TW200424220A - Polymerizable organic composition, shaped article and photochromic article - Google Patents

Abstract

The present invention is directed to a novel polymerizable organic composition comprising one or more radically polymerizable monomers with at least one radically polymerizable monomer having at least two (meth) acryloyl groups that have backbone linkages selected from thiourethane linkages, dithiourethane linkages, combinations of thiourethane linkages and dithiourethane linkages. The present invention is also directed to polymerizates prepared from the polymerizable organic composition, shaped articles prepared from the polymerizable compositions, and photochromic articles that may be prepared from the polymerizable organic composition of the present invention.

Description

IX. Description of the invention: Cross-references to related applications This application requests US Provisional Patent Application Serial No. 6 (No. V166,262 (filed on November 18, 1999, the name of the invention is "optical resin composition"). [Technical field to which the invention belongs] The present invention relates to a polymerizable organic composition, and a polymer obtained therefrom, which has a reflection index of at least 1.6 and an Abbe number of at least 33 and Barcol hardness of at least 1. More particularly, the present invention relates to certain polymerizable organic compositions comprising at least two (meth) acrylfluorenyl groups and selected from the group consisting of sulfur-based gas hydrazones. And / or dithiocarbamate-bonded backbone-bonded free-radically polymerizable monomers. The present invention also relates to photochromic objects made from these polymerizable compositions. [Previous 1 BACKGROUND OF THE INVENTION Several types of organic polymeric materials (eg, plastics) have been developed as alternatives and substitutes for glass in applications such as optical lenses, optical fibers, windows, and transparent objects for automobiles, marine, and aircraft. When used, "glass," the term refers to inorganic glass based on% stone. These polymer materials can provide glass-related advantages, including resistance to shattering, lighter weight for specific applications = lighter than molding and lighter For dyeing. These polymer materials are represented by methyl methacrylate), thermoplastic polycarbonate, and poly (^^ " allyl carbonate)]. Shen ethyl bisphenol double (many polymer materials have a lower reflection index than glass. For example, the poly [diethylene glycol bis (allyl carbonate W has a reflection index of about 150, compared to the piezo number glass, This can range, for example, from 160 to 18. When preparing lenses to correct a specified degree of vision deficiency (e.g., correction of myopia), relative to materials with higher reflectance index (e.g., high index glass) ), The use of polymer materials with a lower reflection index requires thicker lenses. If the required degree of correction is large, such as in severe myopia, lenses made from low-index polymer materials may need to be very thick. Very Thick lenses may offset the weight reduction benefits associated with the equivalent correction obtained from lenses with a higher horseback index (for example, high index glass lenses). In addition, thicker optical lenses are not aesthetically desirable. Polymer materials with a reflection index greater than 1.50 can be made from aromatic monomers and monomers containing carbon atoms and / or sulfur atoms. Materials that can prepare lenses (especially optical lenses) can be classified by their reflection index As known to those skilled in the art, a low index typically includes a reflection index of L50 to 153; a medium index includes a reflection index of 1.54 to 1.57; and a high index generally includes a reflection index of 158 and greater. It has a high reflection Index lenses made from polymeric materials typically also have a lower cobb number (also known as nu value). A lower Abbe number indicates an increased color dispersion, which is typically a lens Light distortion displays at or near the edges. US Patent No. 5,384,379 (Bader et al.) Discloses sulfur-containing poly (meth) acrylates for optical applications. Although the materials disclosed by Bader et al. Can be used as Providing optically-corrected lenses, the disclosed poly (meth) acrylates generally provide inappropriate reflectance and color dispersion. They also generally have poor impact resistance. Therefore, it is desirable to identify new polymerizable organic combinations Materials, which can be used to make damage can have a high reflectance index and a reasonably high Abbe number of ^ breakable polymers, especially optical lenses. Further expectations are σ transparent materials also have at least equal Polymerizations such as polymerization i at a lower index have better physical properties, especially thermal properties. R Also, the car parent is [invention contents] Summary of the invention ^ According to this document, it provides-injectable polymerization organic composition, a Or a radically polymerizable monomer ^, a monomer of a certain polymer # and ancient 5 I, 早 early system with at least one free radical I mouth has at least two selected from, dithioamino The main inventions of S-bond, dithio bond, urethane-bonded urethane-bonded mixture, and disulfide. The basic invention is also related to the methyl-acrylic group derived from the present invention. The present invention made of Huanhe organic composition is further related to the molded article of the present invention. The present invention made of Zhonghe composition is further related to the photochromic article which can be obtained from the present invention. Polymerizable organic composition Detailed description of the invention Unless otherwise indicated, the number of such amounts may be expressed in terms of relevant components and reaction conditions. It is understood that the present invention is related to a kind of polymerizable compound which includes: (a) a first free radical polymerizable monomer having at least two (meth) acryl groups; The first monomer has a backbone bond selected from the group consisting of a thiocarbamate-acid hybrid, a two-claw urethane bond, a thiocarbamate bond, and a dithiocarbamate bond. Bonding, and selective backbone bonding selected from the group consisting of urethane bonding, urea bonding, thiourethane bonding, and mixtures thereof; 〃 (b) selective second free-radically polymerizable Monomer, which is different from the radically polymerizable monomer (a) and has at least diethylenically unsaturated radically polymerizable group, which is selected from the group consisting of vinyl, alkenyl, and (methyl) Propylene amidinyl group; (e) a selective third radically polymerizable monomer, which has at least one ethylenically unsaturated radically polymerizable group and is different from monomer (a) and monomer (b), And is selected from: (0 monovinyl unsaturated monomers; (U) a wild monomer having at least one ethylene unsaturated group, which is different from the monomer ⑴; and (iii) Mixtures of monomers ⑴ and ⑻, and () choose J * sheng's polyperoxide grass with at least two thiol groups. The present invention is also a polymer of this polymerizable organic composition, which has about 157 To about UOC is preferably a reflection index of about 1.60 to about 75); to an Abbe number of about 30 (preferably at least about 33); and an initial Barco hardness of at least 1. In the preferred embodiment, the reflection index is 1.6 less JL (for example, 1.60 to 1.74)

^ Epistar numbers are determined according to the American standard test method (ast⑷ No. D 542-95. Abbe numbers or Nu values are determined using a suitable instrument (for example, B-side h & ABBE-3L reflectometer). Starting bar The hardness (commonly referred to as zero second Barco hardness) is determined according to ASTM number D 2583-95. The first monomer (a) of the polymerizable composition has a member selected from a thiocarbamate bond (ONH-C) (O) -S ·), a dithiocarbamate bond (-NH_C (S) _S_), and a backbone of a mixture thereof. In addition, the first monomer may optionally have a member selected from carbamate Ester bond (-NH-C (O) -O-), urea bond (e.g., unsubstituted urea bond -NH-C (0) -NH- and / or substituted urea bond ν (κμκ: (ο) _νη-, which may be Cl_C4 alkyl), a thiocarbamate bond (-NH-C (S) -O-), and a backbone bond of a mixture thereof. Monomers are typically prepared in a two-step process, in which the precursor that forms the backbone of the first monomer is formed, and then the terminal part of the precursor is functionalized with a (meth) acrylfluorenyl group. The first monomer The precursors of the body are generally made by the following reactions (1) Polythiol monomer having at least two thiol groups; having at least two functional groups selected from the group consisting of lactic acid vinegar (-NCO), isothiocyanate (_NCS), and the like Polycarbonate monomer, and (3) selective anti-m hydrogen material having at least two reactive hydrogen groups selected from the group consisting of a base, a secondary amine, a secondary amine, and a mixture thereof. Polythiol monomer The mercaptan thiol group typically comprises at least 50 mole% of the total molar equivalents of the polythiol monomer and the thiol group of the reactive hydrogen hydrazone, the primary group, the primary amine, and the primary amine group (e.g., at least 80 mol% or at least 90 mol. / 〇). In the precursor for preparing the first monomer, the equivalent ratio of (NCO + NCS) / (SH + OH + NH2 + _ bribe_) is typically G, .25: 1 to 4: 1, for example, 0.5: 1 to 2.1 or 0.8: 1 to 1 2: 1. Therefore, the precursor of the first monomer may have a terminal cyano group, such as isocyanate and / or Isothiocyanate group, or a terminal reactive hydrogen group selected from the group consisting of thiol, hydroxyl, primary amine, secondary amine, and mixtures thereof. When the precursor of the first monomer has a terminal cyanate group, The terminal part of the precursor can be selected by The reactive hydrogen-functional alkyl (meth) acrylate of a hydroxyl group, a thiol, and a primary amine is functionalized. Typically, the precursor terminal cyanate moiety is reacted with a hydroxyalkyl group (methyl ) Acrylate (such as 2-hydroxyethyl methacrylate) to be functionalized. When used herein, "(meth) acrylfluorenyl" and similar terms (such as "(meth) acrylate, ,) Means acrylfluorenyl, methacrylfluorenyl, and a mixture of acrylfluorenyl and methacrylfluorenyl. As used herein, "cyanate ester," and similar terms (such as "polycyanic acid "" And "cyanate group") means an isocyanate group (-NC0), an isothiocyanate group (-NCS), and a mixture of an isocyanate group and an isothiocyanate group. § When the precursor of the first monomer has a reactive hydrogen group (for example, a terminal thiol group), the terminal portion of the precursor can be obtained by reacting with (meth) acrylic anhydride, (meth) acrylic gaseous compound, or ( Meth) acrylate monomers (which have functionality to react with terminal reactive hydrogen groups, such as glycidyl (meth) acrylate, isocyanatoalkyl (fluorenyl) acrylate, or hydroxyalkyl ( Methacrylic acid formic acid vinegar) is an example of functionalization. The first monomer may be a monomer, oligomer or polymer, and thus may have a broad target molecular weight, for example, having a number average of 5000 to 150,000 (or 5000 to 50,000) Molecular weight (Mn), purely by gel permeation of the polyphenylene collimator = spectroscopic mosquito. In the case of Hong Dian, the molecular weight of the first monomer is so that the viscosity of the first monomer will not be too high for the monomer. For example, 200424220, when used to make ophthalmic lenses, the first monomer typically has a viscosity (at 25 C) of less than 800 centipoise (cPs) ', for example, less than 500 cPs. The polythiol monomer used to prepare the precursor of the first monomer has at least two thiol groups and can be selected from 2,5-dimercaptomethyl_, 4_dithiane, 2,2, _thio Diethane 5 thiol, pentaerythritol tetra (3 · mercaptopropionate), pentaerythritol tetra (2-fluorenyl acetate), trimethyl alcohol propane tri (3-mercaptopropionate), trimethylthiopropane Tris (2-mercaptoacetate), 4-fluorenylmethyl · 3,6 · dithia_; ι, 8_octane dithiol, 4-tert-butyl1,2-benzenedithiol, 4,4, -thiodiphenyl mercaptan, benzene dithiol, ethylene glycol bis (2-fluorenyl acetate), ethylene glycol bis (3-fluorenyl propionate), poly (ethylene di 10 Alcohol) bis (2 · thioglycolate), poly (ethylene glycol) bis (3 · thiopropionate). A mixture of polythiols can be used to prepare a precursor of the first monomer. Polythiols represented by the following general formula can also be used to prepare precursors of the first monomer, (I)

