High refractive material based on biomass magnolol and honokiol

Abstract

The present application relates to a high-refractive material based on biomass magnolol and honokiol. Specifically, the high-refractive material of the present application can be obtained by photo-curing reaction of a photo-curable monomer and a plurality of mercaptans / mercaptanols under photo-initiation, wherein the photo-curable monomer is derived from a monomer containing an allyl functional group derived from biomass magnolol and honokiol. The high-refractive material provided by the present application has good optical performance, in particular, it not only has a high refractive index (1.67-1.71) but also has a relatively high Abbe number (35-24).

Description

Technical Field

[0001] This invention relates to the field of optical resins, and more specifically, to a high-refractive-index material based on biomass magnolol and honokiol. Background Technology

[0002] Functional materials with high refractive indices have important applications in modern optical devices. These materials can reduce the thickness and curvature of optical elements, making them more versatile. Meanwhile, the Abbe number also plays a crucial role in optical material applications; it represents the dispersion capability of a medium. Media with high Abbe numbers exhibit lower dispersion, resulting in sharper images. Compared to inorganic materials, such as glass, organic high-refractive-index materials offer advantages such as light weight, ease of processing, and high mechanical strength.

[0003] However, currently developed high-refractive-index materials often face limitations due to difficulties in monomer synthesis or high costs. Meanwhile, lower-cost and easily synthesized materials such as PMMA and PC have low refractive indices, failing to meet the application requirements of many scenarios. In particular, it is difficult to reconcile the refractive index and Abbe number in most materials. Therefore, there is an urgent need in this field for a novel, directly photocurable, simple and efficient optical organic material with high refractive index and high Abbe number. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a resin material with a high refractive index and a high Abbe number, which is prepared by curing copolymerization of magnolol / and magnolol-based monomers with thiol / thiophenol monomers.

[0005] In a first aspect, the present invention provides a curing material prepared by copolymerizing component (a) and component (b):

[0006] (a) A resin monomer; said resin monomer is selected from the group consisting of compounds having the structure shown in formula (I), compounds having the structure shown in formula (II), or combinations thereof;

[0007]

[0008] in,

[0009] R1, R2, R3, and R4 are each independently selected from the following group: hydrogen, C 1-6 Alkyl, C 2-6 alkenyl, C 1-15 Alkylsilyl;

[0010] One or more hydrogen atoms on each of the above groups may optionally be substituted by substituents selected from the group consisting of: halogens, C 1-4 Alkyl, C 2-4alkenyl, C 2-4 Alkyne, phenyl, or with 1, 2 or 3 R groups a Substituted phenyl; R a Selected from the following group: halogens, C 1-6 Alkyl, C 2-6 alkenyl;

