye, a colorant, and a flexibility. Additives and 57 1285651 6. Additives for anti-yellowing additives and mixtures of such additives. 66. The polymer of claim 65, wherein the release agent is a C8 to C16 alkyl phosphate ester. 67. The polymer of claim 65, wherein the additive is present in the polymer in an amount up to 10% by weight of the polymer. 68. The polymer of claim 35, further comprising a photochromic material. 69. A photochromic article derived from a polymer prepared by polymerizing a two component composition comprising: (a) a first component comprising greater than or equal to one greater than or a reactant equivalent to a difunctional group selected from the group consisting of isocyanates, isothiocyanates, or the like, and the reactants are the following reaction products: (1) polysulfide having a dithiol group greater than or equal to An alcohol monomer; and (ii) a monomer having a functional group greater than or equal to two selected from the group consisting of isocyanates, isothiocyanates, or the like; and (b) a second component having greater than or equal to one a polyamine reactant having a functional group greater than or equal to two selected from the group consisting of a primary amine, a secondary amine, or the like; wherein the (NCO + NCS) group of the first component is (·ΝΗ2 + - The NH-) base molar equivalent ratio is from 0.5 to 100, and the first component and the second component are selected such that when they are polymerized, the formed polymer has a refractive index greater than or equal to 1.57 and Greater than or 58 1285651 Sixth, the scope of application for patents is equal to 30 Abbe numbers. 70. The photochromic article of claim 69, wherein the first component further comprises (iii) a reactive hydrogen material having a reactive hydrogen group greater than or equal to two, the reactive hydrogen material being selected from the group consisting of Alcohol, materials having hydroxyl and thiol groups, and mixtures thereof. 71. The photochromic article of claim 69, wherein the relative amounts of (1) and (ii) in the first component are selected such that the molar equivalent ratio of (NC〇+ NCS)/(SH) The system is greater than 1.〇. 72. The photochromic article of claim 70, wherein the relative amounts of (i), (ii) and (iii) of the first component are selected such that (NCO + NCS) / (SH + The molar equivalent ratio of OH) is greater than 1.0. 73. The photochromic article of claim 69, wherein the first component and the second component are selected such that when polymerized, the polymer formed has a refractive index greater than or equal to 1.57, An Abbe number greater than or equal to 30 and an initial Barco hardness greater than or equal to 1. 74. The photochromic article of claim 7 wherein the relative amounts of (1), (H) and (iii) are selected such that the molar equivalent ratio of (NCO + NCS) / (SH + OH) Department ι·2: 1.0 to 4.0: 1.0. 75. The photochromic article of claim 69, wherein the polythiol monosystem is selected from the group consisting of 2,5·dimercaptomethyl-1,4-dithiane, 2,2,-sulfur Ethyl mercaptan, pentaerythritol tetrakis(3-M-propionate), pentaerythritol tetrakis(2-mercaptoacetate), tridecyl alcohol propane tris(3- mercaptopropionate), trimethylolpropane three (2-M-based acetate), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 4_t-butyl-1,2-benzenedithiol 4,4,· 59 1285651 VI. Patent application range thiodiphenyl thiol, benzene dithiol, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3·mercaptopropionate) , poly(ethylene glycol) bis(2-mercaptoacetate) and poly(ethylene glycol) bis(3-mercaptopropionate), a polythiol represented by the following formula: Wherein each of 1 and 112 is an alkyl group substituted with an alkyl group, a cyclic alkyl group, a phenyl group and an alkyl group substituted with CrCp, and an oligomer of the polythiol. And a mixture of the polythiol monomers. 76. The photochromic article of claim 75, wherein the polythiol oligomer is disulfide-bonded and is obtained by reacting a polythiol monomer with sulfur in the presence of a basic catalyst. . 77. The photochromic article of claim 75, wherein the polythiol oligomer is represented by the following formula: Wherein η is an integer from 1 to 21. 78. The photochromic article of claim 75, wherein the polythiol oligomer is represented by the following formula: 60 1285651 6. Patent application scope The center and & each are individually selected from a linear or branched chain of an alkyl group, a cyclic alkyl group, a phenyl group, and an alkyl group substituted with an alkyl group of Cl-c9, and the η and m groups are individually To 整数 to an integer of 21, so that n+m is greater than or equal to 1. 79. The photochromic article of claim 69, wherein the monomer has a polycyanate having greater than or equal to a diisocyanate group. 80. The photochromic article of claim 79, wherein the single system is selected from the group consisting of α,α-biphenylene diisocyanate, α,α,α′,α tetramethylxylene diisocyanate, isophor Keto diisocyanate, bis(isocyanatocyclohexyl)methane, o-anisidine diisocyanate, o-tolyl diisocyanate, o-tolyl diisocyanate and 4,4,-diphenylmethane diisocyanate a mixture of the monomers. 81. The photochromic article of claim 69, wherein the second component of the polyamine reactant is selected from the group consisting of vinylamine, ci_C3 dialkyl toluenediamine, methyldiphenylamine, and tris. Methyl glycol di(p-amino group 61 1285651 VI. Patent application range benzoate), diamine represented by the general formula (A): (A) a diamine represented by the formula (B): (B) And a diamine represented by the formula (C): (C) Η 82. The photochromic article according to claim 81, wherein the diamine represented by the formula (Α) is selected from one of the following Or more, and a mixture of such diamines: 62 1285651 63 1285651 64 1285651 VI. Scope of application for patents Each of R3 and R4 is individually hydrogenated and halogen. 84. The photo-chromic article of claim 81, wherein the diamine represented by the formula (C) is selected from one or more of the following amines: 'and Rs is selected from the group, and the two Wherein each of R3 and R4 is independently a Cl-C3 alkyl group derived from hydrogen and a halogen. 85. The photochromic article of claim 69, and Rs is selected from the second 65 1285651. The polyamine reactant is a diaminotoluene dialkyl sulfide. 