Its center and heart are each selected from the group consisting of straight or branched alkylene, cyclic alkylene, alkylene and Cl_C9 alkyl-substituted alkylene, and these polythiol monomers. mixture. Examples of straight or branched arsenyl groups that can be used for RiAR2 include dimethyl, ethyl, propyl, 20-yl, butyl, 2-, 2-butyl, and phenyl , Hexyl, heptyl, octyl, nonyl, decyl, undecyl, octadecyl, and eicosene, but not limited thereto. Examples of cycloalkenyl groups that can be selected for each of them may be selected from cyclopentyl, cyclohexyl, cycloheptyl 'cyclohexyl 11 200424220, and alkyl substituted derivatives, but not Limited to this. The divalent bonding base and core may also be selected from the group consisting of phenylene and alkynyl substituted phenylene, for example, methyl, ethyl, propyl, isopropyl, and nonyl substituted phenylene. In a preferred embodiment of the present invention, each of rar2 may be methyl or ethyl. 5 Polythiol represented by U Formula 1 can be obtained from 3-acyl · 1,2-propanediol in the presence of a strong acid catalyst (for example, methacylic acid) (Chemical Abstract Service (CAS) Registry Editor 5 Tiger 96-27-5) and thiol functional group acetic acid reaction or transesterification reaction of citric acid or citric acid and simultaneous removal of water or alcohol from the reaction mixture. As used herein, a polythiol monomer (10, for example, thioglycerol bis (2-fluorenyl acetate)) described and named with reference to the general formula refers to any related Co-product oligomeric species and polythiol monomer composition. For example, when the reaction mixture formed from the esterification reaction of 3-fluorenylpropane-alcohol and a thiol-functional carboxylic acid (for example, 2-fluorenylacetic acid) is washed with an excess base (for example, aqueous ammonia), the thiol group Oxidative coupling may occur. This 15 oxidation coupling may cause the formation of oligomeric polythiol species with disulfide bonds (ie, -S-S-bonds). The polythiol monomer used for preparing the first monomer precursor may be a polythiol oligomer having a disulfide bond, which may have a polythiol having at least a dithiol group in the presence of a basic catalyst. It is made by reacting monomer with sulfur. The molar equivalent ratio of the polythiol monomer to sulfur 20 is m to (m-1), where m is an integer of 2 to 21. The polythiol monomer can be selected from the aforementioned examples here, for example, 2,5-diMethylmethyl-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 oligomeric species may comprise a copolymer of the general formula I, which may be of the general formula la 12 200424220 Description: la

Wherein 1 and 112 are as described above, η and m are each an integer of 0 to 21, and 5 n + m is at least 1. It has been shown that the oligomerization reaction can be generated via a disulfide bond between any of the thiol groups in the general structure I. Although all possibilities are not shown, the general formula II is meant to represent all oligomers that may be formed from the general structure I. The basic catalyst used to prepare the disulfide-bonded polythiol oligomer can be selected from ammonia, amines, and mixtures thereof. Examples of amines include alkylamines (e.g., ethylamine and n-butylamine), diamines (e.g., diethylamine), trialkylamines (e.g., triethylamine), morphine, Substituted morphine, luteidine, and substituted piperidine, but are not limited thereto. Basic catalysts are typically based on 0.001 to 10 mole% (e.g., 0.01 to 0.1 mole% 'which is based on the mole number of poly-15 mercaptan monomer present at the beginning of the reaction). The amount exists. The test catalyst may be injected into the reaction vessel together with the polythiol monomer and sulfur, or may be added to the reaction vessel after adding the polythiol monomer and sulfur. Disulfide-bonded polysulfide Sf polymer can be synthesized in solvents (eg, 13 200424220). For example, dendritic hydrocarbons (such as aeroform), aliphatic hydrocarbons (such as hexane), aromatic hydrocarbons (such as, Toluene) and ethers (such as tetrahydrofuran) are present. Polythiol oligomers can be prepared at temperatures ranging from room temperature to the boiling point of the solvent (eg, room temperature to 12 ° C). They can be used in the present invention. The preparation of sulfide-bonded polythiol oligo-5 is described in more detail in U.S. Patent No. 5,961,889, the disclosure of which is incorporated herein by reference. In the embodiment of the present invention, two The sulfide-bonded polythiol oligomer may be selected from those represented by the following general formula II (II)

Where y is an integer from 1 to 21. Polythiol oligomers represented by the general formula π can be prepared from the reaction of 2,5_dimercaptomethyl · 1,4-dioxane and sulfur in the presence of a basic catalyst (the foregoing). . The polycyanate monomer used to prepare the precursor of the first monomer can be selected from the group consisting of polyisocyanate groups having at least 15 diisocyanate groups, and having at least diisothiocyanate groups. Isothiocyanic acid and polyisocyanate with isocyanate and isothionitrate. The types of polyisocyanic acid vinegar monomers that can be selected as heteroacid monomers include (but not limited to) ... aliphatic polyisocyanate g; [olefinically unsaturated polyisocyanate; alicyclic polyisocyanate Cyanate; where the isocyanate group is not directly bonded to the aromatic ^ ring ^ 20 aromatic polyisocyanate (eg, hydrazone, xylene diisocyanate); where = the isocyanate group is directly bonded to the Aromatic polyaromatic acids = eg, benzene diisocyanate); aliphatic polyisocyanates containing sulfide bonds = 14 200424220 aromatic polyisocyanates containing sulfide or disulfide bonds Cyanine purpose; aromatic polyisocyanates containing wind bonds; polyisocyanates of the sulfonate type (for example, 4-methyl-3-isocyanatobenzenesulfonyl 4'-isocyanato-phenol ester Aromatic sulfonamide-type polyisocyanates; sulfur-containing heterocyclic polyisocyanates (for example, thiophene 5-2,5-diisocyanates); halogenation, alkylation, calcination, and confirmation of polyisocyanates belonging to these categories Derivatives of carbodiimide modification, urea modification and double urea modification; and dimerization and trimerization of polyisocyanates belonging to these categories Polymerization product. Particularly preferred sulfur-containing polycyanate monosystems One of the general formula (III): 10 (III)