[0011] (b) Thiol monomers; said thiols monomers are selected from the group consisting of: methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo[2,2,1]heptane-extro-cis-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, bis(2-mercaptoethyl)thiomalate, 2,3-dimercaptosuccinic acid (2-mercaptoethyl) ester, 2,3-dimercapto-1-propanediol, etc. Alcohol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tri(2-mercaptoacetate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane), 5,7-dimercaptomethyl-1,11- Dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiazide, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4- bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethyloxy)benzene, 1,3-bis(mercaptomethyloxy)benzene, 1,4-bis(mercaptomethyloxy)benzene, 1,2-bis(mercaptoethyloxy)benzene, 1,3-bis(mercaptoethyloxy)benzene, 1,4-bis(mercaptoethyloxy)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,4-Tris(mercaptomethyloxy)benzene, 1,3,5-Tris(mercaptomethyloxy)benzene, 1,2,3-Tris(mercaptoethyloxy)benzene, 1,2,4-Tris(mercaptoethyloxy)benzene, 1,3,5-Tris(mercaptoethyloxy)benzene, 1,2,3,4-Tetramercaptobenzene, 1,2,3,5-Tetramercaptobenzene, 1,2,3,4-Tetra(mercaptomethyl)benzene, 1,2,3,5-Tetra(mercaptomethyl)benzene, 1,2,4,5-Tetra(mercaptomethyl)benzene, 1,2,3,4-Tetra(mercaptoethyl)benzene, 1,2,3,5-Tetra(mercaptoethyl)benzene, 1,2,3,4-Tetra(mercaptoethyl)benzene, 1,2,3,4-Tetra(mercaptoethyl)benzene, 1,2, 3,5-Tetra(mercaptomethyloxy)benzene, 1,2,4,5-Tetra(mercaptomethyloxy)benzene, 1,2,3,4-Tetra(mercaptoethyloxy)benzene, 1,2,3,5-Tetra(mercaptoethyloxy)benzene, 1,2,4,5-Tetra(mercaptoethyloxy)benzene, 2,2'-Dimercaptobiphenyl, 4,4'-Dimercaptobiphenyl, 4,4'-Dimercaptobibenzyl, 2,5-Toluenedithiophenol, 3,4-Toluenedithiophenol, 1,4-Naphthalenedithiophenol, 1,5-Naphthalenedithiophenol, 2,6-Naphthalenedithiophenol, 2,7-Naphthalenedithiophenol, 2,4-Dimethylbenzene-1,3-dithiophenol, 4,5-Dimethylbenzene-1,3-dithiophenol, 9,10-Anthracenedimethylthiol, 1,3-Di(p-methoxyphenyl)propane-2, 2-Dithiol, 1,3-Diphenylpropane-2,2-Dithiol, Phenylmethane-1,1-Dithiol, 2,4-Di(p-mercaptophenyl)pentane, 2-Methylamino-4,6-dimercapto-triazine, 2-Ethylamino-4,6-dimercapto-triazine, 2-Amino-4,6-dimercapto-triazine, 2-Morpholino-4,6-dimercapto-triazine, 2-Cyclohexylamino-4,6-dimercapto-triazine, 2-Methoxy-4,6-dimercapto-triazine, 2-Phenoxy-4,6-dimercapto-triazine, 2-Thiophenoxy-4,6-dimercapto-triazine, 2-Thiobutyloxy-4,6-dimercapto-triazine, 1,2-Bis(mercaptomethylthio)benzene, 1,3-Bis(mercaptomethylthio)benzene, 1,4-Bis(mercaptomethylthio)benzene, 1,2-Bis(mercaptoethylthio)benzene, 1,3-Bis(mercaptoethylthio)benzene, 1,4-Bis(mercaptoethylthio)benzene, 1,2,3-Tris(mercaptomethylthio)benzene, 1,2,4-Tris(mercaptomethylthio)benzene, 1,3,5-Tris(mercaptomethylthio)benzene, 1,2,3-Tris(mercaptoethylthio)benzene, 1,2,4-Tris(mercaptoethylthio)benzene, 1,3,5-Tris(mercaptomethylthio)benzene, 1,2,3,4-Tetra(mercaptomethylthio)benzene, 1,2,3,5-Tetra(mercaptomethylthio)benzene, 1,2,4,5-Tetra(mercaptomethylthio)benzene, 1,2,3,4-Tetra(mercaptoethylthio)benzene, 1,2,3,5-Tetra(mercaptoethylthio)benzene, 1,2,4,5-Tetra(mercaptoethylthio)benzene, bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropyl)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris( 3-Mercaptopropylthio)propane, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, 1,5-dimercapto-3-thiapentane, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide Bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), mercaptoacetic acid bis(2-mercaptoethyl ester), thionyl dipropionate bis(2-mercaptoethyl ester), 4,4-thionyl dibutyrate bis(2-mercaptoethyl ester), dithionyl dipropionate Bis(2-mercaptoethyl) acetate, bis(2-mercaptoethyl) dithionate, bis(2-mercaptoethyl) 4,4-dithionobutyrate, bis(2,3-dimercaptopropyl) thionodiacetate, bis(2,3-dimercaptopropyl) thionodiacetate, bis(2,3-dimercaptopropyl) dithionate, bis(2,3-dimercaptopropyl) dithionate, 2,2'-thiodiethylthiol, biphenyl-4,4'-dithiol, biphenyl-4,4'-dithiol, 4,4'-thiodiphenylthiol, bis(2-mercaptoethyl) ether, 3,3'-dimercaptopropyl ether, 2,5-dimethylmercapto-1,4-dithiane, 2,3-dithio(2-mercapto)-1-propanethiol, 2,3-Dithio(2-mercapto)-1-propanethiol, butanediol bis(mercaptoacetate), butanediol bis(mercaptopropionate), diethylene glycol bis(mercaptoacetate), diethylene glycol bis(mercaptopropionate), 2-[(2-mercaptoethyl)thio]-1,3-propanedithiol, 2,2'-[[2-[[2-[(2-mercaptoethyl)thio]ethyl]thio]-1,3-propanediyl]bis(thio)]bis[ethanethiol], 7-[[(2-mercaptoethyl)thio]methyl]-3,6,9,12-tetrathiotetradecane-1,14-dithiol, 1,3,4,6-tetra(2-mercaptoethyl)tetrahydroimidazo[4,5-d]imidazo-2,5(1H,3H)-dione, dicyclic thiomethyl sulfide, or combinations thereof.

[0012] In another preferred embodiment, R1, R2, R3, and R4 are each independently selected from the group consisting of: hydrogen, C 1-4 Alkyl, C 2-4 alkenyl, C 1-12 Alkylsilyl group.

[0013] In another preferred embodiment, R1, R2, R3 and R4 are allallyl.