86. The photochromic article of claim 85, wherein the diaminotoluene dialkyl sulfide is a 2,6-diaminotoluene-3,5-dialkyl sulfide of the formula: Wherein R6 and R*7 are linear, branched or cyclic (^ to c2G alkyl 〇87. The photochromic article of claim 69, wherein a catalyst is added to the two component composition to promote the The photochromic article of claim 87, wherein the catalyst is selected from the group consisting of tertiary amines and organometallic compounds. 89. The photochromic article of claim 69, wherein the polymerization The reaction method further comprises the step of mixing the first component and the second component. 90. The photochromic article of claim 69, wherein the polymerization further comprises the step of degassing the first component 91. The photochromic article of claim 69, wherein the polymerization further comprises the step of degassing the second component. 92. The photochromic article of claim 69, wherein The polymerization further comprises the step of adding a mixture of the first component and the second component to a mold. 66 1285651 VIII. Patent Application Serial No. 93. The photochromic article of claim 92, wherein the polymerization further comprises the step of heating the mold and the mixture therein. 4. The photochromic article of claim 93, wherein the heating step further comprises heating the mold and the mixture to 1 Torr during 0.5 to 16 hours. 〇 to 140. (: The temperature. 95. The photochromic article of claim 69, wherein the first component and the second component are sufficient to provide (NCNH+ NCS)-based (_NH2 + -NH-) groups. An equivalent ratio of 〇.5 to 10 is polymerized together. 96. The photochromic article of claim 69, wherein the first component and the second component are sufficient to provide (NC〇+ NCS The molar equivalent ratio of the base pair (_NH2 + -NH-) group is 〇·5 to 5, and is aggregated together. A A • The photochromic article of claim 69, further packaged Containing an additive selected from the group consisting of a light stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorbing J' release agent, a static (non-photochromic) dye, a colorant and a flexible additive, and an anti-yellowing additive, and the like mixture. 98. The photochromic article of claim 97, wherein the additive is present in the polymer in an amount up to 1 〇 ❶/❷ of the polymer. "·For example, the photochromic article of claim 97, wherein the release agent is a Cs to C16 alkyl sulphate. 67 1285651 VI. Scope of Application Patent 100. The photochromic article of claim 69, which further comprises a photochromic material. The photochromic article of claim 100, wherein the photochromic material is mixed with the first component. 102. The photochromic article of claim 100, wherein the photochromic material is mixed with the second component. 103. The photochromic article of claim 1, wherein the photochromic material is applied to the photo-photometric unit at a surface of from 0.15 to 0.35 mg per square centimeter of the surface of the photochromic article. Color changing objects. 104. The photochromic article according to claim 0000, wherein the photochromic material is selected from the group consisting of snail (tetra) oxime) naphthoazine, snail (π 嘌 嘌) benzoxazine, chromene, benzene And pyran, naphthopyran, organometallic dithiazolidine salt, (square-based gas)-thiocarbamic acid aryl-branched salt, pickling salt, fulgic acid anhydride, cuminimide, 3 - furan-based fulgide, 3_thenyl-based fulgide, 3-σ-fusyl-haloquinone imine, and 3-σ 基 浮 浮 & amp &&&>imine, and such photochromic materials a mixture. 105. The photochromic article of claim 1, wherein the photochromic material has a maximum active absorption in the visible range of 590 to 700 nm. 106. The photochromic article of claim 1, wherein the photochromic material has a maximum active absorption in the visible range of 400 to 500 nm. 107. The photochromic article of claim 100, wherein the photochromic material has a living range of from 500 to 700 nm in the visible range of 68 1285651. 108. The photochromic article of claim 100, wherein the photochromic material is selected from the group consisting of casting curing, coating in an organic polymer substrate, and incorporating the two component composition prior to curing. The method within is applied or incorporated into the photochromic article. 109. The photochromic article of claim 100, wherein the photochromic material is applied by absorbing the photochromic article such that penetration of the photochromic material into the polymer is achieved. 110. The photochromic article of claim 109, wherein the absorption method comprises solvent assisted transfer absorption. 111. A photochromic article according to claim 1 wherein the method of absorption comprises vapor phase transfer. 112. The photochromic article of claim 100, wherein the photochromic material is applied to the surface of the photochromic article by a coating. 113. The photochromic article of claim 109 Wherein the absorption method comprises the steps of: coating the photochromic article with a photochromic material; heating the surface of the photochromic article; and removing residual coating from the surface of the photochromic article. 114. The photochromic article of claim 1, wherein the photochromic article is an optical lens for correcting visual loss. 115. The photochromic article of claim 69, wherein the monomer contains one or more sulfur atoms in its backbone. 69 1285651 6. Patent application scope 116. The photochromic article of claim 115, wherein the monomer having one or more sulfur atoms in its backbone has the following formula: NCO 0CN\r/ Wherein each of R10 and Ru is an alkyl group of (^ to ^). The method of claim 1, wherein the polymerization is carried out by reaction injection molding, wherein the first component and the first component The parent of the two components is metered from a cylindrical mixing head and injected into a molding machine. 118. The polymer of claim 35, wherein the first component is polymerized by reaction injection molding. The second component is prepared, wherein each of the first component and the second component is metered from a cylinder through a mixing head and injected into a molding machine. 119. a photochromic article obtained by polymerizing the first component and the second component by reaction injection molding, wherein each of the first component and the second component is from a cylinder = mixing head Metered and injected into a molding machine. 70