Wherein each of R10 and Rn is an alkyl group of (^ to (: 3). Examples of aliphatic polyisocyanates that can be used as precursors of the first monomer include ethylidene diisocyanate and triphenylene. Diisocyanate, tetramethylene 15-based diisocyanate, hexamethylene methyl diisocyanate, octamethyl diisocyanate, nona methyl diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4 -Trimethylhexane diisocyanate, decylfluorenyl diisocyanate, 2,4,4-trimethylhexamethyl diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6- Hexamethylidene triisocyanate, 1,8-diisocyanate-4_ (isocyanate 20-methyl) octane, 2,5,7-trimethyl-1,8 · diisocyanate- 5- (isocyanatofluorenyl) octane, bis (isocyanatoethyl) -carbonate, bis (isocyanatoethyl) ether, 2-isocyanatopropyl-2,6- Diisocyanate hexanoate, lysine 15 200424220 amino acid diisocyanate methyl ester and lysine triisocyanate methyl ester, but is not limited thereto. Examples of ethylene unsaturated polyisocyanates include butene diisocyanate and 1,3-butadiene-1,4-diisocyanate, but it is not limited to this. The cycloaliphatic polyisocyanate that can be selected to prepare the precursor of the first monomer includes isophorone diisocyanate, cyclic Hexane diisocyanate, fluorenyl cyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatocyclohexyl) -2,2 -Propane, bis (isocyanatocyclohexyl) -1,2-ethane, 2-isocyanatofluorenyl-3- (3-isocyanatopropyl) -5-isocyanate Methyl-bis [2.2.1] -heptane, 2-isocyanatofluorenyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-1-bicyclo [2.2. 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] heptane, 2-isocyanate Acid methyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bisacid [2.2.1] -heptane, 2-isocyanatomethyl-3- ( 3-15 isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanate Acid propyl) -5- (2-isocyanatoethyl) -bicyclo [2 .2.1] -heptane and 2-isocyanatofluorenyl-2 (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, However, it is not limited thereto. 20 Examples of the aromatic polyisocyanate in which the isocyanate group is not directly bonded to the aromatic ring include bis (isocyanatoethyl) benzene, α, α, α ′, α′-tetramethyldiamine Toluene diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, bis (isocyanatobutyl) benzene, fluorene (isocyanatofluorenyl) naphthalene, bis ( Isocyanatofluorenyl) diphenyl ether, bis (isocyanatoethyl) phthalate, lyssaiso 16 200424220 cyanate and 2,5-bis (isocyanatomethyl) furan, but Not limited to this. Examples of aromatic polyisocyanates that can be used to prepare the first monomer precursor with isocyanate groups directly bonded to the aromatic ring include phenylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate Isocyanate, dimethyl phenyl diisocyanate, diethyl phenyl diisocyanate, diisopropyl phenyl diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, Biphenyl diisocyanate, di-o-toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, bis (3-methyl-4-isocyanatophenyl) methane, bis (isocyanatobenzene) Group) ethylene 10, 3,3'-dioxo-bisphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymerized 4,4'-diphenylmethane diisocyanate, naphthalenetris Isocyanate, diphenylmethane-2,4,4 '· triisocyanate, 4-methyldiphenylmethane-3,5-2', 4'6'-pentaisocyanate, diphenyl ether diisocyanate, bis ( Isocyanatophenyl ether) ethylene glycol, bis (isocyanatophenyl) ) -1,3-propanediol, 15 benzophenone diisocyanate, carbachol oxazole diisocyanate, ethylene diisocyanate, Ji Kaba oxazole and two gas carbachol oxazole diisocyanate, but is not limited thereto. Sulfide-containing aliphatic polyisocyanates that can be used to prepare the first monomer precursor can be selected from, for example, thiodiethyldiisocyanate, thiodipropyldiisocyanate, dithiodihexyldi Isocyanate, Dimethyl Di 20 isocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, and dicyclohexyl sulfide-4,4'-diisocyanate . Examples of aromatic polyisocyanates containing sulfide or disulfide bonds include diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'- Dimethoxy-4,4'-diisocyanatodiphenyl 17 200424220 methyl thioether, bis (4-isocyanatomethylbenzene) -sulfide, diphenyl disulfide-4 , 4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'- Diisocyanate, 3,3'-dimethyldiphenyl disulfide 6,6'-diisocyanate, 4,4'_dimethyl-5yl diphenyl disulfide-5,5'-diisocyanate, 3 , 3'-dimethoxydiphenyl disulfide-4,4'-diisocyanate and 4,4'-dimethoxydiphenyl disulfide 3,3'-diisocyanate, but not limited thereto . The wind-bonded aromatic polyisocyanate that can be used to prepare the first monomer precursor can be selected from, for example, diphenyl wind-4,4'-diisocyanate, diphenyl wind 10 -3.3 '-Diisocyanate, benzidine wind-4,4'-diisocyanate, diphenylmethane wind-4,4'-diisocyanate, 4-methyldiphenylmethane wind-2,4'-diisocyanate, 4 , 4'-dimethoxydiphenylwind-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodiphenylmethyl wind, 4,4 '-Difluorenyldiphenylwind-3,3'-diisocyanate, 4,4'-di-third-butyl-diphenylwind-3,3'-diisocyanate 15 and 4,4'-di Air diphenyl wind 3,3'-diisocyanate. Examples of aromatic sulfonamide-type polyisocyanates that can be used to prepare monomer precursors include 4-methyl-3_isocyanato-benzene-sulfonamido-3'-methyl-4'- Isocyanates, diphenylsulfonyl · ethylenediamine-4,4'-diisocyanate, 4,4'-methoxybenzenesulfonyl · ethylenediamine'-3,3'_diisocyanate and 4-methyl -3-Isocyano 20-acid-benzene-sulfoanilide-4-ethyl-3'-isocyanate, but is not limited thereto. The types of polyisocyanates that can be used to prepare the first monomer precursor include: aliphatic polyisothiocyanates; cycloaliphatic polyisothiocyanates (eg, cyclohexane diisothiocyanate) ); An aromatic polyisothiocyanate in which the isothiocyanate group is not directly bonded to the aromatic ring (eg, α, α'-diphenylbenzenediisothio 18 200424220 cyanate); Aromatic polyisothiocyanate in which the isothiocyanate group is directly bonded to the aromatic ring (for example, phenylene diisothiocyanate); heterocyclic polyisothiocyanate (For example, 2,4,6-triisothiocyanato-1,3,5-triamidine and thiophene-2,5-diisothiocyanate); carbonyl polyisothiocyanate; Contains sulfide 5-bonded aliphatic polyisothiocyanates (for example, thiobis (3-isothiocyanopropane); polymerization of sulfur atoms other than isothiocyanate groups Isothiocyanates; halogenated, alkylated, alkoxylated, nitrated, carbodiimide modified, urea modified and diurea modified derivatives of polyisothiocyanates belonging to these categories; Polyisosulfur Di- and 10-trimer products of cyanocyanate, but are not limited to this. Examples of aliphatic polyisothiocyanates that can be used to prepare the first monomer precursor include 1,2-diisothio Cyanoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, and 1,6-diisothiocyanatohexane, but not Limited to this. Examples of aromatic polyisothiocyanates having 15 isothiocyanate ester groups directly bonded to aromatic alkane include 1,2-diisothiocyanatobenzene, 1,3- Diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-di Toluene, 4,4'-diisothiocyanato-1, Γ-biphenyl, 1, Γ-phenylenebis (4-isothiocyanatobenzene), 1, Γ-methylidenebis (4-isothiocyanato20-2-methylbenzene), 1, Γ · methylenebis (4-isothiocyanato-3-fluorenylbenzene), 1 · 1 '_ (1 , 2_ethanediyl) bis (4_isothiocyanatobenzene), 4 · 4'_diisothiocyanatobenzophenone, phenylanilide-3,4'-diisosulfide Cyanic acid , Diphenyl ether_4,4'_diisothiocyanate and diphenylamine-4,4'-diisothiocyanate, but not limited to this. 19 200424220 can be used to prepare the One monomer precursor carbonyl polyisocyanate includes hexane-dicarbonyl diisothiocyanate, nonaedioyl diisothiocyanate, diisothiocarbonate carbonate, 1,3-benzenedicarbonyl diisocyanate Thiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, and (2,2'_dipyridine) _4,4'_dicarbonyldiiso5thiocyanate, but not limited to this Examples of aromatic polyisothiocyanates containing sulfur atoms other than isothiocyanate groups that can be used to prepare the first monomer precursor include 1-isothiocyanato-4 -[(2-isothiocyanato) sulfofluorenyl] benzene, thiobis (4-isothiocyanatobenzene), sulfobis (4-isothiocyanatobenzene), Thiothiobis (4-isothiocyanatobenzene), dithio10-based bis (4-isothiocyanatobenzene), 4-isothiocyanato-l-[(4-isothio Cyanophenyl) -sulfofluorenyl] -2-methoxybenzene, 4-methyl-3-isothiocyanatobenzene-sulfofluorenyl-4'-isothiocyanate Ester phenyl ester and 4-methyl-3-isothiocyanatobenzene-sulfonamidoaniline 3'-methyl-4'-isothiocyanate, but are not limited thereto. 15 The polycyanate monomer used to prepare the first monomer precursor may also be selected from polycyanate monomers having isocyanate and isothiocyanate groups, which may be, for example, aliphatic, alicyclic Family, aromatic, heterocyclic or containing sulfur atoms other than isothiocyanate groups. Examples of these compounds include 1-isocyanato-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 20 1-isocyanato-6 -Isothiocyanatohexane, isocyanatocarbonyl isothiocyanate, 1-isocyanato-4-isothiocyanatohexane, 1-isocyanato-4-iso Thiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1, 3,5-trifluorene, 4-isocyanato-4'-isothiocyanato-diphenyl sulfur 20 200424220 10 15 20 compounds and 2-isocyanato-2'-isothiocyanate Diethyl disulfide, but is not limited thereto. A reactive hydrogen material having at least two reactive hydrogen groups can be selectively used to prepare a precursor of the first monomer. The reactive hydrogen material may be selected from polyols, five polyamines having at least a secondary amine and / or secondary amine group, and materials having hydroxyl and amine functional groups. As used herein, "reactive hydrogen material" means a material having a reactive amidine group capable of forming a covalent bond with an isocyanate and an isothiocyanate group, and can be used to prepare a gallbladder ~~ Polyols (e.g., 2-ethanediol, 1,3-propanediol, 1,2-propanediolase, 1,4-butanediol, 1,4-butanediol, 1,4-butanediol) 3-butanediol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, dimethyltrimethylolpropane, erythritol, pentaerythritol, and di-pentaerythritol); Alkyl glycols (e.g., diethylene glycol, propylene glycol), and higher polyalkylene glycols (e.g., with 200 to 2000 g / mole (e.g., as fine as 2 ° 〇〇〜 莫尔) of several molecular weight materials ethyl glycol); Polyols (for example, cyclocyclocyclohexane, cyclohexanetriol, cyclohexane dimethanol, propylpropyl and cyclopentadiene Diethyl is _ multi-tree, such as, ^ Benben, Benben methyl alcohol and diacryl toluene; double hope (for example, 4 :, 4 two double hope double hope (for example, 4, 4, different _, 4,4, _isopropylidenebis (2,6_ 二 _ and 4,4, _isoside, ,, 6_tetra_); bis-oxygenated _ such as, with ^ 21 200424220 oxygen (for example, ethoxy, propoxy, α-butoxy and S-butoxy) Alkoxylated 4,4'-isopropylidene diphenols); and dicyclohexanols that can be prepared by hydrogenating the corresponding bisphenols (eg, 4,4'-isopropylidene-biscyclohexane) Alcohol, 4,4'-oxydicyclohexanol, 4,4'-thiodicyclohexanol and bis (4-hydroxycyclohexanol) methane, 5 but is not limited thereto. It contains one or more hydroxyl groups and one or Many thiol-based compounds can be used to prepare the precursor of the first monomer. Examples of materials having hydroxyl and thiol groups include 2-fluorenylethanol, 3-fluorenyl-1,2-propanediol , Glycerol bis (2-mercaptoacetate), glycerol bis (3-fluorenylpropionate), 1-hydroxy-4-M-cyclohexane, 10 2,4-dimercaptophenol, 2-mercaptohydroquinone Ketones, 4-M-based phenols, 1,3-diamidino-2-propanol, 2,3-diamidino-1 -propanol, 1,2-diamidino-1,3-butanediol, Trimethylol propane bis (2-fluorenyl acetate), trimethyl alcohol propane bis (3-fluorenyl propionate), pentaerythritol mono (2-fluorenyl acetate), pentaerythritol bis (2_ 酼Acetate), Pentaerythritol tris (2-mercaptoacetate), pentaerythritol mono (3-fluorenyl propionate), 15 pentaerythritol bis (3-fluorenyl propionate), pentaerythritol tri (3-fluorenyl propionate), hydroxyl Methyl-tris (fluorenylethylthiomethyl) methane, 1-hydroxyethylthio-3-fluorenylethylthiobenzene, 4-hydroxy-4'-fluorenyldiphenyl, dihydroxy Ethyl sulfide mono (3-M-based propionate) and hydroxyethylthiomethyl · tris (fluorenylethylthio) methane, but are not limited thereto. 20 Can be selectively used to prepare the first The monomeric polyamine has at least two functional groups selected from the group consisting of a primary amine (-NH2), a secondary amine (-NH-), and a mixture thereof. Preferably, the selective polyamine has at least a secondary amine group. The polyamines that can be used to prepare the first monomer precursor can be selected from any of the ethylenediamine family, for example, ethylenediamine (EDA), diethylenetriamine (DETA), triethylene glycol 200424220 Tetraamine (TETA), Tetraethylenepentamine (TEA), Pentaethylenehexamine (PEA) > ^ L · ^ m (DEOA)) A2-m ^ piperazine. The selective polyamine may also be selected from one or more of the isomers of dialkyltoluenediamine of Q-C3, 3,5-dimethyl-2,4 · toluenediamine, 3,5-di Methyl-2,6-5 toluenediamine, 3,5-diethyl-2,4-diphenylene diamine, 3,5-diethyl-2,6-toluenediamine, 3,5-di Isopropyl_2,4_fluorenediphenyldiamine, 3,5-diisopropyl-2,6-toluenediamine and mixtures thereof. Other examples of polyamines that can be used to prepare the first monomer precursor include butylene butylene diphenylamine and triethylene glycol bis (p-aminophenyl benzoate), but are not limited thereto. 10 [Embodiment] Detailed description of the preferred embodiment In the embodiment of the present invention, the selective polyamine reactant can be generally described as one having the following general structure (IV-VI): (IV)

15 (V)

23 (VI) (VI) 200424220

Particularly preferred structures include one or more diamines represented by the general structure νπ-χχ, 5 (VII)

(VIII)

24 (XI) 200424220 5 (XIII) (XII) (XIV) (XV)

25 (XVI) 10 200424220 (XVII) (XVIII)

(χιχ)

(xx)

10 wherein each of R3 and R4 is a CrC3 alkyl group, and R5 is selected from hydrogen and 26 200424 ^ ° halogen (for example, gas and bromine). The diamine represented by the general formula VII can be generally described as 4,4'-methylene-bis (dialkylaniline). Specific examples of the diamine represented by the general formula VII include 4,4'-methylene-bis (2,6-dimethylaniline), 4,4, _methylene-bis0,6-diethyl Aniline), 4,4, -methylene-bis (2-ethyl-6-methylaniline), 4,4, _methylene-bis (2,6-diisopropylaniline), 4, 4, _Methyl-bis (2-isopropyl-6-methylaniline) and 4,4'-methyl-bis (2,6-diethyl-3-chloroaniline), but not limited to this. A preferred diamine-based 4,4, -methylene-bis (2,6_ > ethyl-3-aeroaniline) represented by the general formula VII. In another embodiment of the present invention, the polyamine reactant may be a 2,6-diaminotoluene 3,5 · dialkyl sulfide having the general formula XXI below (XXI)