[0014] In another preferred embodiment, the resin monomer is selected from the group consisting of:

[0015]

[0016] In a preferred embodiment, the thiol monomer is selected from the group consisting of 4,4'-thiodiphenylthiol, 2,5-dimethylmercapto-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, dicyclic thiomethyl sulfide, 2,3-dithio(2-mercapto)-1-propanethiol, pentaerythritol tetra(2-mercaptoacetate), or combinations thereof.

[0017] In a preferred embodiment, the molar ratio of the resin monomer to the thiol monomer is 1:(1-4).

[0018] In another preferred embodiment, the ratio of the number of olefin functional groups in the resin monomer to the number of thio functional groups in the thiol monomer is 1:(0.5 to 1.5); preferably 1:1.

[0019] In another preferred embodiment, the cured material is prepared by photocuring a resin monomer and a thiol monomer.

[0020] In a preferred embodiment, the cured material is prepared by copolymerization of components (a) and (b) in the presence of a photoinitiator;

[0021] The photoinitiator is selected from the group consisting of: 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, and benzophenone. 4-Phenylacetone, 2-Phenylacetyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, photoinitiator 754 (a mixture of benzoylcarbamates), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-1-(4-(2-hydroxy-2-methylpropionylphenyl)benzyl)-2-methyl-1-propanone, bis(2,6-difluoro-3-pyrrolephenyldicenoctanetane), ethyl 4-dimethylaminobenzoate;

[0022] Preferably, the photoinitiator is selected from the group consisting of benzoin dimethyl ether, 1-hydroxy-cyclohexyl-phenyl ketone, or combinations thereof.

[0023] A second aspect of the present invention provides a method for preparing a curable material as described in the first aspect of the present invention, comprising the steps of: copolymerizing components (a) and (b) in the presence of a photoinitiator to prepare the curable material.

[0024] In a preferred embodiment, the reaction is carried out under solvent-free conditions and includes the following steps:

[0025] A1. Mix resin monomers, thiol monomers and photoinitiators to obtain a prepolymer;

[0026] B2. The prepolymer is molded to obtain a preform;

[0027] C1. The preform is placed under the irradiation of light source B to carry out a photocuring reaction to obtain a high refractive material.

[0028] In a preferred embodiment, the light source B has a wavelength of 310-400 nm ultraviolet light.

[0029] In another preferred embodiment, the intensity of the light source B is 80-130 μW / cm². 2 Preferably 100-120 uW / cm 2 .

[0030] In another preferred embodiment, in step C1, the irradiation time of the light source B is 10 to 300 min; preferably 10 to 60 min; more preferably 10 to 30 min.

[0031] In another preferred embodiment, in step C1, the irradiation time of the light source B is 120 to 250 minutes.

[0032] In another preferred embodiment, in step C1, the irradiation time of the light source B is 180–240 min.

[0033] In another preferred embodiment, the temperature of the photocuring reaction is 20–30°C.

[0034] In a preferred embodiment, the photocuring reaction is carried out in the presence of solvent A and includes the following steps:

[0035] A2. Mix resin monomers, thiol monomers, solvent A, and photoinitiator to obtain a prepolymer mixed solution; remove solvent A from the prepolymer mixed solution to obtain the prepolymer;

[0036] B2. The prepolymer is molded to obtain a preform;

[0037] C2. The preform is placed under the irradiation of light source B to carry out a photocuring reaction to obtain a high refractive material;

[0038] The boiling point of solvent A is in the range of 30-150℃.

[0039] In a preferred embodiment, solvent A is selected from the group consisting of dichloromethane, tetrahydrofuran, ethanol, ethyl acetate, n-hexane, diethyl ether, or combinations thereof.

[0040] In another preferred embodiment, step A2 includes the following steps: heating the prepolymer mixture to the solvent boiling point, causing solvent A to evaporate and be removed from the prepolymer mixture to obtain the prepolymer.

[0041] In another preferred embodiment, step A2 includes the following steps: placing the prepolymer mixture solution under a light source A for irradiation, causing solvent A to evaporate and be removed from the prepolymer mixture solution to obtain the prepolymer.

[0042] In another preferred embodiment, in step A2, the light source A is ultraviolet light with a wavelength of 310-400nm.

[0043] In another preferred embodiment, in step A2, the intensity of the light source A is 80-130 μW / cm². 2 Preferably 100-120 uW / cm 2 .

[0044] In another preferred embodiment, in step A2, the irradiation time of the light source A is 1 to 3 hours; preferably 1 to 2 hours.

[0045] In another preferred embodiment, in step C2, the irradiation time of the light source B is 10 to 300 min; preferably 120 to 250 min; more preferably 180 to 240 min.

[0046] In another preferred embodiment, in step C2, the irradiation time of the light source B is 10 to 60 minutes.

[0047] In another preferred embodiment, in step C2, the irradiation time of the light source B is 10 to 30 minutes.

[0048] In another preferred embodiment, the reaction is carried out in the presence of solvent B and includes the following steps:

[0049] A3. Mix resin monomers, thiol monomers, solvent B and photoinitiator to obtain a prepolymer solution;

[0050] B3. The prepolymer solution is molded to obtain a preform;

[0051] C3. Place the preform under the irradiation of light source B to carry out a photocuring reaction to obtain a high refractive material;

[0052] The boiling point of solvent B is 100℃-200℃.

[0053] In another preferred embodiment, the solvent B is selected from the group consisting of benzene, toluene, xylene, trimethylbenzene, chlorobenzene, chloroform, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, or combinations thereof.

[0054] In another preferred embodiment, the prepolymer solution can also be obtained by the step of redissolving the prepolymer in solvent B.

[0055] In a preferred embodiment, the molding process is selected from the group consisting of: casting, drop coating, solution drop coating, solution spin coating, or a combination thereof.

[0056] In another preferred embodiment, the molding process includes the following steps: applying a prepolymer onto a substrate to obtain a preform.

[0057] In another preferred embodiment, the substrate is a frosted glass substrate or a flat glass substrate.

[0058] In another preferred embodiment, the molding process includes the following steps: pouring the prepolymer into a mold to obtain a preformed body.

[0059] In another preferred embodiment, the molding process includes the following steps: drop-coating a prepolymer solution to obtain a preform.

[0060] In another preferred embodiment, the molding process includes the following steps: spin-coating a prepolymer solution to obtain a preform.

[0061] A third aspect of the present invention provides an use of a curing material as described in the first aspect of the present invention, characterized in that it is used to prepare a high-refractive-index material.

[0062] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here. Attached Figure Description

[0063] Figure 1 The refractive index and Abbe number of the optical resin materials P1-P8 of the present invention are shown.

[0064] Figure 2 The storage modulus and glass transition temperature of the optical resin materials P3, P6, P8 and P4 of the present invention are shown.

[0065] Figure 3 The storage modulus and glass transition temperature of the optical resin materials P1, P5, P7 and P2 of the present invention are shown. Detailed Implementation Plan

[0066] Through extensive and in-depth experimental research and numerous screenings, the inventors have, for the first time, developed a class of allyl-containing functional monomers derived from biomass magnolol and honokiol. Furthermore, via a thiol-olefin reaction, these alkenyl-containing monomers can be converted into optical materials with both high refractive index and high Abbe number. The monomers of this invention are easy to synthesize, readily purified, and have a simple polymerization process, making them suitable as matrix resins for applications in the lens industry (e.g., manufacturing optical lenses), anti-reflective coatings for infrared emitting materials and optical devices, encapsulation resins for light-emitting diodes (LEDs), and microlenses for complementary metal-oxide-semiconductor image sensors in digital devices. Based on this, the inventors completed this invention.

[0067] the term

[0068] In this invention, unless otherwise specified, all terms have a general meaning known to those skilled in the art.

[0069] Unless otherwise specified, terms in the form of "C" are... 1-n The expression "" indicates that the group has 1-n carbon atoms, for example, "C 1-12 The expression "" indicates that the group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms; "C 6～10 "This refers to a group having 6, 7, 8, 9, or 10 carbon atoms."

[0070] Term "C" 2-6 "Alkenylphenyl" refers to a substituted C 2-6 Alkenyl groups are formed by losing a hydrogen atom from the benzene ring, such as styryl, 1-propenylphenyl, 1-butenylphenyl, etc.

[0071] Term "C" 1-15 "alkylsilyl" refers to Groups, wherein R1, R2, and R3 are each independently C 1-6 Alkyl groups, such as trimethylsilyl, triethylsilyl, triisopropylsilyl, tributylsilyl, etc.

[0072] The term "halogen" refers to F, Cl, Br, or I.

[0073] Term "C" 1-6 "Alkyl" refers to a straight-chain or branched alkyl group comprising 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, pteropentyl, or similar groups. "C" 1-4 "Alkyl" has a similar meaning.

[0074] Term "C" 2-6 "Alkenyl" refers to a straight-chain or branched alkenyl group with 2-6 carbon atoms and containing one double bond, and includes, without limitation, vinyl, propenyl, butenyl, isobutenyl, pentenyl, and hexenyl groups. 2-4 "Alkenyl" has a similar meaning.

[0075] Term "C" 2-4 "Alynyl" refers to a straight-chain or branched alkynyl group with 2-4 carbon atoms and a triple bond, including, without limitation, ethynyl, propynyl, butynyl, isobutynyl, etc.