Among them, R6 and R7 are linear, branched or cyclic (: 1 to (: 2 () alkyl). Preferred compounds of the general formula XXI are 2,6 · diaminotoluene 3,5 · dimethylsulfide and 15 2,6-diaminotoluene 3,5-diethyl sulfide. The diamine represented by the general formula VII can be generally described as 4,4'_extended methyl_bis (dialkylaniline). Specific examples of the diamine represented by the formula VII include 4,4, -methylene-bis (2,6 · dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline) ), 4,4'-methylidene-bis (2-ethyl-6-methylaniline), 4,4, methylidene · bis (2,6-di-20 isopropylaniline), 4,4M Methyl methyl-bis (2-isopropyl-6-methylaniline) and 4,4, _ fluorenyl-bis (2,6-diethyl · 3 · aminoaniline) 'are not limited thereto. Vi! 27 200424220 is a preferred diamine-based 4,4, -methylene-bis (2, budiethyl-3_aniline). The precursor of the first monomer can be prepared in the presence of a catalyst. Catalysts that can be used to prepare the first monomer precursor include, for example, tertiary amines (e.g., triethylamine, diisopropylamine, and N, N-dimethylbenzylamine) and organometallic compounds 5 things (e.g., ditin Tin dilaurate, dibutyltin diacetate, and tin octoate. Another example series of tertiary amines is shown in Block 10, Lines 6 to 38 of US Patent No. 5,693,738, and the disclosure thereof is hereby disclosed. A series of other examples of organometallic compounds as catalysts is shown in lines 4 to 26 of U.S. Pat. No. 5,631,339, the disclosure of which is incorporated herein by reference. The amount of catalyst is typically less than 5% by weight (preferably less than 3% by weight, and more preferably less than 丨% by weight), which is based on polythiol monomer, polycyanate monomer, and selectivity. The total weight of the reactive hydrogen material is based on the basis.) The polymerizable composition of the present invention may optionally include a second radical polymerizable monomer, which is different from the first radical polymerizable monomer. Second The 5 monomer has a radical polymerizable group selected from ethylene, allyl, and (meth) acryl. From the embodiment of the present invention, the second single system has at least diethylene group ^ Aromatic monomers. Examples of aromatic > monomers that can be used in the polymerizable organic composition of the present invention : Divinylbenzene (for example, a mixture of structural isomers of 1,2 · diethylene benzene,: 0 diethylene benzene, 1,4-diethylene benzene, and divinylbenzene) , Iso-isopropenylbenzene (for example, a mixture of structural isomers of -diisopropylbenzene, I "diisopropylbenzene, 1,4 · diisopropylbenzene, and diisopropenylbenzene) Diethylene glycol (for example, a mixture of structural isomers of ι, 2,4-trivinylbenzene, -vinylbenzene, and divinylbenzene); diethylene 28 200424220 based naphthalene (for example, 2,6 -Divinylnaphthalene, 1,7_divinylnaphthalene, mixtures of the structural isomers of divinylnaphthalene and divinylnaphthalene); Diethyl, Guimebenzylisopropylbenzene, Triethyl Diphenylbenzene and divinyl-substituted derivatives (eg, 2-gas-1,4 · divinylbenzene); and mixtures of these aromatic monomers5, but are not limited thereto. In a preferred embodiment of the present invention, an aromatic monosystem divinylbenzene. In another embodiment of the present invention, the second free-radically polymerizable monomer (b) having at least divinyl unsaturated group has a (meth) acrylfluorenyl group, and is selected from: XXII monomer (XXII)

Each of m and η is a positive number, and the sum of m and η is 0 to 70, preferably 2 to 40, and more preferably 5 to 20, each of R3 and R4 is hydrogen or methyl, 15 R5 & Each of R6 is hydrogen or hydrogen to alkyl, and A is selected from linear or branched alkylene (generally containing 1 to 8 carbon atoms), cyclic alkylene (generally 5 to 8 carbon atoms), phenylene, CrC9 alkyl-substituted phenylene, and a divalent bonding group of the group represented by the following general formula XXIII, wherein each of R7 and R8 is (^-匸 4alkyl, Chlorine or bromine, 20 (XXIII)

29 200424220 Each of P and q is an integer of 0 to 4 represents a divalent phenyl group or a divalent cyclohexane group, and when it is a divalent phenyl group, X is 0, S, -S (〇2) _, _C (〇)-

CH2-, _CH = CH ·, C (CH3) 2-, -C (CH3) (C6H5) _ or 5 and when it is a divalent cyclohexane group, X is o, s, -ch2- or -c ( ch3) 2- 9 9 (11) bis [(meth) acrylfluorenyl-terminal] poly (ethylene glycol) monomer, which is different from monomer (i) and has a number of 200 to 2,000 g / mole Average molecular weight; and (ex) the 10 monomers of the poly (meth) acrylfluorenyl terminal represented by the following general formula XXIV, (XXIV)

Among them, R 'is a polyvalent group of a polyhydric alcohol, R9 is hydrogen or methyl, R5 is hydrogen or ^ to alkyl, d is a number from 0 to 20, and j is an integer from 3 to 6, preferably 3 15 To 4, more preferably 3; and (iv) a mixture of monomers selected from monomers (i), (ii) and (iii). The polymerizable second monomer ⑴ represented by the general formula IV can be prepared by a method known in the industry 30 200424220. When the sum of m and η is greater than 0, these commonly used methods include a two-step method. In the first step, a polyol (e.g., 4,4'-isopropylidene diphenol) and an alkylene oxide-containing substance (e.g., ethylene oxide, propylene oxide, α-butylene oxide) Or butylene oxide) to form an ethoxylated, propoxylated, or butoxylated polyol commonly referred to as having a hydroxyl 5 functional group. In the second step, ethoxylated, propoxylated or butoxylated polyols are α- / 3 unsubstituted acids or esters (such as methacrylic acid, (^ to (: 6 alkyl methacrylic acid) Ester, acrylic acid, CrC6 alkyl acrylate, or a mixture thereof) esterification or transesterification. The second step results in the formation of a radical polymerizable monomer 10 represented by the general formula IV. When the sum of m and η is At 0, the monomer fluorene can be obtained by using a polyol (for example, 4,4'-isopropylidene dimer) and an α-point unsubstituted acid or ester (such as methacrylic acid, (^ to (: 6 alkyl methacrylate, acrylic acid, CrC 6 alkyl acrylate, or a mixture thereof) is prepared by an esterification or transesterification reaction. Appropriate multiples for preparing the second monomer ⑴ represented by the general formula IV 15 examples of alcohols include: straight chain alkylene glycols (such as ethylene glycol, propylene glycol, trimethylol, tetramethylol or diethylene glycol, triethylene glycol) : Branched alkylene glycol (such as 1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol ); Cyclic alkylene glycols (such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol) 20: phenylene glycol (such as, O-, m-, and p-dihydroxybenzene); alkyl-substituted phenylene glycols (such as 2,6-dihydroxytoluene, 3-methylcatechol, 4-methylcatechol, 2-hydroxy Benzyl alcohol, 3-hydroxybenzyl alcohol and 4-hydroxybenzyl alcohol); dihydroxybiphenyls (such as 4,4'-dihydroxybiphenyl and 2,2'-dihydroxybiphenyl); Bisphenols (such as 4,4'-isopropylidene diphenol); 4,4'-oxybisphenol; 4,4'-bis31 200424220 hydroxybenzophenone; 4,4'-thiobisphenol Phenolphthalein; bis (4-hydroxyphenyl) pinene; 4,4 '-(1,2 · ethanediyl) bisphenol; and 4,4'-sulfofluorenylbisphenol; dendritic bisphenols (such as , 4,4'-isopropylidene bis (2,6-dibromophenol), 4,4, -isopropylidene bis (2,6-one-ranpan), and 4,4 -isopropylidene Bis (2,3,5,6-tetrakipan)); and dicyclohexyl-5 alcohols (which can be prepared by hydrogenating the corresponding bisphenols, such as 4,4, -isopropyl and bicyclohexanol ); 4,4'-oxydicyclohexanol; 4,4'-thiodicyclohexanol; and bis (4-hydroxy ring Alcohol) methane, but is not limited thereto. In a preferred embodiment of the present invention, in the general formula Iν & ν, C (CH3) 2 ·, 10 15 < 2) represents a divalent phenyl group, p and Each of q is 0, each of heart and ^ is methyl 'R · 5 and R · 6 are each hydrogen, and the sum of m & n is 5 to 20. The second polymerizable monomer ⑼ It is different from the first monomer (i) and can be self-polymerized (ethylene glycol) and an unsubstituted acid or vinegar (such as methyl acrylic acid, methyl ethyl, methyl ethyl)酉 Zhi, _ acid, Xuan Ji Bing Zhi or their age)) or the reverse material. Dimethyl) acryl-based 'terminal] poly (ethylene glycol) monomers are preferably 200 to 120 () (more preferably to Cheek) grams / mole averaged by gel permeation chromatography In addition, the second monomer of good standard polyphenylene terephthalate is a bismethyl propylene material of polyethylene glycol, which has a number average molecular weight of 600 g / mole. Eighth, the polymerizable second monomer (iii) (prepared by the method known in the industry. When the recording is greater than ㈣, the one described in 11) can be used in a two-step method. The first such polyols (such as 32 20 200424220, trimethyl alcohol propane) are related to epoxy-containing substances (for example, ethylene oxide, propylene oxide, alpha epoxy butadiene or stone). -Butylene oxide) reaction to form-generally known as ethoxylated, propionized or butylated. 5 10 In the second step, ethoxylated, propoxylated or butoxylated polyols are treated with α-unsubstituted unsubstituted acids (such as f-based acrylic acid, Mα silk methacrylate, acrylic acid , Ci_q-based acrylic vinegar or its present compounds), or vinegarization. The second step results in the formation of a polymerizable second green body. When d is 0, the second monomer ㈣ can be obtained by using a polyhydric alcohol (for example, trimethyl-propionate) and α · red unsubstituted acid or 8-base (such as methylpropionate, Cjc6 alkyl). Methyl acrylic, acrylic acid, acrylic acid, or a mixture thereof) is prepared by the conversion or conversion reaction of S. 15 Examples of polyhydric alcohols suitable for the preparation of the polymerizable second monomer 甘油 include glycerol, trimethyl alcohol, CD · tris (2 · ethylethyl) isocyanurate, dimethyl alcohol, quaternary alcohol And second quarter fine alcohol, but not limited to this. The preferred polymerizable second monomer ㈣ can be defined with reference to general formula VI, wherein R is a radical of pentaerythritol, _, ′ is 3 or 4, and j_R9 is hydrogen. , "Polyvalent polyvalent radicals of the polyhydric alcohols-word system M in the preparation of the polymerizable third monomer ㈣ polyvalent polyvalent residue 20 push 4 for example 1 in the case of pentaerythritol tetraacrylic acid S purpose (for ^ is 0, j In the case of ',' and 仏 is the quaternary group of pentaerythritol (ie, tetramethylene methyl) R methyl alcohol ton trisuccinic acid Sl (for d_, j is 3 and 9 ^ 'R 'It is a trivalent radical of trimethylolpropane (ie, U, l-trimethylinner courtyard). In a further embodiment of the present invention, there are two or more ethyl alcohols 33 200424220 And the polymerizable second monomer has allyl group and is represented by the following general formula XXV

J (XXV) R- [〇-C (0) _0-Ri〇] i where R is a group derived from a polyhydric alcohol, R10 is a group derived from a two-base group or a substituted propyl group, and i It is an integer from 2 to 6. The polymerizable second monomer represented by the general formula XXV is further described as a polyol (allyl carbonate) monomer. Polyol (allyl carbonate) single system linear or branched aliphatic or aromatic liquid polyenzyme allyl carbonate which can be used in the aforementioned fluorene polymerized organic composition, for example, aliphatic dienzyme double (Allyl 10-based carbonate) compounds and alkylidene bisphenol bis (allyl carbonate) compounds. These monomers can also be described as unsaturated polycarbonates of polyhydric alcohols, such as diols and bisphenols. Polyol (allyl carbonate) monomers can be prepared by procedures known in the industry, for example, as described in U.S. Patent Nos. 2,370,567 and 2,403,113. 15 With reference to the general formula XXV, R10 is available at the 2 position. Allyl-derived groups substituted with halogen (especially gas or bromine) or an alkyl group containing 1 to 4 (eg, 1 to 2) carbon atoms. Generally, the alkyl substituent is methyl or ethyl. The Rio group can be represented by the following general formula XXVI: (XXVI) H2C = C (Rn) -CH2- 20 where Rii is hydrogen, halogen, or (^ to (: 4 alkyl groups. Most commonly, Ru is hydrogen, so R10 Is an unsubstituted allyl group, H2C = CH_CH2 ·. With reference to the general formula XXV, R is an aliphatic, cycloaliphatic or aromatic polyol which may contain 2, 3, 4, 5 or 6 radicals. Derived polyvalent radicals. Typically, polyols contain 2 light radicals, that is, diols or bisphenols. Aliphatic polyols can be linear or 34 200424220 branched and contain 2 to 10 carbon atoms. Generally, aliphatic polyvalents Alcohols are dialkylene glycols with 2 to 4 carbon atoms, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, or poly (C ^ C4) alkylene glycols (e.g. , Diethylene glycol, diethylene glycol, etc.). Other useful polyols include aromatic polyalcohols such as bisphenols, such as 4,4, -isopropylidene diphenol, and cyclic Aliphatic polyols (such as dicyclohexanol, for example, 4,4, -isopropylidene bicyclohexanol). Polyol (allyl carbonate) monomers that can be used in the polymerizable organic composition of the present invention Specific examples of body include Di-fermented bis (2-Gapropenyl carbonate), Glycol bis (dilute propyl carbonate), Diethylene glycol bis (2-Methene 10propyl carbonate), Diethylene glycol Diol bis (allyl carbonate | purpose), ethylene glycol bis (allyl carbonate), propylene glycol bis (2-ethylallyl carbonate), 1'3-propanediol Bis (dilute propyl carbonate g), 1,3-butanediol bisallyl carbonate), 1,4-butanediol bis (2-bromoallyl carbonate), dimethylene Diethylene glycol bis (allyl carbonate), Triethylene glycol bis (2-ethylallyl carbonate) 15, Pentamethyl glycol bis (dilute propyl carbonate), 4, 4, -Isopropylidene bis (allyl carbonate) and 4,4, -isopropylidene dicyclohexanol bis (allyl carbonate) 'but not limited to this. The preferred polyol (allyl Carbonate) Monosystem 4,4, _Isopropylenedidiol bis (allyl carbonate). More detailed description of the polyol (allyl carbonate) monomers suitable for the present invention Found in U.S. Patent No. 4,637,698, 3rd, 3rd, and 3rd to 5th, 61th lines. Disclosure Incorporated herein by reference and as reviewed above. When used in the description of the present invention with reference to Formula VII, a polyol (dilute propyl carbonate) monomer or similar noun (eg, diethylene glycol) Bis (allyl carbonic acid ')) is intended to mean and include the indicated monomers and their prepolymers and any related monomers discovered as a result of the method used to synthesize the monomers 35 2004 242 20 Or oligomeric species. The polymerizable composition of the present invention may optionally further include a third free, polymerizable monomer, which is a monomer different from the first and second free radical polymerizable monomers. The second free-radically polymerizable monomer may be selected from a monoethylenically unsaturated precursor. Examples of these monoethylenically unsaturated monomers include acrylic acid, methacrylic acid, vinegar of acrylic acid (such as methyl or ethyl acrylates and 2-methylethyl acrylate), methyl Acrylic vinegar (such as methyl or ethyl methacrylic acid, phenoxyethyl methyl acrylic acid, isobornyl propyl acrylate 10, cyclohexyl methacrylate and 2-hydroxy Ethyl methacrylate), dilute vinegars (such as vinyl acetic acid, styrene and vinyl vapors, and thiol-based monoethyl fluorene and monomers (such as sulfoethyl (methyl Base) Acrylic acid, ethylene thiol and allyl mercaptan, but not limited to this. Preferred monoethylenically unsaturated monomers include methyl methyl acrylate, isobornyl methyl propylene 15 Feminine vinegar, phenoxyethyl methyl acrylic acid, cyclohexyl methyl acrylic acid, vinyl gasification, M-ethyl ethyl (meth) acrylate, vinyl mercaptan and allyl sulfur Alcohol and mixtures thereof. If a polymerizable composition is used, the third monomer (e) (i) is typically not more than 30% by weight (preferably not more than 20% by weight, and more Is present in an amount of not more than 10% by weight), which is based on the total weight of the polymerizable 20 composition. Further optionally included in the composition of the present invention is an anhydride monomer having at least one polymerizable ethylenically unsaturated group. Is preferably a radically polymerizable base, which is described in the description of the third monomer (c) (ii) above. Specific examples of suitable anhydride monomers include methacrylic anhydride, acrylic anhydride, and maleic acid. Needle, 1_ 36 200424220 cyclopentane, 1,2_-anhydroanhydride, itaconic anhydride, and a mixture of these anhydride monomers, but not limited to this. If used in polymerizable compositions, anhydride monomers) (Along typical The upper part is present in an amount of not more than 40% by weight (preferably not more than 35% by weight, and more preferably not more than 30% by weight), which is the polymerizable composition of the present invention based on the total weight of the polymerizable composition It may further optionally include a polythiol monomer (d) having at least one thiol group. The polythiol monomer (d) may be selected from those described herein in connection with the preparation of the first monomer The polymerization of one or more of the thiol monomers in the polymerizable organic composition It is added by adding an initial content of a material capable of generating free radicals, such as an organic peroxy compound or an azobis (organonitrile) compound, that is, a starter. There is a radical polymerizable group-containing monomer in between. The polymerization reaction method of the composition Η = is known in the industry, and any familiar technique can be used to polymerize the aforementioned polymerizable 5-polymer organic composition. These polymerization methods include thermal polymerization methods, photopolymerization methods, or Mixtures of these. / Suitable organic peroxy compounds that can be used as initiators for thermal polymerization reactions 2 :: Contains: vinegar such as' third butyl peroxy 2-ethylhexyl carbonate and dibutyl peroxy Oxyisopropyl carbonate; peroxyketals, such as 丨 a * one-one (ηξ 2,4_ dagger ~ butyl peroxy) · 3,3,5-trimethylcyclohexane; peroxy Dicarbonate, such as (2-ethylhexyl) peroxydicarbonate, di (secondary butyl) peroxide, and diisopropylperoxydicarbonate; dimeryl peroxide, such as ~ benzene Fluorenyl peroxide, isobutyl fluorenyl peroxide, ': matter, Shi 4 36 Toggan, soil peroxide 4 soil peroxide, C Base peroxide, acetamyl peroxide 4 37 200424220, phenylfluorenyl peroxide, p-phenylbenzyl peroxide; peroxy vinegar, such as second butylperoxyvalerate, Tributylperoxyoctanoate and tertiary butylperoxyisobutyric acid; methyl ethyl methoxide, and ethyl acetocyclohexanoyl peroxide. Preferred thermal initiators are those which do not discolor the polymer 5 formed. A particularly preferred thermal initiator is U-di- (third butyl peroxy) -3,3,5_dimethylhexanol, which is commercially available under the trade name LUPERSOL 23 from mf At () ehem. Examples of suitable azobis (organic riding) compounds that can be used as initiators for thermal polymerization include azobis (isobutyronitrile) and azobis (2,4 • dimethyltetravaleronitrile). The amount of the thermal polymerization reaction initiator used to initiate and polymerize the polymerizable organic composition of the present invention can vary and depends on the particular initiator used. : Only the amount needed to start and maintain the polymerization reaction, that is, the starting amount. Regarding the preferred peroxy compound, di- (third butyl peroxy) > 3Λ5 • trimethylcyclohexyl I5 alkane is typically a single system per unit portion of the polymer present in the polymerizable organic composition. A starter between 3.0 and 3.0 parts (phm) is used. More generally, between 0 μ and 1.0 ophm is used to initiate the polymerization reaction. Typically, thermal curing is included in the presence of the initiator, in During the period of 2 hours to 48 hours, the polymerizable organic composition is heated from room temperature to 85 ° C to 13.0. 20 The photopolymerization reaction of the polymerizable organic composition according to the present invention may be used as a photopolymerization initiator. Existence is accomplished by using ultraviolet, visible light, or a mixture thereof. Examples of suitable photopolymerization initiators include benzoin, benzoic acid, benzoin isobutyl fine, benzophenone, ethylbenzene, etc. Digas benzophenol, diethoxyethynyl phenol, hydroxymethyl 丨 · benzyl 38 200424220 propan-l-Sig, 1-methylcyclohexylphenyl ketone, 2-isopropyl thixanthone and 2,4 , 6-Dimethylphenylphosphonium diphenylphosphine oxide. Photopolymerization for initiating and polymerizing the polymerizable organic composition of the present invention The amount of the reaction initiator may vary and depends on the particular initiator used. It only needs to be used to start and maintain the polymerization amount 5, that is, the starting amount. The preferred photopolymerization initiator is 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide. Photopolymerization initiators are typically 0.001 to 2% by weight (which is based on the total weight of the monomer components). The light source used for the photopolymerization reaction is preferably selected from those who emit ultraviolet light. The light source 10 is preferably a mercury lamp, a germicidal lamp, or a xenon lamp. Visible light (for example, sunlight) can also be used. Exposure The time may vary depending on, for example, the wavelength and intensity of the light source and the shape of the mold, and is typically determined experimentally. The amount of thermal polymerization initiator or photopolymerization initiator and / or the curing cycle should be appropriately Produces a polymer according to the invention having a Barco hardness of 15 at least 1 (zero seconds), preferably at least 4, for example, 4 to 35. It is understood that the polymerizable organic composition of the invention may Polymerization in a polymerization initiator. In particular, the present invention Polymerization of the organic composition can be achieved in the absence of any externally added photopolymerization initiator or thermal initiator. Various conventional additives can be combined with the polymerizable organic composition of the present invention. These additives include Photo tinctures, heat agents, antioxidants, UV absorbers, mold release agents, static (non-photochromic) dyes, colorants, inhibitors to promote stabilizers during storage, and non-radiative polymerization flexibility Chemical 39 200424220 Additives, such as alkoxylated phenol benzoate and poly (alkylene glycol) dibenzoate. Anti-yellowing additives, such as 3-methyl-2-butenol, organic pyrocarbonate Ester and triphenylphosphite (CAS registration number 101_〇2_〇) can also be added to the polymerizable organic composition of the present invention to promote anti-yellowing effect. These fifth-grade additives are typically less than 10% by weight (preferably less than 5% by weight) and more preferably less than 3% by weight ❽ / ❻, and the amount is based on the total weight of the polymerizable composition ) Is present in the composition of the invention. It is also contemplated that a polymerization moderator or a mixture of polymerization moderators may be added to the polymerizable organic composition of the present invention to minimize distortion formation (such as streaks) in the polymer obtained from it. Suitable polymerization moderators include, for example, dilaurylthiodipropionate, onionene, isopropyl-4-methyl-i, 4-cyclohexadiene, isopropyl-4 • Methyl j, cyclocyclohexadiene, methylstyrene, 2,4-diphenyl_4-methyl_1_pentene, 1,1-diphenylethylene, cis-1,2-di Phenylethylene, 2,6_dimethyl_2,4,6_octatriene, 4-15 tert-butyl pyrocatechol and mixtures thereof. The polymerization moderator may be from 0.01 to 10% by weight (preferably from 0.01 to 8% by weight, and more preferably from 0.3 to 5% by weight), which is polymerizable. To the polymerizable organic composition of the present invention. The polymer 20 obtained from the polymerization reaction of the polymerizable organic composition of the present invention is solid and preferably transparent, for example, suitable for optical or ophthalmic applications. The polymers of the present invention also have a reflection index of about 1.57 to about 1.80 (preferably about 1.60 to about h75); a suitably high Abbe number, such as an Abbe number of at least about 30 (preferably at least about 33) ; And at least the initial (zero second) Barco hardness. More preferably, the reflection index is at least i 6, more preferably at least 163, and most preferably 654 40 200424220, and has an Abbe number of at least 35. Solid objects that can be made from the polymerizable organic composition of the present invention include optical lenses (such as flat and ophthalmic lenses), sunglasses, automotive transparents (e.g., window shields, side and rear lights), and aircraft Transparent materials and the like, but are not limited thereto. 5 When used to prepare photochromic objects (e.g. lenses), the polymer may be part of the electromagnetic spectrum of the photochromic substance that is activated and incorporated into the substrate (i.e., produces photochromic in a colored or open form) The ultraviolet (UV) wavelength of a substance and the part of the visible light spectrum that absorbs the maximum wavelength of a photochromic material contained in its UV-activated form (ie, open form) are transparent. Photochromic materials that can be used with the polymer of the present invention are organic photochromic compounds or materials containing those that can be incorporated (e.g., dissolved, dispersed, or diffused) into such polymers. The first type of organic photochromic material considered to form the photochromic article of the present invention is one having a maximum value of activated absorption, during which the visible light range is greater than 590 nm, for example, greater than 590 to 700 nm. When exposed to UV rays in solvents or substrates, such materials typically exhibit blue, blue-green, or blue-violet. Examples of such materials that can be used in the present invention include, but are not limited to, spiro (indolin) naphthoxanthene and spiro (indolin) benzoxoxan. These and other kinds of this photochromic material are described in the open literature. See, for example, U.S. Patent Nos. 3,562,172; 3,578,602; 4,215,010; 20 4,342,668; 5,405,958; 4,637,698; 4,931,219; 4,816,584; 4,880,667; 4,818,096. See also, for example, Japanese Patent Publication 62/195383, and textbook 'Chemical Techniques' Book III, "Photochromic Theory", Chapter 3, Glenn H. Brown, Editor, John Wiley & Sons, Inc New York, 1971 o 41 200424220 Considering the second type of organic photochromic material used to form the photochromic article of the present invention is one having at least one absorption maximum and preferably two absorption maximums, in which the visible light range is 400 And less than 500nm. These materials typically exhibit a yellow-orange color when exposed to ultraviolet light in a suitable solvent or substrate. These compounds include certain color dilutions, namely, benzopyrene and naphthalene. Many of these chromenes are described in open literature, for example, U.S. Patent Nos. 3,567,605; 4,826,977; 5,066,818; 4,826,977; 5,066,818; 5,466,398; 5,384,077; 5,238,931; and 5,274,132. The third type of organic light 10 considered to be used to form the photochromic article of the present invention is a photochromic material having an absorption maximum between a visible light range of 400 to 500 nm and another absorption maximum between a visible light range of 500 to 700 nm. Valuers. These materials typically exhibit yellow / brown to purple / gray when exposed to ultraviolet light in a suitable solvent or substrate. Examples of these materials include certain 15-benzyl-0-pyran compounds with substituents at the 2-position of the laran ring and substituted or unsubstituted heterocycles, such as those compounded to benzo'1-pyran Benzobenzobenzo or benzofuran. These materials are the subject of US Patent No. 5,429,774. Other photochromic materials under consideration are photochromic organometallic disulfonium salts, that is, (aryl azo) -thiothioformyl aryl hydrazine salts, such as mercury 20-thiazole salts, which are described in For example, U.S. Patent No. 3,361,706 captures anhydride and psodium imine (e.g., 3-furanyl and 3-calyl-based succinic anhydride and psodium imine) are described in U.S. Patent No. 4,931, Block 220, line 5 to block 21, line 38. The disclosures regarding the photochromic materials in the aforementioned patents are all incorporated herein by reference. The photochromic 42 200424220 of the present invention may contain a photochromic material or a mixture of photochromic materials, which is determined according to the desire. Mixtures of photochromic materials can be used to obtain certain activated colors, such as near neutral gray or brown. Each of the photochromic materials described herein can be applied to a mixture of compounds or the polymers incorporated therein to exhibit the desired color formation (eg, substantially neutral when activated by filtered sunlight) Colors, such as gray or brown shades, that is, the amount and proportion of specific colors of activated photochromic materials that are as close to neutral as possible) are used. The relative content of the aforementioned photochromic materials used will vary and depends in part on the relative intensity of the color of the activated species of these compounds and the final desired color. The photochromic compounds or materials described herein can be applied or incorporated into polymers by various methods described in the industry. These methods include dissolving or dispersing the materials in the polymer, for example, by immersing the polymer in the heat / valley of the photochromic material or by inhaling the photochromic material into the polymer 15 by thermal transfer. ; Providing the photochromic material in separate layers between adjacent polymer layers, for example, as part of a polymer film or polymer layer; and as a coating or coating on a polymer surface or The photochromic material is applied to a part of the polymer layer. "Inhalation," is used to mean that the photochromic material is penetrated into the polymer, the solvent helps the photochromic material to transfer and absorb into the water-based polymer, vapor phase transfer and other such transfer mechanisms. Inhalation An example of the method includes the steps of coating the photochromic article with a photochromic material, heating the surface of the photochromic article, and then removing the residual coating from the surface of the photochromic article. Applying or incorporating polymerization 43 200424220 b L of photochromic material or composition containing it is not important, as long as a sufficient amount is used to produce naked eye-identifiable photochromic effect during activation. Generally, this content can be described by photochromic amount. Sishu δ generally depends on the intensity of the color when it is irradiated and the method of combining or using photochromic materials. Typically, the more photochromic materials that are applied or incorporated, the greater the color intensity. Generally The total range of the photochromic material incorporated or applied to the photochromic optical polymer ranges from 0% grams per square centimeter of the surface of the photochromic material incorporated or applied. The photochromic material can be added to the polymerizable organic composition of the present invention before curing. However, when this is the case, the photochromic material side is preferably similar to the possible starting / Or the potential adverse interactions of polythiol monomers and sulfide bonds formed in the polymer are resistant. These adverse interactions can cause photochromism by making up in open or closed form The material loses its activity. The photochromic material can also contain 15 photochromic materials and organic photochromic materials coated in metal oxides, the latter being described in US Patent Nos. 4,166,043 and 4,367,170. Full Photochromic materials (described in U.S. Patent No. 4,931,220) coated in an organic polymer substrate can also be incorporated into the polymerizable organic composition of the present invention before curing. Example 1 Sulfur-based Glycerol bis (2-fluorenylacetate) is the preferred polythiol monomer of the present invention, wherein each of them is a fluorenyl group with reference to the general idea of I. Thioglycerol bis (2 · sulfoethyl Ester) is prepared from the following components.