[0076] The term "Abbe number" is a physical quantity used to measure the degree of light dispersion in a transparent medium. The smaller the Abbe number, the more severe the dispersion. The commonly used formula is (nd-1) / (nF-nC), where nd, nF, and nC are the refractive indices of the material under d-ray, F-ray, and C-ray, respectively.

[0077] The term "room temperature" refers to 20–30°C.

[0078] The main advantages of this invention are:

[0079] 1. The magnolol and honokiol used in this application have a biphenyl structure, which can contribute a high refractive index, and the allyl group in their structure can form crosslinking points, which is beneficial to the formation of copolymer materials.

[0080] 2. The magnolol and honokiol used in this application are derived from plants and can be used directly without complex synthesis processes. Furthermore, they are easy to derivatize and easy to synthesize photocurable monomers (i.e., resin monomers).

[0081] 3. The high-refractive-index material of this application can be obtained by photocurable monomers and various thiols / thiophenol monomers under photoinitiation curing reaction. The preparation method is simple, convenient and efficient. The curable monomers are derived from allyl functional groups derived from biomass magnolol and honokiol.

[0082] 4. The optical resin material in this application has excellent optical properties. Among existing optical resin materials, optical resins with high refractive index usually have low Abbe numbers. For example, optical resins with a refractive index of about 1.7 have only an Abbe number of 10-20. However, the optical resin in this application not only has a high refractive index (1.67-1.71) but also a high Abbe number (35-24).

[0083] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0084] Unless otherwise stated, percentages and portions are by weight.

[0085] Unless otherwise stated, the reaction is carried out at room temperature.

[0086] Example 1 Preparation of 5,5'-di-2-propen-1-yl-2,2'-bis(2-propen-1-yloxy)-1,1'-biphenyl (magnolithyl dielyl ether) (S1)

[0087]

[0088] At room temperature (rt), magnolol (10.654 g) and dimethyl sulfoxide (DMSO) were added to a 500 mL three-necked flask and stirred until dissolved to form a yellow solution. Sodium hydride (60%, 3.6 g in total) was added in 10-15 batches. After addition, the solution gradually became a suspension with foam floating on the surface. After stirring for about 40 minutes, it turned into an orange-brown solution. At this time, 3-bromopropene (12.582 g) was added and stirred for about 4-5 hours to obtain an orange-yellow solution. The solution was washed with water several times and separated. After extraction, the solvent was removed under reduced pressure. After rapid column chromatography, 13.80 g of a slightly yellow transparent oil was obtained, with a yield of about 99%. HPLC monitoring showed that the main product was about 93%. Secondary column chromatography separation yielded 11.80 g of an almost colorless transparent oil (S1) with a purity of about 99.5%. The total yield of the target product was about 84.7%.

[0089] 1H NMR(400MHz,cdcl3)δ7.17–7.05(m,4H),6.89(d,J=8.1Hz,2H),6.12–5.78(m,4H),5.24(dq ,J=17.3,1.7Hz,2H),5.17–5.02(m,6H),4.49(dt,J=4.8,1.7Hz,4H),3.38(d,J=6.7Hz,4H).

[0090] 13 C NMR (126MHz, CDCl3) δ154.54, 137.91, 133.81, 131.85 (d, J = 3.3Hz), 128.27 (d, J = 4.9Hz), 116.36, 115.50, 112.55, 69.21, 39.47.

[0091] Example 2 Preparation of 3',5-di-2-propen-1-yl-2,4'-bis(2-propen-1-yloxy)-1,1'-biphenyl (and magnolol diallyl ether) (S4)

[0092]

[0093] At room temperature (rt), magnolol (2.651 g) and 40 mL of dimethyl sulfoxide were added to a 100 mL three-necked flask and stirred until dissolved to form a brown solution. Sodium hydride (60%, 900 mg total) was added in 10-15 batches. After addition, the solution gradually became a suspension with foam floating on the surface. After stirring for about 40 minutes, it turned into a dark brown solution. At this time, 3-bromopropene (3.196 g) was added and stirred for about 4-5 hours to obtain a brown solution. The solution was washed with water several times and separated. After extraction, the solvent was removed under reduced pressure. After rapid column chromatography, 3.18 g of a pale yellow transparent oil (S4) was obtained, with a yield of about 92%. HPLC monitoring showed that the main product was about 99.0%.

[0094] 1 H NMR (500MHz, CDCl3) δ7.51–7.37(m,1H),7.24–7.05(m,1H),6.93(dd,J=8.4,4.4Hz,1H),6.35–5.85(m,2H),5 .59–5.22(m,2H),5.22–5.00(m,2H),4.59(ddt,J=44.1,4.9,1.7Hz,2H),3.47(ddd,J=49.3,6.8,1.6Hz,2H).

[0095] 13C NMR(126MHz, CDCl3)δ155.38,153.92,137.82,137.07,133.60(d,J=14.1Hz),132.63,131.25,131.15–130.72(m),12 8.27(d,J=2.1Hz),127.86,116.86(d,J=12.4Hz),115.54(d,J=14.1Hz),113.18,111.21,69.37,68.86,39.49,34.59.

[0096] Example 3: Copolymerization reaction of magnolol-based dielyl ether and 2,3-dithio(2-mercapto)-1-propanethiol to prepare optical resin material P1

[0097]

[0098] Take a 20mL glass sample bottle, add resin monomer S1 (1.040g), thiol monomer S2 (1.042g) and 1-hydroxycyclohexyl phenyl ketone (60mg), mix and stir until uniform to obtain a colorless clear oily liquid (i.e., prepolymer).

[0099] The above-mentioned mixed liquid was drop-coated onto a glass substrate. Another glass substrate was then flattened into a circular liquid film (preform) and transferred to a UV curing chamber. The film was cured using 315-400nm wavelength radiation at 115mW / cm². 2 Irradiation with an energy density (hv) for at least 10 minutes can yield a colorless and transparent thin film (i.e., the high-refractive-index material described in this invention). Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0100] Example 4: Copolymerization of magnolol-based dielyl ether and 4,4'-thiodiphenylthiol to prepare optical resin material P2

[0101]

[0102] Take a 20mL glass sample bottle, add resin monomer S1 (1.040g), thiol monomer S3 (1.502g) and 1-hydroxycyclohexyl phenyl ketone (250mg), then add 7-10mL of dichloromethane, mix and stir until uniform to obtain a colorless and clear solution (i.e., prepolymer mixed solution).

[0103] The solution was transferred to a UV curing chamber and cured with 315-400nm wavelength radiation at 115mW / cm². 2 Irradiate with an energy density for at least 100 minutes, and the solvent evaporates to obtain a slightly yellow viscous liquid (i.e., prepolymer);

[0104] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0105] The aforementioned liquid film was transferred to a UV curing chamber and cured using 315-400 nm wavelength radiation at 115 mW / cm². 2 Irradiation with an energy density for at least 120 minutes yields a pale yellow transparent film (i.e., the high-refractive-index material described in this invention). Specifically, the substrate can be a frosted glass substrate or a flat glass substrate. n is 2-10000; preferably 2-5000.

[0106] Example 5: Copolymerization of magnolol-based dielyl ether and 4,4'-thiodiphenylthiol to prepare optical resin material P2

[0107]

[0108] Take a 20mL glass sample bottle, add monomers S1 (1.040g), S3 (1.502g), and 1-hydroxycyclohexyl phenyl ketone (250mg), then add dichloromethane dropwise until all the solids are dissolved. Stir until homogeneous to obtain a slightly yellow viscous liquid (i.e., prepolymer mixed solution).

[0109] The above prepolymer mixture solution is heated to allow all the solvent to evaporate and be removed, resulting in a mixed liquid (i.e., the prepolymer).

[0110] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is taken and flattened into a circular liquid film (i.e., a preform).

[0111] The above-mentioned film was transferred to a UV curing chamber and cured using 315-400nm wavelength radiation at 115mW / cm². 2 Irradiation at an energy density for at least 180 minutes yields a pale yellow, transparent film. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0112] Example 6: Copolymerization of magnolol dielyl ether and 2,3-dithio(2-mercapto)-1-propanethiol to prepare optical resin material P3

[0113]

[0114] Take a 20mL glass sample bottle, add monomers S4 (1.040g), S2 (1.042g), and 1-hydroxycyclohexylphenyl ketone (60mg), mix and stir until homogeneous to obtain an almost colorless, clear, oily liquid (i.e., prepolymer).

[0115] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0116] The aforementioned liquid film was transferred to a UV curing chamber and cured using 315-400 nm wavelength radiation at 115 mW / cm². 2 By irradiating with an energy density of [energy density] for at least 10 minutes, a colorless and transparent film can be obtained. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0117] Example 7: Copolymerization of magnolol diallyl ether and 4,4'-thiodiphenylthiol to prepare optical resin material P4

[0118]

[0119] Take a 20mL glass sample bottle, add monomers S1 (1.040g), S3 (1.502g), 1-hydroxycyclohexyl phenyl ketone (250mg), and then add 7-10mL of dichloromethane. Mix and stir until homogeneous to obtain a colorless and clear solution (i.e., prepolymer mixed solution).

[0120] The above liquid was transferred to a UV curing chamber and irradiated with 315-400nm wavelength radiation light at an energy density of 115mW / cm2 for at least 100 minutes. The solvent evaporated to obtain a slightly yellow viscous liquid (i.e., prepolymer).

[0121] The above liquid is dripped onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0122] The aforementioned film is transferred to an ultraviolet curing chamber and irradiated with 315-400nm wavelength radiation light at an energy density of 115mW / cm² for at least 120 minutes to obtain a pale yellow transparent film. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0123] Example 8: Copolymerization of magnolol-based dielyl ether and 4,4'-thiodiphenylthiol to prepare optical resin material P4

[0124]

[0125] Take a 20mL glass sample bottle, add monomers S1 (1.040g), S3 (1.502g), and 1-hydroxycyclohexyl phenyl ketone (250mg), then add dichloromethane dropwise until all the solids are dissolved. Stir until homogeneous to obtain a slightly yellow viscous liquid (i.e., prepolymer mixed solution).

[0126] The above prepolymer mixture solution is heated to allow all the solvent to evaporate and be removed, resulting in a mixed liquid (i.e., the prepolymer).

[0127] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0128] The aforementioned liquid film was transferred to a UV curing chamber and cured using 315-400 nm wavelength radiation at 115 mW / cm². 2 Irradiation at an energy density for at least 180 minutes yields a pale yellow, transparent film. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0129] Example 9: Copolymerization of magnolol-based dielyl ether and pentaerythritol tetrakis(3-mercaptopropionic acid) ester to prepare optical resin material P5

[0130]

[0131] Take a 20mL glass sample bottle, add monomers S1 (1.040g), S5 (1.538g), and 1-hydroxycyclohexyl phenyl ketone (80mg), mix and stir until uniform to obtain a colorless, clear, oily liquid (i.e., prepolymer).

[0132] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0133] The liquid film is transferred to an ultraviolet curing chamber and irradiated with 315-400nm wavelength radiation at an energy density of 115mW / cm² for at least 10 minutes to obtain a colorless and transparent film. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0134] Example 10: Copolymerization of magnolol dielyl ether and pentaerythritol tetrakis(3-mercaptopropionic acid) ester thiol to prepare optical resin material P6

[0135]

[0136] Take a 20mL glass sample bottle, add monomers S4 (1.040g), S5 (1.538g), and 1-hydroxycyclohexyl phenyl ketone (80mg), mix and stir until uniform to obtain a colorless, clear, oily liquid (i.e., prepolymer).

[0137] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0138] The liquid film is transferred to an ultraviolet curing chamber and irradiated with 315-400nm wavelength radiation at an energy density of 115mW / cm² for at least 10 minutes to obtain a colorless and transparent film. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0139] Example 11: Copolymerization of magnolol-based dielyl ether and 2,5-dimethylmercapto-1,4-dithiazide mercaptan to prepare optical resin material P7

[0140]

[0141] Take a 20mL glass sample bottle, add monomers S1 (1.040g), S6 (1.258g), and 1-hydroxycyclohexyl phenyl ketone (75mg), mix and stir until uniform to obtain a colorless, clear, oily liquid (i.e., prepolymer).

[0142] The above-mentioned mixed liquid is drop-coated onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0143] The aforementioned film is transferred to an ultraviolet curing chamber and irradiated with 315-400nm wavelength radiation light at an energy density of 115mW / cm² for at least 10 minutes to obtain a colorless and transparent film. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0144] Example 12: Copolymerization of magnolol diallyl ether and 2,5-dimethylmercapto-1,4-dithiazide mercaptan to prepare optical resin material P8

[0145]

[0146] Take a 20mL glass sample bottle, add monomers S4 (1.040g), S6 (1.258g), and 1-hydroxycyclohexyl phenyl ketone (75mg), mix and stir until uniform to obtain a colorless, clear, oily liquid (i.e., prepolymer).

[0147] The above liquid is dripped onto a glass substrate, and another glass substrate is flattened into a circular liquid film (i.e., a preform).

[0148] The aforementioned liquid film was transferred to a UV curing chamber and cured using 315-400 nm wavelength radiation at 115 mW / cm². 2By irradiating with an energy density of [energy density] for at least 10 minutes, a colorless and transparent film can be obtained. Specifically, the substrate can be a frosted quartz glass substrate or a planar quartz glass substrate. n is 2-10000; preferably 2-5000.

[0149] Example 13: Study on the optical properties of optical resin materials P1-P8 prepared by copolymerization of magnolol and magnolol-based dielyl ether resin monomers.

[0150] 1. Experimental Methods

[0151] 1.1 Refractive Index Test

[0152] The sample thin film was tested using an ellipsometer (model: ELLIP-SR-I) with a test wavelength range of 300nm-1000nm and a step size of 10nm.

[0153] 1.2 Abbe Number Test

[0154] Calculation formula: (nd-1) / (nF-nC)

[0155] Wherein, nd, nF, and nC are the refractive indices of the material under d-ray, F-ray, and C-ray conditions, respectively, and d-ray, F-ray, and C-ray refer to light in the 486.3nm, 589.1nm, and 656.1nm wavelength bands, respectively.

[0156] 2. Experimental Results

[0157] Copolymer thin film resin materials (i.e., the optical resin materials described in this application) P1-P8 loaded on glass substrates were obtained using frosted glass substrates or planar glass substrates as assisted molding. Their refractive index and Abbe number were measured, and the experimental results are shown in Table 1 below. Figure 1 As shown.

[0158] Table 1. Refractive indices and Abbe numbers of optical resin materials P1-P8

[0159]

[0160] 3. Experimental Conclusions

[0161] Experimental results show that the optical resin materials prepared from the compounds of this application have high refractive index (1.67-1.71) and high Abbe number (35-24), and excellent optical properties.

[0162] Example 14 DMA test of optical resin materials P1-P8 prepared by copolymerization of magnolol and magnolol-based dielyl ether resin monomers

[0163] 1. Experimental Methods

[0164] Dynamic thermomechanical analysis (DMA) was performed using a DMA / Q800 instrument under a nitrogen atmosphere with a heating rate of 5℃ / min. The storage modulus and glass transition temperature of the optical resin material obtained are shown in Table 2 below. Figure 2 and Figure 3 As shown.

[0165] 2. Experimental Results

[0166] Table 2. Storage modulus and glass transition temperature of optical resin materials P1-P8

[0167]

[0168]

[0169] 3. Experimental Conclusions

[0170] Experimental results show that the optical resin material prepared from the compound of this application has a high storage modulus and a high glass transition temperature, and excellent thermomechanical properties.

[0171] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A cured material used as an optical resin material, characterized in that, The method for preparing the cured material includes the following steps: in the presence of a photoinitiator, components (a) and (b) are photocured to obtain the cured material; and the refractive index of the cured material is 1.67-1.71, and the Abbe number of the cured material is 35-24. (a) A resin monomer; said resin monomer is selected from the group consisting of compounds having the structure shown in formula (I), compounds having the structure shown in formula (II), or combinations thereof; in, R1, R2, R3, and R4 are each independently C 2-4 alkenyl; (b) Thiol monomer; said thiol monomer is selected from the group consisting of 4,4'-thiodiphenylthiol, 2,5-dimethylmercapto-1,4-dithiane, 2,3-dithio(2-mercapto)-1-propanethiol, or combinations thereof; The molar ratio of the resin monomer to the thiol monomer is 1:(1~4); The wavelength of ultraviolet light used for photocuring is 310-400 nm; The intensity of the ultraviolet light used for photocuring is 80-130 uW / cm². 2 .

2. The curing material as described in claim 1, characterized in that, The photoinitiator is selected from the group consisting of: 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, 2-isopropylthioxanthone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, and methyl o-benzoylbenzoate. Benzophenone, 4-phenylbenzophenone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, photoinitiator 754, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-1-(4-(2-hydroxy-2-methylpropionylphenyl)benzyl)-2-methyl-1-propanone, bis(2,6-difluoro-3-pyrrolephenyldicenoctanetane), ethyl 4-dimethylaminobenzoate.

3. The method for preparing the cured material as described in claim 1, characterized in that, The process includes the following steps: in the presence of a photoinitiator, components (a) and (b) undergo a photocuring reaction to prepare the cured material.

4. The preparation method according to claim 3, characterized in that, The photocuring reaction is carried out under solvent-free conditions and includes the following steps: A1. Mix resin monomers, thiol monomers, and photoinitiators to obtain a prepolymer; B2. The prepolymer is molded to obtain a preform; C1. The preform is placed under the irradiation of light source B to carry out a photocuring reaction to obtain a high refractive material.

5. The preparation method according to claim 4, characterized in that, The light source B is ultraviolet light with a wavelength of 310-400 nm.

6. The preparation method according to claim 3, characterized in that, The photocuring reaction is carried out in the presence of solvent A and includes the following steps: A2. Mix resin monomers, thiol monomers, solvent A, and photoinitiator to obtain a prepolymer mixed solution; remove solvent A from the prepolymer mixed solution to obtain the prepolymer; B2. The prepolymer is molded to obtain a preform; C2. The preform is placed under the irradiation of light source B to carry out a photocuring reaction to obtain a high refractive material; The boiling point of solvent A is in the range of 30-150℃.

7. The preparation method according to claim 6, characterized in that, Solvent A is selected from the group consisting of dichloromethane, tetrahydrofuran, ethanol, ethyl acetate, n-hexane, diethyl ether, or combinations thereof.

8. The preparation method according to claim 4 or 6, characterized in that, The molding process is selected from the group consisting of: casting, drop coating, solution spin coating, or a combination thereof.

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