44 200424220 3-M-based 1,2-propanediol Injection 1 1995 2-Aminoacetic acid 2333 Methanesulfonic acid 14.2 Aqueous ammonia Injection 2 4218 (a) 5% by weight aqueous ammonia solution. The component of charge 1 was added to a 5-liter round bottom flask (which was equipped with a magnetic stirrer, a thermocouple, and a heating hood coupled with a temperature feedback control device and a vacuum distillation column). A vacuum of 5 to 10 millimeters (mm) Hg was sucked in, and the reaction mixture was heated and kept at 70 ° C for 4 to 5 hours while water was collected from the distillation column. When no more water was observed to be collected from the distillation column, the reaction mixture was cooled to room temperature and transferred to a 6-liter round-bottom flask (equipped with a motor-driven stirring blade, thermocouple, and water-cooled sleeve ). Shot 2 was added to mix 10 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 left to accumulate an upper ammonia layer, which was removed by suction with a pipette. The remaining lower layer was washed 3 times, each time with 2 liters of deionized water. Water was vacuum stripped from the cleaned layer to produce 1995 grams of thioglycerol bis (2.mercaptoacetate), which was in the form of a yellow oil and had a reflection index of 15 1.5825. Example 2 This example demonstrates the synthesis of the UV-curable sulfur-based gas-based formic acid acetate monomer of the present invention. In a 2004 2004220 reactor trough equipped with a mixing, thermometer, and water-cooled reflux condenser, 1 equivalent of tolyl_2,4_diisocyanate (TDi) and 3 equivalent of 2,2'-thiodiethane Triol (DMDS) is mixed under ambient conditions for "hours" to produce a liquid thiocarbamate prepolymer. One equivalent of the prepolymer is warmed, and one equivalent of isocyanatoethylmethyl is added thereto. Acrylate. The resulting mixture was stirred at 70 C for 1.5 hours to produce a clear adhesive monomer. Example 3 This example demonstrates the synthesis of a polymer prepared using the UV-curable thiourethane monomer of Example 2. The polymer coating composition is as follows: Component composition (wt%) ~ Thiocarbamate monomer 35 Double enzyme A 2EO dimethacrylate 30 Styrene 30 2,2'-thiodiethyl Burned mercaptan 5 Darocure 4265 starter 1 QS 10 乏 织 细 fine oxide group wound was injected into the container and mixed for several minutes. The mixture was placed in the UV-transmissive glass mold of Erping, which had 3.2 Cavity thickness of mm. The mixture of 15 in the mold is caused by passing the mold under the UV light source. Photopolymerized. The filled mold passes UV light for the first time to expose the first side of the mold to the uV light source. Then, the mold is turned over and passes the UV light for the second time to expose the second (opposite) side of the mold. To a UV light source. The mold was then held at 120 ° C for 1 hour, after which it was allowed to cool to ambient temperature. The solid polymer sheet was removed from the mold 20 and had a reflection index (D-line, 1.60) 20.0, Abbe numbers from 34 to 35, and a Barco hardness of 934 from 18. 46 200424220 The invention has been described with reference to preferred embodiments. Obvious improvements and modifications can be made by reading and understanding the detailed description. The desire is to make the present invention be interpreted to include all such improvements and changes (which are within the scope of the attached patent application) or their equivalents. 5 [Simplified description of the drawing] None. [Description of the main element symbols] None 0 47

Claims (1)

200424220 10. Scope of patent application: 1. A polymerizable organic composition comprising one or more free-radically polymerizable monomers, at least one of which is a first monomer having at least di (meth) acrylic acid. And contains one or more backbone linkages selected from the group consisting of thiocarbamate linkages and dithiocarbamate linkages. 2. The polymerizable organic composition according to item 1 of the patent application scope, further comprising at least one monomer selected from the following: (a) a second radical polymerizable monomer, which is different from the first A monomer and having at least two kinds of ethylenically unsaturated radically polymerizable groups, which are selected from the group consisting of vinyl, allyl, and (fluorenyl) acrylfluorenyl; (b) a third radically polymerizable monomer, It has at least one ethylenically unsaturated radically polymerizable group and is different from the first monomer and the second monomer, and is selected from: ⑴monovinyl unsaturated monomer; (ii) having at least one The ethylenically unsaturated anhydride monomer is different from the monomers (i); and (c) a polythiol monomer having at least two kinds of thiol groups. 3. The polymerizable organic composition according to item 1 of the patent application scope, wherein the precursor of the first monomer is a self-reactive hydrogen material (which is a polythiol monomer having at least a dithiol group) and polycarbonate An ester monomer (having at least two functional groups selected from at least one of an isocyanate and an isothiocyanate) is prepared by the reaction of a polymerizable organic composition as claimed in item 3 of the patent application, which has a terminal The precursor of the first monomer of the reactive hydrogen group is selected from the group consisting of (fluorenyl) acrylic anhydride, (fluorenyl) propenyl gas, glycidyl (meth) acrylate, isocyanatoalkane One or more of (meth) acrylate, hydroxyalkyl (meth) acrylate, and hydroxyethyl methacrylate 48 200424220 react with each other to be functionalized. 5. For example, the polymerizable organic composition in the scope of patent application item 3, wherein the molar equivalent ratio of (NCO + NCS) / (SH) is 0.25: 1 to 4: Bu 6. As in the scope of patent application item 3, Polymerizable organic composition, wherein the reactive hydrogen material further comprises at least two reactive hydrogen groups selected from the group consisting of a hydroxyl group, a primary amine, a secondary amine, and a compound having one or more thiols and one or more radicals. . 7. The polymerizable organic composition according to item 6 of the application, wherein the reactive hydrogen material is a polyamine selected from ethylenediamine, Q-C3 dialkyltoluenediamine, methylenediphenylamine, Triethylene glycol bis (p-aminophenylbenzoate), a diamine represented by the general formula (A): (A) Diamine represented by general formula (B): (B) And a diamine represented by the general formula (C): (C) 8. The polymerizable organic composition according to item 7 of the application, wherein the general diamine of formula (A) is selected from one or more of the following: Each of R3 and R4 is a CrC3 alkyl group, and R5 is selected from hydrogen and halogen, and a mixture of these diamines. 9. The polymerizable organic composition according to item 7 of the scope of patent application, wherein the general diamine of formula (B) is selected from one or more of the following: Wherein each of R3 and R4 is an CrC3 alkyl group, and I is selected from hydrogen and dentin, and a mixture of these diamines. 10. The polymerizable organic composition according to item 7 of the scope of patent application, wherein the diamine of formula (C) 51 200424220 is selected from one or more of the following: Each of R3 and R4 is a CrC3 alkyl group, and R5 is selected from hydrogen and halogen, and a mixture of these diamines. 11. The polymerizable organic composition according to item 6 of the patent application, wherein the molar equivalent ratio of (NCO + NCS) / (SH + OH + NH2 + _NH ·) is 0.25: 1 to 4: 1. 12. If the polymerizable organic composition of item 6 of the patent application range, wherein the surface of the poly 52 200424220 thiol monomer is privately contained, it is called a polythiol monomer and the reactive hydrogen material. The total molar equivalents of the silk grade, county grade, grade grade silk and grade amine group are used as the basis. 13. The polymerizable organic composition according to item 2 of the patent application, wherein the second single system has an aromatic monomer of at least diethylene and is selected from the group consisting of dioxinylbenzene and diisopropylenyl Tooth-substituted derivatives of benzene, triethylbenzene, diethylnaphthalene, diethylbenzene, diisofluorenylbenzene, triethylbenzene, and diethylnaphthalene, and mixtures thereof. 14. The polymerizable organic composition according to item 2 of the scope of patent application, wherein the second monomer has a (meth) acrylfluorenyl group and is selected from one or more of the following. (I) is represented by the following general formula The monomer: „1” such as Guangqiyi. Ding 4 wherein each of the domains 11 is a positive number, and the sum of m and η is 0 to ^ & and each of R4 is hydrogen or methyl, and each of ^ is hydrogen or & to q , And A is a divalent bonding group selected from the group consisting of straight or branched stretched filaments, cyclic stretched scorching groups, phenylene groups, CrC9 alkyl-substituted phenylene groups, and groups represented by the following formula: Wherein each of 仏 and ^ is a CrC4 alkyl group, chlorine or bromine, each of p and q is an integer of 0 to 4, Θ represents a divalent phenyl group or a divalent 53 200424220 cyclohexane group, and when ® is two In the case of a valent phenyl group, X is selected from the group consisting of 0, S,, -CH2-, -CH = CH ·, C (CH3) 2-, -C (CH3) (C6H5)-, and when it represents a divalent cyclohexane group, X is selected from 〇0, S, -CH2-, and -C (CH3) 2 ·; (ii) bis [(meth) propenyl · terminal] poly (ethylene glycol) monomer, which is different from mono And (iii) a poly (meth) acrylfluorene-terminated monomer represented by the following general formula, and having a number average molecular weight of 200 to 2,000 g / mole; Among them, R is a polyvalent group of a polyhydric alcohol, I is hydrogen or methyl, R5 is hydrogen or & to C2 alkyl, and d is a number from 0 to 20, and j is an integer from 3 to 6. 15. The polymerizable organic composition according to item 14 of the scope of the patent application, wherein the χ is _C (CH3) 2, and ^ represents a divalent phenyl 'p & q, each of which is One is fluorenyl ′ I and I are each hydrogen, the sum of m and η is 5 to 20, R is a radical of pivalitritol, ′ is 3, r9 is hydrogen, and d is 54 200424220 16. For example, the polymerizable organic composition according to the second patent application range, wherein the second monomer has an allyl group and is represented by the following general formula: R- [OC (O) _O-R10] i, where R is from a polyol Derived group, R10 is a group derived from allyl or substituted allyl, and i is an integer of 2 to 6. 17. The polymerizable organic composition according to item 16 of the application, wherein the polyol derived from R is 4,4'-isopropylidene diphenol, i is 2, and R10 is derived from allyl The base. 18. The polymerizable organic composition according to item 2 of the patent application, wherein the polyol mono system is selected from one or more of the following: 2,5-difluorenylmethyl-1,4-dithiane , 2,2'_thiodiethane mercaptan, pentaerythritol tetrakis (3-fluorenylpropionate), pentaerythritol tetrakis (2-amidinoacetate), trimethyl methanopropane tris (3-fluorene Propionate), trimethylthiopropane tris (2-fluorenyl acetate), 4 · fluorenylmethyl_3,6_dithia-1,8_octane dithiol, 4_ Tributyl1,2-benzenedithiol, 4,4'-thiodiphenylthiol, benzenedithiol, ethylene glycol bis (2-fluorenyl acetate), ethylene glycol bis (3- Fluorenyl propionate), poly (ethylene glycol) bis (2-fluorenyl acetate), poly (ethylene glycol) bis (3-fluorenyl propionate), polythiol represented by the following formula : SH L (% p Ο-CH—CH2-0- 丨 --R2 SH where 1 and 112 are each independently selected from straight or branched chain alkylene, cyclic alkylene, phenylene and CrCg alkyl substituted phenylene, and oligomers of these polythiol monomers. 55 200424220 19. The polymerizable organic composition according to item 18 of the scope of patent application, wherein Thiol-based oligomer represented by the following general formula: S-Ri- ( Each of 1 and 112 is individually selected from linear or branched alkylene, cyclic alkylene, phenylene, and alkyl substituted phenylene of CrC9, and η and m are individually 0 to An integer of 21, so n + m is at least 1020. For a polymerizable organic composition according to item 18 of the scope of the patent application, wherein the polythiol oligomer is represented by the following general formula: Q Where η is an integer from 1 to 21. 21. The polymerizable organic composition according to item 2 of the application, wherein the monoethylene unsaturated mono system is selected from the group consisting of styrene, methylmethacrylate, isobornylfluorenyl acrylate, and phenoxyethyl One or more of methacrylate, cyclohexyl methacrylate, vinyl acetate, vinyl vapor, fluorenyl 56 200424220 ethyl (meth) acrylate, vinyl mercaptan, and allyl mercaptan By. 22. The polymerizable organic composition according to item 2 of the application, wherein the anhydride monosystem is selected from the group consisting of methacrylic anhydride, acrylic anhydride, maleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, Itaconic anhydride and a mixture of these monomers. 23. The polymerizable organic composition according to claim 3, wherein the polycyanate monomer having at least a difunctional group has one or more sulfur atoms in its backbone. 24. The polymerizable organic composition as claimed in claim 23, wherein the polycyanate monomer containing one or more sulfur atoms in its trunk has the following general formula: Each of R10 and Rn is individually a dagger to a dagger alkyl group. 25. A shaped article formed by a polymerization reaction of a polymerizable organic composition according to item 1 of the patent application. 26. A photochromic article formed by polymerizing a polymerizable organic composition, the composition comprising one or more free-radically polymerizable monomers, at least one of which is the first A body having at least di (meth) acryl group and containing one or more backbone bonds selected from the group consisting of thiourethane bonding and dithiocarbamate bonding. 27. For example, the photochromic article of the scope of application for patent No. 26, further comprising at least one monomer selected from the following: 57 200424220 (a) a second radical polymerizable monomer, which is different from the first One monomer with at least two ethylenically unsaturated, radically polymerizable groups selected from the group consisting of vinyl, allyl, and (meth) acrylfluorene; (b) a third radically polymerizable monomer , Which has at least one ethylenically unsaturated radically polymerizable group and is different from the first monomer and the second monomer, and is selected from: ⑴monovinyl unsaturated monomer; (ii) having at least Monoethylene unsaturated anhydride monomers are different from monomers (i); and (c) polythiol monomers having at least two thiol groups. 28. The photochromic article according to item 26 of the application, wherein the precursor of the first monomer is a self-reactive hydrogen material (which is a polythiol monomer having at least a dithiol group) and polycarbonate A monomer obtained by reacting at least two functional groups selected from at least one of isocyanate and isothiocyanate. 29. For example, the photochromic article of the scope of application for patent No. 28, wherein the molar equivalent ratio of (NCO + NCS) / (SH) is 0.25: 1 to 4: 1. 30. The photochromic article according to item 28 of the application, wherein the reactive hydrogen material further comprises at least two members selected from the group consisting of a hydroxyl group, a primary amine, a secondary amine, and one or more thiols and one or more of them. Reactive hydrogen radicals of compounds based on radicals. 31. The photochromic article according to item 30 of the application, wherein the reactive hydrogen material is a polyamine, which is selected from the group consisting of ethylenediamine, CrC3 dialkyltoluenediamine, methylenediphenylamine, and tridextrin. Diglycol di (p-aminobenzoate), a diamine represented by the general formula (A): (A) 58 200424220 Diamine represented by general formula (B): (B) And a diamine represented by the general formula (C): (C) Η 32. The photochromic article according to item 31 of the scope of patent application, wherein the diamine of the general formula (A) is selected from one or more of the following: 59 200424220 wherein each of R3 and R4 is a CVC3 alkyl group, and R5 is selected from hydrogen and halogen, and a mixture of these diamines. 33. The photochromic article according to item 31 of the application, wherein the diamine of the general formula (B) is selected from one or more of the following: 60 200424220 wherein each of R3 and R4 is a CrCs alkyl group, and R5 is selected from hydrogen and halogen, and a mixture of these diamines. 34. The photochromic article according to item 31 of the application, wherein the diamine of the general formula (C) is selected from one or more of the following: 61 200424220, and Each of R3 and R4 is a CrC3 alkyl group, and R5 is selected from hydrogen and halogen, and a mixture of these diamines. 35. For the photochromic article under the scope of application for patent No. 30, the molar equivalent ratio of (NCO + NCS) / (SH + OH + NH2 + _NH_) is 0.25: 1 to 4: 1. 36. The photochromic article according to item 30 of the application, wherein the thiol group of the polythiol monomer contains at least 50 mol% of the thiol of the polythiol monomer and the reactive hydrogen material The total molar equivalents of the amino group, the hydroxyl group, the primary amine group and the secondary amine group are used as the basis. 37. The photochromic article according to item 27 of the application, wherein the second single system has an aromatic monomer of at least divinyl, and is selected from the group consisting of divinylbenzene, diisopropylbenzene, triphenylene Ethylbenzene, diethylenenaphthalene, diethylenebenzene, diisopropenylbenzene, trivinylbenzene, and divinyl substituted derivatives, and mixtures thereof. 38. If the photochromic article in the scope of patent application No. 27, wherein the second single 62 200424220 body (meth) acryl group is transferred from one or more of the following: (i) expressed by the following general formula monomer: — CH h2c: 0—CH—CH2 Rs = CH: where m and n are positive numbers, and the sum of mAn is used to make ㈣, each of R sand 4 is hydrogen or methyl, and R5 ^ each is money machine to ^ burning group ' And A is a divalent bonding group selected from linear or segmented stretched filaments, cyclic stretched radicals, stretched phenylene radicals, stretched phenylene radicals substituted with CVCV silk, and radicals represented by the following general formula: Wherein each of R7 and R8 is a CVC4 alkyl group, chlorine, or molybdenum, and each of p and q is an integer of 0 to 4, Θ represents a monovalent phenyl group or a divalent cyclohexane group, and when G) is In the case of divalent phenyl, X is selected from 〇, 3, -3 (〇2)-,-(^ (0)-, -CH2-, -CH = CH ·, C (CH3) 2 "-c (CH3 ) (C6H5)-and when it represents a divalent cyclohexane group, X is selected from ο 0, s, -ch2-, and -C (CH3) 2-; (ii) bis [(meth) acrylfluorenyl · terminal ] Poly (ethylene glycol) monomer, which is 63 200424220, is different from monomer (i) and has a number average molecular weight of 200 to 2, g / mol. 聚 Poly (meth) acrylic acid represented by the following general formula Fermentation matrix, as early as 0-R -〇 ** ~ ^ 312 'CH 0-—I j-—qj T 2 ~ (5 Xg where R' is a polyvalent group of a polyhydric alcohol, R9 is hydrogen or methyl, and R5 is Nitrogen or (^ to ^ alkyl, d is a number from 0 to 20, and j is an integer from 3 to 6. 39. The photochromic article according to item 38 of the patent application scope, wherein the X is -C (CH3) 2- > represents a divalent phenyl group, each of p and q is 0, r3 and R4 are methyl, each of Rs and R0 is hydrogen, and the total is 5 to 20 ′ R, which is the pentaerythritol. Radical, j system 3, & system hydrogen, ⑽ ^. 40. For example, the photochromic article under the scope of patent application No. 27, wherein the second monomer has an allyl group and is represented by the following general formula: R " [0 " C (0) -0-Rj 〇] ^ where R is a group derived from a polyhydric alcohol, r1q is a group derived from a dilute propyl group or a substituted allyl group, and i is an integer from 2 to 6. Photochromic articles, in which the polyol derived from R is 4,4, · isopropylidene diphenol, i is 2, and 111 () is a group derived from allyl. 42. If the scope of patent application The photochromic article of item 27, wherein the polyhydric alcohol monosystem is selected from one or more of the following: 2,5-difluorenylmethyl-1,4 · dithia 64 200424220 alkane, 2,2 ' _Thiodiethane mercaptan, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), trimethyl alcohol propane tris (3-mercaptopropionate), trimethyl Thiopropane tris (2-fluorenyl acetate), 4 · fluorenylmethyl · 3,6 · dithia-1,8-octane dithiol, 4-tert-butyl1,2-benzenediphenyl Thiols, 4,4'-thiodiphenylthiol, benzenedithiol, ethylene glycol bis (2-mercaptoacetic acid) ), Ethylene glycol bis (3-M-based propionate), poly (ethylene glycol) bis (2-M-based acetate), poly (ethylene glycol) bis (3-fluorenyl propionate), Polythiol represented by the following formula: Each of 1 ^ and 112 is individually selected from linear or branched alkylene, cyclic alkylene, alkylene substituted alkylene and alkylene substituted alkylene, and those of these polythiol monomers Oligomer. 43. The photochromic article according to item 42 of the application, wherein the polythiol oligomer is represented by the following general formula: 65 200424220 wherein each of 1 ^ and 112 is individually selected from linear or branched alkylene, cyclic alkylene, phenylene, and alkyl substituted phenylene of Q-C9, and η and m Each is an integer from 0 to 21, so n + m is at least 1 44. For a photochromic article according to item 42 of the patent application, the polythiol oligomer is represented by the following general formula: Where η is an integer from 1 to 21. 45. The photochromic article according to item 27 of the application, wherein the monoethylenically unsaturated monosystem is selected from the group consisting of styrene, fluorenyl methacrylate, isobornyl fluorenyl acrylate, and phenoxyethyl methyl One or more of methacrylic acid ester, cyclohexylfluorenyl acrylate, vinyl acetate, vinyl gasification, fluorenyl ethyl (meth) acrylate, vinyl mercaptan and allyl mercaptan 46. For example, the photochromic article of item 27 of the patent application, wherein the anhydride monosystem is selected from methacrylic anhydride, acrylic anhydride, maleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, itaconic anhydride And mixtures of these monomers. 47. The photochromic article of item 26 of the patent application has an initial Barco hardness of at least 1, a reflection index of 1.57 to 1.80, and an Abbe number of at least 30. 48. For example, the photochromic article according to item 26 of the patent application scope, further comprising one or more additives, which are selected from the group consisting of light stabilizers, heat stabilizers, anti-66 200424220 oxidants, ultraviolet absorbers, release agents, Static (non-photochromic) dyes, colorants and flexibilizing additives and anti-yellowing additives; and mixtures of these additives. 49. The photochromic article according to item 48 of the application, wherein the additive is present in an amount of up to 10% by weight of the polymer. 50. The photochromic article according to item 26 of the patent application scope, further comprising a photochromic material. 51. The photochromic article as claimed in claim 50, wherein the photochromic material is applied to the surface of the polymerized polymerizable organic composition. 52. The photochromic article according to item 50 of the patent application scope, wherein the photochromic material is applied to the polymerizable polymerizable organic compound at a concentration of 0.15 to 0.35 mg per square centimeter of the surface of the photochromic article. combination. 53. The photochromic article according to item 50 of the scope of application for a patent, wherein the photochromic material is selected from the group consisting of spiron (gadotodol) naphthoxanthine, spiro (, indole), benzoxanthine, and chromene. , Benzopyran, naphthopyran, organometallic dioxazolium salt, (aryl azo) -thiocarbamic acid aryl hydrazine salt, mercury dithiazole salt, hydrazine, serotonin, amine _, 3_ fluorenyl capture acid anhydride, 3 · succinyl spermidine imimine and 3 ♦ sylpyrosin imidate; and a mixture of these photochromic materials. Λ 54. The photochromic article according to item 50 of the scope of patent application, wherein the photochromic material is a material having an activated absorption in the visible light range of 590 to 7 nm. 55. The photochromic article according to item 50 of the patent application range, wherein the photochromic material has an activation value in the visible light range of 400 to 200 nm ⑽ 67 200424220 maximum. 56. For example, the photochromic article of the scope of application for patent No. 50, wherein the photochromic material has a maximum activation absorption in the visible light range of 500 to 700nm. 57. For example, a photochromic article according to item 50 of the application, wherein the photochromic material is selected from the group consisting of dissolving in the polymer, dispersing in the polymer, and encapsulating the organic polymer substrate before curing. The method of covering and incorporating into the polymerizable organic composition is applied or incorporated into the photochromic article. 58. The photochromic article according to item 50 of the application, wherein the photochromic material is applied by absorbing the photochromic article so that the penetration of the photochromic material into the polymer is achieved. 59. The photochromic article according to item 58 of the patent application, wherein the absorption method comprises solvent-assisted transfer absorption. 60. The photochromic article according to item 58 of the patent application, wherein the absorption method includes vapor phase transfer. 61. The photochromic article according to item 50 of the application, wherein the photochromic material is applied as a coating to the surface of the photochromic article. 62. The photochromic article according to item 58 of the patent application scope, wherein the absorption method includes the following steps: coating the photochromic article with a photochromic material; heating the surface of the photochromic article; and self-photochromic Remove any residual coating on the surface of the discolored object. 63. For example, the photochromic object of the scope of application for patent No. 50, wherein the photochromic object 68 200424220 color object is used to bridge the lack of orthographic vision. 64. The photochromic article according to item 28 of the application, wherein the polycyanate monomer having at least a difunctional group has one or more sulfur atoms in its trunk. 65. The photochromic article according to item 64 of the application, wherein the polycyanate monomer having one or more sulfur atoms in its trunk has the following formula: Among them, each of R10 and Rn is an (^ to (: 3 alkyl group). 69 200424220 VII. Designated Representative Map: (1) The designated representative map in this case is: (). (II) The components of the representative map Brief explanation of symbols: 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: