Polymer materials and methods for preparing them, compositions, optical components, and devices.

Abstract

The present application provides a polymeric material comprising a repeating unit. The repeating unit comprises a functional group and a flexible chain segment bonded to the functional group. The functional group comprises an aryl group. The refractive index of the polymeric material is 1.56 or more, and the water absorption rate is 0.1% or less. The present application further provides a method for preparing the polymeric material, as well as compositions, optical components, and devices in which the polymeric material is used. The polymeric material can achieve a balance between the characteristics of the polymeric material, such as light transmittance, refractive index, heat resistance, and water absorption rate, and the application range of the material has been expanded.

Description

Technical Field

[0001] Cross-reference to Related Applications This application claims priority to Chinese Patent Application No. 202110246031.5, filed with the China National Intellectual Property Administration on March 5, 2021, entitled "Polymer Material and Its Preparation Method, Composition, Optical Component, and Device", the entire content of which is incorporated herein by reference.

[0002] This application relates to the field of polymer materials, particularly polymer materials and their preparation methods, compositions and optical components containing the polymer materials, and devices containing the optical components.

Background Art

[0003] Currently, the polymer materials used in the optical field mainly include polycarbonate (PC), polyimide (PI), cycloolefin polymer (cyclic olefin copolymer / cycloolefin polymer, COC / COP), poly(methyl methacrylate) (PMMA), polyethylene terephthalate (PET), poly(ethylene naphthalate) (PEN), polystyrene (PS), modified cellulose, etc. For polymers used in the optical field, the focus is mainly on the light transmittance, refractive index, birefringence, heat resistance, water absorption rate, and other properties of the materials. Conventional materials have advantages and disadvantages regarding the above properties. For example, the PC material has high heat resistance, a high refractive index, and other advantages, and can be used in optical images, polarizers, etc. based on the difference in birefringence performance. However, since polar groups exist in PC, the material has a high water absorption rate. This limits the design of optical devices. The COC material is a pure hydrocarbon polymer, has a very low water absorption rate and high thermal stability, but the refractive index of the material is low. The PS material has a lower water absorption rate and a higher refractive index than the COC material. However, the PS material has a serious birefringence phenomenon and poor thermal stability, and can hardly be used as an optical material. The PS material is mainly used in fields such as structural materials and packaging materials.

Summary of the Invention

[0004] A first embodiment of the present invention provides a polymer material comprising repeating units, the repeating units comprising a functional group and a flexible chain segment bonded to the functional group, the functional group comprising an aryl group, the refractive index of the polymer material being 1.56 or higher and the water absorption rate being 0.1% or lower.

[0005] Functional groups in polymer materials primarily provide the refractive properties and heat resistance of the polymer material. Flexible chain segments primarily regulate the heat resistance and mechanical properties of the polymer material. In polymer materials, a balance of material characteristics such as light transmittance, refractive index, heat resistance, and water absorption is achieved, expanding the range of applications of the material, and the material has a great advantage in application to high-end optical devices. Polymer materials have a high refractive index of 1.56 or higher, a low water absorption of 0.1% or less, good heat resistance with a glass transition temperature of 120°C or higher, and good light transmittance with an Abbe number of 17 or higher.

[0006] In the implementation of this application, the flexible chain segment includes at least one of an alkyl chain segment, a polyethylene glycol chain segment, and a poly(ethanedithiol) chain segment.

[0007] In the implementation of this application, the general structural formula of the aryl group is at least one of the following general formulas (1), (2), (3), and (4). [ka] [ka] [ka] [ka]

[0008] In general formulas (1) to (4), R and R' are, respectively, an oxygen atom, a sulfur atom, a -(OR2)tO- group, and the following fluorene group: [ka] , Selected from alkylidene groups having 1 to 10 carbon atoms, or arylene groups having 1 to 30 carbon atoms; m, k, m', and k' are integers between 0 and 5, inclusive; R1, R2, R3, R4, R5, and R6 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, or a thiol group; d, e, f, d', e', and f' are each integers between 0 and 4, inclusive; In the aforementioned -(OR2)tO- group, R2 is an alkylidene group having 1 to 4 carbon atoms, and t is an integer between 1 and 10; In the fluorene group, R7, R8, R9, and R10 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, or a thiol group, s and s' are each integers between 0 and 5, and g, h, g', and h' are each integers between 0 and 4.

[0009] In the implementation of this application, when the general structural formula of the aryl group is general formula (1), R is the fluorene group, k=k'=0, and the general structural formula of the aryl group is as follows. [ka]

[0010] In the implementation of this application, when the general structural formula of the aryl group is general formula (3) and m=m'=0, the general structural formula of the aryl group is as follows. [ka]

[0011] In the implementation of this application, the functional group further includes an alicyclic group.

[0012] In the implementation of this application, the alicyclic group is a group containing a bridged ring structure, a group containing a helical ring structure, or a ring structure containing a heteroatom.

[0013] In the implementation of this application, the structural formula of the alicyclic group is at least one of the following.

Chemical formula

[0014] In the implementation of this application, the structural formula of the repeating unit is as follows.

Chemical formula

[0015] In the implementation of this application, the structural formula of the repeating unit is one or more of the following.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0016] In the implementation of this application, the structural formula of the repeating unit is as follows: [ka] (A and A' represent aryl groups, respectively, and -O- represents a flexible chain segment.)

[0017] In the implementation of this application, the flexible chain segment is selected from at least one of a polyethylene glycol chain segment having a degree of polymerization of less than 10, a poly(ethanedithiol) chain segment having a degree of polymerization of less than 10, and a substituted or unsubstituted alkylidene group chain segment having fewer than 20 carbon atoms.

[0018] In the implementation of this application, the structural formula of the flexible chain segment is as follows. [ka] (In the formula, X and Y represent either an oxygen atom or a sulfur atom, respectively; R11 represents an alkylidene group having 1 to 4 carbon atoms; and i is an integer between 0 and 10.)

[0019] In the implementation of this application, the structural formula of the flexible chain segment is as follows. [ka] (In the formula, X and Y represent either an O atom or an S atom, respectively; R11 represents an alkylidene group having 1 to 4 carbon atoms; R12 represents an alkylidene group having 1 to 10 carbon atoms; and i is an integer between 0 and 10.)

[0020] In the implementation of this application, the structural formula of the flexible chain segment is as follows. [ka] [ka] (In the formula, X and Y represent either an O atom or an S atom, respectively; R11 represents an alkylidene group having 1 to 4 carbon atoms; R12 and R13 represent an alkylidene group having 1 to 10 carbon atoms; and i is an integer between 0 and 10.)

[0021] In the implementation of this application, the glass transition temperature of the polymer material is 120°C or higher.

[0022] In the implementation of this application, the Abbe number of the polymer material is 17 or more.

[0023] A second embodiment of the present application provides a composition comprising the aforementioned polymer material.

[0024] In the practice of this application, the composition further comprises at least one of a filler, a dye, an antioxidant, a light stabilizer, a plasticizer, a flame retardant, an antistatic agent, and a mold release agent.

[0025] A third embodiment of the present invention provides an optical component comprising the polymer material or composition described above.

[0026] In the implementation of this application, the optical component is an optical lens, an optical film, a light guide plate, or an optical disc.

[0027] A fourth embodiment of the embodiments of this application provides a device including an optical component described in either the third embodiment of the embodiments of this application or an embodiment of the third embodiment.

[0028] In the aforementioned polymer material, a balance can be achieved between material characteristics such as light transmittance, refractive index, birefringence, heat resistance, and water absorption. Therefore, the range of applications for the material is broadened, and the material is considerably advantageous for applications in high-end optical devices.

[0029] A fifth aspect of the embodiments of this application provides a method for preparing the polymer material described above. The method is as follows: To prepare a diene monomer comprising a functional group containing an aryl group and a flexible chain segment bonded to the functional group; The process involves causing a metathesis reaction of the diene monomer to obtain an intermediate product containing a carbon-carbon double bond, and then causing a hydrogenation reaction of the intermediate product to produce a polymer material comprising repeating units including the functional group and the flexible chain segment bonded to the functional group. Includes.

[0030] The reaction in the above preparation method is divided into two steps. In the first step, the diene monomer undergoes a metathesis reaction to obtain an intermediate product containing a carbon-carbon double bond. In the second step, the double bond in the intermediate product is added to obtain the final polymer.

[0031] In the implementation of this application, the structural formula of the diene monomer is as follows: [ka] (In the formula, A is an aryl group, RA1 and RA2 represent flexible chain segments, RA3 and RA4 are selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group, respectively, and RA5, RA6, RA7, and RA8 are selected from a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkane having fewer than 5 carbon atoms, respectively.)

[0032] In the implementation of this application, the diene monomer further comprises a diene monomer whose functional group is an alicyclic group.

[0033] A sixth aspect of the embodiments of this application provides a method for preparing the polymer material described above. The method is as follows: To prepare a diene monomer comprising a functional group containing an aryl group and a flexible chain segment bonded to the functional group; To prepare the dithiol monomer; An addition reaction occurs between the thiol group of the dithiol monomer and the carbon-carbon double bond of the diene monomer to produce a polymer material comprising repeating units including the functional group and the flexible chain segment bonded to the functional group. Includes.

[0034] In the above preparation method, an addition reaction occurs between the thiol group of the dithiol monomer and the carbon-carbon double bond of the diene monomer, thereby producing a polymer material.

[0035] In the implementation of this application, the structural formula of the diene monomer is as follows: [ka] (In the formula, A is an aryl group, RA1 and RA2 each represent a flexible chain segment, RA3 and RA4 are selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group, and RA5, RA6, RA7, and RA8 are selected from a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkane having fewer than 5 carbon atoms, respectively.)

[0036] In the implementation of this application, the diene monomer further comprises a diene monomer whose functional group is an alicyclic group.

[0037] In the implementation of this application, the dithiol monomer includes at least one of the following: [ka] [ka] [ka] It contains at least one substituted or unsubstituted aliphatic dithiol. (In the formula, A' is an aryl group, B is an alicyclic group, and RA1', RA2', RB1, and RB2 each represent a flexible chain segment.)

[0038] A seventh aspect of the embodiments of this application provides a method for preparing the above-described polymer. The method is as follows: To prepare a monomer comprising a functional group containing an aryl group and a phenol group bonded to the functional group; To induce a nucleophilic substitution reaction between the phenol group of the monomer and the halogenated aromatic compound, thereby producing a polymer material comprising repeating units including the functional group and a flexible chain segment bonded to the functional group, Includes.

[0039] In the above preparation method, the nucleophilic substitution reaction occurs between the phenol group and the halogenated aromatic compound, producing a polymer having the same structure as a polyaryl ether.

[0040] In the implementation of this application, the structural formula of the monomer is as follows: [ka] (In the formula, A is an aryl group.) The structural formula of the aforementioned halogenated aromatic compound is as follows. [ka] (In the formula, A' is an aryl group, and X1 and X2 are halogen atoms, respectively.)

[0041] A polymer material prepared according to the method for preparing a polymer material provided in the fifth to seventh embodiments of this application has a refractive index of 1.56 or higher and a water absorption rate of 0.1% by weight or less. Furthermore, the performance of the polymer material further includes a glass transition temperature of 120°C or higher and / or an Abbe number of 17 or higher. [Brief explanation of the drawing]

[0042] [Figure 1] Figure 1 shows the hydrogen-1 nuclear magnetic resonance spectrum of a monomer according to Example 1 of this application.

[0043] [Figure 2] Figure 2 shows the hydrogen-1 nuclear magnetic resonance spectra of the reaction intermediate product and polymer according to Example 1 of this application.

[0044] [Figure 3] Figure 3 shows the hydrogen-1 nuclear magnetic resonance spectrum of the monomer according to Example 2 of this application. [Modes for carrying out the invention]

[0045] The embodiments of this application will be described below with reference to the accompanying drawings.

[0046] Conventional optical polymer materials cannot achieve a balance between light transmittance, refractive index, heat resistance, water absorption, and other properties. Therefore, their range of applications has been limited.

[0047] This application provides a polymer material. It is possible to achieve a balance of material characteristics such as light transmittance, refractive index, heat resistance, and water absorption, expanding the range of applications of the material, and the material has great advantages in application to high-end optical devices. The polymer material has a high refractive index of 1.56 or higher, a low water absorption rate of 0.1% or less, good heat resistance with a glass transition temperature of 120°C or higher, and good light transmittance with an Abbe number of 17 or higher.

[0048] The polymer material comprises repeating units. Each repeating unit comprises a functional group and a flexible chain segment bonded to the functional group. The functional group comprises an aryl group. The flexible chain segment comprises at least one of an alkyl group, a polyethylene glycol chain segment, and a poly(ethanedithiol) chain segment. It can be understood that the flexible chain segment of this application may further comprise an oxygen atom and a chemical bond to the oxygen atom, e.g., -O-. The functional group primarily provides the refractive and heat resistance properties of the polymer material. The flexible chain segment primarily modulates the heat resistance and mechanical properties of the polymer material. Generally, a higher proportion of flexible chain segments in the polymer indicates a lower glass transition temperature, strength, and internal stress of the polymer. In some embodiments, it can be understood that, in addition to the repeating units of the type described above, the polymer material may further comprise another type of repeating unit (which does not satisfy the requirements described above). In some embodiments, the polymer material comprises only the repeating units of the type described above.

[0049] The general structural formula of the aryl group is at least one of the following general formulas (1), (2), (3), and (4). [ka] [ka] [ka] [ka]

[0050] In general formulas (1) to (4), R and R' are, respectively, an oxygen atom, a sulfur atom, a -(OR2)tO- group, and a fluorene group: [ka] , Selected from alkylidene groups having 1 to 10 carbon atoms, or arylene groups having 1 to 30 carbon atoms; m, k, m', and k' are integers between 0 and 5, inclusive.

[0051] In general formulas (1) to (4), (R1)d indicates that d R1 substituents are bonded to the corresponding benzene ring in the general formula, and the d R1 substituents bonded to the benzene ring are either the same or different; (R2)d' indicates that d' R2 substituents are bonded to the corresponding benzene ring in the general formula, and the d' R2 substituents bonded to the benzene ring are either the same or different; (R3)e indicates that e R3 substituents are bonded to the corresponding benzene ring in the general formula, and the e R3 substituents bonded to the benzene ring are either the same or different. This indicates that; (R4)e' indicates that e' R4 substituents are bonded to the corresponding benzene ring in the general formula, and the e' R4 substituents bonded to the benzene ring are either the same or different; (R5)f indicates that f R5 substituents are bonded to the corresponding benzene ring in the general formula, and the f R5 substituents bonded to the benzene ring are either the same or different; (R6)f' indicates that f' R6 substituents are bonded to the corresponding benzene ring in the general formula, and the f' R6 substituents bonded to the benzene ring are either the same or different. R1, R2, R3, R4, R5, and R6 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, or an atom or atomic group that can substitute for the above groups, and d, e, f, d', e', and f' are each integers between 0 and 4.

[0052] In the -(OR2)tO- group, R2 is an alkylidene group having 1 to 4 carbon atoms, and t is an integer between 1 and 10.

[0053] In the fluorene group, (R7)g indicates that g R7 substituents are bonded to the corresponding benzene ring in the general formula, and the g R7 substituents bonded to the benzene ring are either the same or different; (R8)g' indicates that g' R8 substituents are bonded to the corresponding benzene ring in the general formula, and the g' R8 substituents bonded to the benzene ring are either the same or different; (R9)h indicates that h R9 substituents are bonded to the corresponding benzene ring in the general formula, and the h R9 substituents bonded to the benzene ring are either the same or different; (R10)h' indicates that h' R10 substituents are bonded to the corresponding benzene ring in the general formula, and the h' R10 substituents bonded to the benzene ring are either the same or different. R7, R8, R9, and R10 are selected from hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, cyano groups, amino groups, thiol groups, or atoms or atomic groups that can substitute for the above groups. s and s' are integers between 0 and 5, respectively. g, h, g', and h' are integers between 0 and 4, respectively.

[0054] When the general structural formula of the aryl group is the general formula (1), R is the fluorene group, k=k'=0, and the general structural formula of the aryl group is as follows. [ka]

[0055] When the general structural formula of the aryl group is general formula (3) and m=m'=0, the general structural formula of the aryl group is as follows: [ka]

[0056] The functional group further comprises an alicyclic group. The alicyclic group is a group containing a bridged ring structure, a group containing a helical ring structure, or a ring structure containing a heteroatom. The structural formula of the alicyclic group is one of the following, and the chemical bonding sites are the same atom or different atoms within the ring structure. [ka] (In the formula, m21 and m22 are integers between 0 and 5, and m23 is an integer between 1 and 5, respectively.)

[0057] During the synthesis of polymer materials, monomers can be polymerized and bonded via one of the following: CO, CS, or CC bonds. CO, CS, and CC bonds have high thermal stability and low polarity. To achieve extremely low water absorption, the main chain of the polymer material does not need to contain structures such as C=X and C≡X (where X is a heteroatom), which have high water absorption, nor does it contain any of the unstable structures such as XX and XCX (where X is a heteroatom).

[0058] In one embodiment, the structural formula of the repeating unit is as follows: [ka] (In the formula, A is an aryl group, RA1 and RA2 each represent a flexible chain segment, and RA3 and RA4 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group.)

[0059] In other embodiments, the structural formula of the repeating unit is one or more of the following: [ka] [ka] [ka] [ka] (In the formula, RA9, RA10, RA11, RA1', RA2', RB1, and RB2 each represent a flexible chain segment, A and A' each represent an aryl group, and B is an alicyclic group.)

[0060] In yet another embodiment, the structural formula of the repeating unit is as follows: [ka] (A and A' represent aryl groups, respectively, and -O- can represent a flexible chain segment.)

[0061] The flexible chain segment is selected from at least one of a polyethylene glycol chain segment having a degree of polymerization of less than 10, a poly(ethanedithiol) chain segment having a degree of polymerization of less than 10, and a substituted or unsubstituted alkylidene group chain segment having fewer than 20 carbon atoms.

[0062] In one embodiment, the structural formula of the flexible chain segment may be as follows. [ka] (In the formula, X and Y represent an O atom or an S atom, respectively, R11 represents an alkylidene group having 1 to 4 carbon atoms, and i is an integer between 0 and 10. In particular, when i=0, the following applies: [ka] (This is a chemical bond.)

[0063] The structural formula of the aforementioned flexible chain segment can be as follows: [ka] (In the formula, X and Y represent an O atom or an S atom, respectively; R11 represents an alkylidene group having 1 to 4 carbon atoms; R12 represents an alkylidene group having 1 to 10 carbon atoms; and i is an integer between 0 and 10. In particular, when i=0, the following applies: [ka] (This is a chemical bond.)

[0064] The structural formula of the aforementioned flexible chain segment can be as follows: [ka] [ka] (In the formula, X and Y represent an O atom or an S atom, respectively; R11 represents an alkylidene group having 1 to 4 carbon atoms; R12 and R13 represent an alkylidene group having 1 to 10 carbon atoms; and i is an integer between 0 and 10. In particular, when i=0, the following applies: [ka] (This is a chemical bond.)

[0065] This application further provides compositions comprising the polymer material described above. In practice, the composition may further comprise at least one of a filler, a dye, an antioxidant, a light stabilizer, a plasticizer, a flame retardant, an antistatic agent, and a mold release agent.

[0066] This application further provides optical components comprising the polymer material or composition described above. In the implementation of this application, the optical component may be an optical lens, an optical film, a light guide plate, an optical disc, etc.

[0067] This application further provides a device including the optical components described above. For example, the device may be a camera module using an optical lens, various optical devices using an optical film, or a backlight module using a light guide plate.

[0068] This application further provides methods for preparing the polymer material described above. A total of three preparation methods: ADMET( acyclic These include diene metathesis polymerization, thiol-enclyck reactions, and nucleophilic substitution reactions.

[0069] The first method for preparing polymer materials (ADMET polymerization) is: To prepare a diene monomer comprising a functional group containing an aryl group and a flexible chain segment bonded to the functional group; The process involves causing a metathesis reaction of the diene monomer to obtain an intermediate product containing a carbon-carbon double bond, then causing a hydrogenation reaction of the intermediate product to remove the carbon-carbon double bond and produce a polymer material. Includes.

[0070] The general structural formula of the aforementioned diene monomer is as follows: [ka] (In the formula, A is an aryl group, RA1 and RA2 represent flexible chain segments, RA3 and RA4 are selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group, respectively, and RA5, RA6, RA7, and RA8 are selected from a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkane having fewer than 5 carbon atoms, respectively.)

[0071] The diene monomer may further include a diene monomer whose functional group is an alicyclic group. In this application, polymer materials can also be obtained by copolymerizing a diene monomer containing a functional group (aryl group and alicyclic group) with another diene monomer or a cycloolefin polymer.

[0072] The ADMET polymerization reaction process can be divided into two steps. In the first step, the diene monomer undergoes a metathesis reaction under the action of a catalyst, as follows: [ka] Remove the following intermediate products: [ka] It generates [the substance]. The specific reaction equation is as follows: [ka]

[0073] The first step of the polymerization reaction takes place in an inert gas atmosphere, which can be nitrogen, argon, etc. The polymerization reaction system mainly comprises a diene monomer, a catalyst, a solvent, and a stopper. The catalyst can be one or more of the following: a W compound, a Ru compound, a Mo compound, a Re compound, a V compound, etc. The Ru compound can be a Grubbs catalyst, for example, the first-generation catalyst benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, or the second-generation catalyst tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-dihydroimidazole-2-ylidene][(phenylthio)methylene]ruthenium(II) dichloride. The Mo compound can be a Schrock catalyst, MoO3, MoCl5, etc. The W compound can be WCl6, WOCl4, W(CO)6, etc. The Re compound can be ReCl5, Re2O7, ReOCl3, etc. The V compound can be VCl4, VOCl3, V2O5, etc. The solvent can be, for example, a branched alkane, a cycloalkane, an aromatic compound (e.g., benzene or toluene), HaloalcanThe stopper can be a common organic solvent capable of dissolving one or more reactants and the resulting polymer, such as dichloromethane, chlorobutane, or bromohexane, saturated carboxylates (e.g., ethyl acetate, n-butyl acetate, isobutyl acetate, or methyl propionate), or ethers (e.g., dibutyl ether, tetrahydrofuran, or dimethoxyethane). In some implementations of this application, the solvent is an alicyclic hydrocarbon such as cyclohexane or an aromatic compound such as toluene, capable of dissolving the diene monomer, catalyst, and resulting polymer, or a combination of several types of solvents may be used. The stopper primarily has two functions: specifically, selectively removing transition metals from the ends of the polymer chain segments to stop the reaction; and introducing specific functional groups to the ends of the chain segments. For example, the stopper selected in this application may be a vinyl ether compound.

[0074] In the implementation of this application, the mass concentration of the diene monomer in the polymerization reaction system can be 2% to 20% by weight, and moreover, 5% to 15% by weight. The ratio of the total molar amount of diene monomer to the molar amount of catalyst can be greater than 500 / 1, and moreover, greater than 1000 / 1. The polymerization reaction temperature can be 25°C to 180°C, and moreover, 40°C to 100°C. The reaction time can be set according to the actual requirements, specifically 0.1 hours to 10 hours, moreover, 0.1 hours to 5 hours, and moreover, 0.1 hours to 3 hours.

[0075] In the implementation of this application, known methods can also be used in the second step, specifically, the hydrogenation step of the unsaturated polymer obtained by the polymerization reaction. In the implementation of this application, the hydrogenation rate of the unsaturated polymer is greater than 80%. In some implementations of this application, the hydrogenation rate is greater than 90%, even greater than 95%, and even greater than 99%. The specific reaction equation is as follows. [ka]

[0076] The polymer material obtained by the first preparation method contains the following repeating units. [ka] The repeating unit comprises a functional group A and flexible chain segments RA1 and RA2 bonded to the functional group A. R1 and R2 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group.

[0077] The second method for preparing the polymer material, namely the thiol-enclyc reaction, To prepare a diene monomer comprising a functional group containing an aryl group and a flexible chain segment bonded to the functional group; To prepare the dithiol monomer; An addition reaction occurs between the thiol group of the dithiol monomer and the carbon-carbon double bond of the diene monomer to produce a polymer material. Includes.

[0078] The preceding diene monomer may further include diene monomers whose functional group is an alicyclic group.

[0079] The specific reaction equation for the second preparation method is as follows: [ka] (In the formula, RT and RT' represent an aryl group, an alicyclic group, or a flexible chain segment; RA3 and RA4 are selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group, respectively; and RA5, RA6, RA7, and RA8 are selected from a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkane having fewer than 5 carbon atoms, respectively.)

[0080] The polymerization reaction in the second preparation method takes place in an inert gas atmosphere, the inert gas can be nitrogen, argon, etc. The solvent can be, for example, branched alkanes, cycloalkanes, aromatic compounds (e.g., benzene or toluene), Haloalcan The solvent can be a common organic solvent capable of dissolving one or more reactants and the resulting polymer, such as (e.g., dichloromethane, chlorobutane, or bromohexane), saturated carboxylates (e.g., ethyl acetate, n-butyl acetate, isobutyl acetate, or methyl propionate), or ethers (e.g., dibutyl ether, tetrahydrofuran, or dimethoxyethane). The polymerization reaction must occur in the presence of a radical initiator, which can be initiated by several methods, such as heating, illumination, or ultrasound. The radical initiator can be selected from azo initiators such as 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethyl)valeronitrile, or dimethyl-2,2'-azobis(2-methyl propionate), organic peroxide compounds such as benzoyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, or dicumyl peroxide, or other radical initiators. During the polymerization reaction, the molar ratio of diene monomer to dithiol monomer is in the range of 0.90:1 to 1.10:1, preferably in the range of 0.95:1 to 1.05:1, and more preferably in the range of 0.99:1 to 1.01:1. The reaction time can be set according to the actual requirements, specifically from 0.1 hours to 10 hours, further from 0.1 hours to 5 hours, and further from 0.1 hours to 3 hours.

[0081] In the implementation of this application, it is necessary to add an endcapping agent after the polymerization reaction to convert the active end groups of the polymer into inactive end groups. Based on various supply ratios, the endcapping agent can be selected from monoolefin compounds such as styrene, methyl methacrylate, butyl methacrylate, or butyl acrylate, or from monothiol compounds such as 1-dodecanethiol, benzyl mercaptan, or 2-phenylethanethiol.

[0082] The general structural formula of the aforementioned diene monomer is as follows: [ka] (In the formula, A is an aryl group, RA1 and RA2 represent flexible chain segments, RA3 and RA4 are selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group, respectively, and RA5, RA6, RA7, and RA8 are selected from a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkane having fewer than 5 carbon atoms, respectively.)

[0083] The dithiol monomer is as follows: [ka] [ka] [ka] It comprises at least one substituted or unsubstituted (cyclic) aliphatic dithiol. (In the formula, A' is an aryl group, B is an alicyclic group, and RA1', RA2', RB1, and RB2 each represent a flexible chain segment.)

[0084] The polymer material obtained by the second preparation method contains one or more of the following repeating units. [ka] [ka] [ka] [ka] (In the formula, RA9, RA10, RA11, RA1', RA2', RB1, and RB2 represent flexible chain segments, A and A' represent aryl groups, and B is an alicyclic group.)

[0085] A third method for preparing polymer materials (nucleophilic substitution reaction) is, To prepare a monomer comprising a functional group containing an aryl group and a phenol group bonded to the functional group; To induce a nucleophilic substitution reaction between the phenol group of the monomer and the halogenated aromatic compound, thereby producing a polymer material, Includes.

[0086] The structural formula of the above monomer is as follows: [ka] (In the formula, A is an aryl group.)

[0087] The structural formula of the aforementioned halogenated aromatic compound is as follows: [ka] (In the formula, A' is an aryl group, and X1 and X2 are halogen atoms, respectively.)

[0088] In the polymerization reaction system of the third preparation method, the molar ratio of diphenol monomer to dihalogenated monomer is in the range of 0.90:1 to 1.10:1, preferably in the range of 0.95:1 to 1.05:1, and more preferably in the range of 0.99:1 to 1.01:1. An alkaline reagent is required to be used in the polymerization reaction. The alkaline reagent can be one or more of the following: sodium hydroxide, potassium hydroxide, potassium carbonate, lithium carbonate, sodium bicarbonate, cesium carbonate, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, sodium borohydride, sodium benzoate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. The solvent can be a general polar organic solvent with a high boiling point that can dissolve all reactants and the resulting polymer, such as N,N-dimethylformamide, N,N-dimethylacetamide, 1,4-dioxane, and dimethyl sulfoxide. The reaction temperature is 60°C to 150°C, and the reaction time is 20 minutes to 10 hours.

[0089] The specific reaction equation is as follows: [ka]

[0090] The polymer material obtained by the third preparation method contains repeating units linked by CO bonds, the structural formula of the repeating units is as follows. [ka] (In the formula, A and A' each represent an aryl group.)

[0091] The polymer material obtained by any one of the first to third preparation methods has a refractive index of 1.56 or higher and a water absorption rate of 0.1% by weight or less. Furthermore, the performance of the polymer material further includes having a glass transition temperature of 120°C or higher and / or an Abbe number of 17 or higher.

[0092] The technical solutions in the embodiments of this application will be further described below with specific examples.

[0093] Example 1 Synthesis of Fu-C5ene monomer: 4,4'-(9-fluorenylidene)diphenol (CAS: 3236-71-3, 1 equivalent, 0.1 mol), 5-bromo-1-pentene (CAS: 1119-51-3, 3 equivalents, 0.3 mol), and potassium carbonate (3 equivalents, 0.3 mol) were dissolved in 200 mL of acetone. The air in the reaction system was replaced with nitrogen. The reaction was carried out overnight at 80°C. Pure Fu-C5ene was obtained by separation based on column chromatography. The yield was 92%. The specific reaction equation is as follows: [ka]

[0094] Figure 1 shows the hydrogen-1 nuclear magnetic resonance (1H NMR) spectrum of the monomer product. Characteristic peaks 1 and 2 in Figure 1 correspond to the hydrogen atoms at positions 1 and 2 in the reactive Fu-C5ene monomer.

[0095] ADMET polymerization reaction of Fu-C5ene: 200 mL of Fu-C5ene (0.05 mol) monomer was dissolved in toluene, and Grubbs catalyst (0.5 mmol) was added to initiate the reaction. The solution was placed in a liquid nitrogen atmosphere. Heating and reflow were performed at 50°C for 4 hours, and excess ethyl vinyl ether (reaction stopper) was added. The mixture was stirred further at room temperature for 20 minutes. The reaction solution was reprecipitated in methanol, the precipitate was washed three times with methanol, and then dried overnight in a vacuum drying oven to obtain a polymer with a main chain containing unsaturated double bonds.

[0096] Hydrogenation: A polymer containing unsaturated double bonds was added to a 250 mL round-bottom flask, and a catalyst (Pd-B / γ-Al2O3 amorphous mixture, 1 wt%) was added. The air in the reaction system was replaced with nitrogen, then hydrogen was injected, and the hydrogen pressure was maintained at 1.5 MPa. The reaction system was vigorously stirred at 110 °C for 6 hours and separated by vacuum distillation. The mixed solution obtained from the reaction was reprecipitation in methanol, filtered, and a white solid was obtained. The white solid was washed with deionized water, dissolved in warm toluene, and then reprecipitation in toluene. The above filtration, dissolution, and reprecipitation steps were repeated twice. The white solid obtained by filtration was dried in a vacuum oven for 24 hours, and the resulting solid was a saturated polymer.

[0097] The reaction equations for polymerization and hydrogenation are as follows: [ka]

[0098] The hydrogen-1 nuclear magnetic resonance spectra of polymers containing unsaturated double bonds are shown in the upper part of Figure 2. Characteristic peaks 1 and 2 of the unsaturated double bond appeared at approximately the position indicated by 5.13. The hydrogen-1 nuclear magnetic resonance spectra of the final polymer obtained by hydrogenation are shown in the lower part of Figure 2. In Figure 2, two characteristic hydrogen peaks appeared at the position of the unsaturated double bond before hydrogenation. These two characteristic hydrogen peaks disappeared after hydrogenation, indicating that a double bond had been added.

[0099] Example 2 Synthesis of an aryl group-containing diene monomer (Fu-C3ene): 4,4'-(9-fluorenylidene)diphenol (CAS: 3236-71-3, 1 equivalent, 0.1 mol), allyl bromide (CAS: 106-95-6, 3 equivalents, 0.3 mol), and potassium carbonate (3 equivalents, 0.3 mol) were dissolved in 200 mL of acetone. The air in the reaction system was replaced with nitrogen. The reaction occurred at 80°C. Pure Fu-C3ene was obtained by separation based on column chromatography. The yield was 95%. The specific reaction equation is as follows: [ka]

[0100] The 1H NMR spectrum of Fu-C3ene is shown in Figure 3.

[0101] Synthesis of Fu-ESH monomer: 4,4'-(9-fluorenylidene)diphenol (CAS: 3236-71-3, 1 equivalent, 0.1 mol), ethylene sulfide (CAS: 420-12-2, 2.2 equivalents, 0.22 mol), and potassium carbonate (1.2 equivalents, 0.12 mol) were dissolved in 200 mL of acetone. The air in the reaction system was replaced with nitrogen. The reaction proceeded at 60°C for 4 hours. Pure Fu-ESH was obtained by separation based on column chromatography. The yield was 90%. The specific reaction equation was as follows: [ka]

[0102] Polymerization of diene monomer (Fu-C3ene) and Fu-ESH monomer: Fu-C3ene (1 equivalent, 0.1 mol), Fu-ESH (1.02 equivalents, 0.102 mol), and 2,2'-azobis(2-methylpropionitrile) (AIBN, 0.05 equivalents, 0.005 mol, as initiator) were dissolved in 300 mL of toluene. The air in the reaction system was replaced with nitrogen. The reaction proceeded at 60°C for 8 hours. Then, styrene (0.1 equivalents, 0.01 mol) was added and the mixture was stirred for a further 2 hours. The function of styrene was as follows. Due to excess thiols, styrene was added for end-capping of the polymer to improve its stability. The polymer was then reprecipitation in toluene, and the precipitate was washed three times with methanol. The white solid obtained by filtration was dried in a vacuum oven for 24 hours. The specific reaction equation was as follows. [ka]

[0103] Example 3 Synthesis of isosorbide-ene monomer: Isosorbide dinitrate (CAS: 87-33-2, 1 equivalent, 15 mmol) and tetrabutylammonium bromide (TBABr, 0.9 mmol) were placed in a round-bottom flask and dissolved in 50% KOH aqueous solution (90 mmol), and stirred for 15 minutes. Allyl bromide (6 equivalents, 90 mmol) was gradually added, and the mixture was stirred at 100°C for 7 hours. After the reaction was complete, the solution was cooled to room temperature. The organic layer was washed three times with dichloromethane and brine solution, and water was removed from the organic layer with magnesium. Sulfur trioxide was added, and then the mixture was filtered. Separation and production by column chromatography yielded a yellow oily isosorbide-ene solution. The yield was 94%. The specific reaction equation was as follows: [ka]

[0104] ADMET polymerization of isosorbide-ene and Fu-C5ene: Fu-C5ene (0.025 mol) monomer and isosorbide-ene (0.025 mol) were dissolved in 200 mL of toluene, and Grubbs catalyst (0.5 mmol) was added to initiate the reaction. The solution was placed in a liquid nitrogen atmosphere. Heating and reflow were performed at 50°C for 4 hours, and excess ethyl vinyl ether was added. The mixture was stirred further at room temperature for 20 minutes. The reaction solution was reprecipitated in methanol, the precipitate was washed three times with methanol, and then dried overnight in a vacuum drying oven to obtain a polymer with an unsaturated double bond in the main chain. The specific reaction equation was as follows: [ka]

[0105] Hydrogenation: A polymer containing unsaturated double bonds was added to a 250 mL round-bottom flask, and a catalyst (Pd-B / γ-Al2O3 amorphous mixture, 1 wt%) was added. The air in the reaction system was replaced with nitrogen, then hydrogen was injected, and the hydrogen pressure was maintained at 1.5 MPa. The reaction system was vigorously stirred at 110 °C for 6 hours and separated by vacuum distillation. The mixed solution obtained from the reaction was reprecipitation in methanol, filtered, and a white solid was obtained. The white solid was washed with deionized water, dissolved in warm toluene, and then reprecipitation in toluene. The above filtration, dissolution, and reprecipitation steps were repeated twice. The white solid obtained by filtration was dried in a vacuum oven for 24 hours, and the resulting solid was a saturated polymer.

[0106] Example 4 0.8 mol of 9,9-bis(4-hydroxyphenyl)fluorene (CAS: 3236-71-3), 0.4 mol of 4-[(4-hydroxyphenoxy)methoxy]phenol (CAS: 86072-79-9), 1.2 mol of 9,9-bis(4-fluorophenyl)fluorene (CAS: 117766-42-4), and 10 L of N,N-dimethylacetamide (DMAc, solvent) were added to the reactor. The temperature was raised to 120°C, and 0.05 mol of potassium carbonate was added while stirring. The reaction occurred in 3.5 hours. The temperature was then rapidly reduced to room temperature. Precipitation and washing were then performed to obtain the polyaryl ether resin. The specific reaction equation was as follows. [ka]

[0107] In the product, x:y=2:1.

[0108] Example 5 0.96 mol of 9,9-bis(4-hydroxyphenyl)fluorene (CAS: 3236-71-3), 0.24 mol of 4-[(4-hydroxyphenoxy)methoxy]phenol (CAS: 86072-79-9), 1.2 mol of 9,9-bis(4-fluorophenyl)fluorene (CAS: 117766-42-4), and 10 L of DMAc were added to the reactor. The temperature was raised to 120°C. 0.05 mol of potassium carbonate was added while stirring. The reaction occurred in 5 hours. The temperature was then rapidly reduced to room temperature. Precipitation and washing were then performed to obtain a polyaryl ether resin. The specific reaction equation was as follows. [ka]

[0109] In the product, x:y=4:1.

[0110] Comparative Example Synthesis of polycarbonate: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (CAS: 117344-32-8 (0.1 mol)), 0.2 mol of diphenyl carbonate, and 0.015 mol of sodium bicarbonate were added to a flask. The flask was placed in a 300 ml four-necked flask equipped with a stirrer and distillation apparatus, and heated to 180°C at 760 mmHg under a nitrogen atmosphere. After heating for 10 minutes, complete dissolution of the starting materials was confirmed. The mixture was then stirred under the same conditions for 110 minutes. Subsequently, the vacuum level was adjusted to 200 mmHg, and the temperature was increased to 200°C at a rate of 60°C / hour, confirming the start of distillation of phenol by-products. The temperature was then maintained for 20 minutes to allow the reaction to proceed. Subsequently, the temperature was increased to 230°C at a rate of 75°C / hour. After the temperature increase was complete, the temperature was maintained, and after 10 minutes, within 1 hour, the vacuum level was set to less than 1 mmHg. Subsequently, the temperature was increased to 240°C at a rate of 60°C / hour, and the reaction occurred in 30 minutes. After the reaction was complete, nitrogen was injected and the pressure was reduced to atmospheric pressure to obtain the polycarbonate resin material.

[0111] The molecular weight, molecular weight distribution, glass transition temperature (Tg), refractive index, Abbe number, and water absorption rate of the polymers in Examples 1-5 and the polycarbonate in the comparative examples were tested. The specific test results are shown in the table below.

[0112] The test methods were as follows: Refractive index was tested in accordance with ASTM D542 standard specified by the American Society for Testing and Materials. Transmittance and temperature were tested in accordance with ASTM D1003 standard specified by the American Society for Testing and Materials. Water absorption was tested in accordance with ASTM D590 standard specified by the American Society for Testing and Materials. [Table 1]

[0113] This table shows that, compared to the comparative example polycarbonate, the polymer materials of Examples 1-5 achieve a balance of material properties such as light transmittance, refractive index, and heat resistance while ensuring extremely low water absorption. This expands the range of applications for the materials.

[0114] It should be noted that the above description is merely a specific implementation of the present application and is not intended to limit the scope of protection of the present application. Any modification or substitution that is readily understandable to a person skilled in the art within the scope of the technical scope disclosed in the present application shall be included in the scope of protection of the present application. Where there is no conflict, the implementations and features of the present application may be combined with each other. Therefore, the scope of protection of the present application should be subject to the scope of protection of the claims.

Claims

1. A polymer material containing repeating units, The aforementioned repeating unit has the following general structural formula: 【Chemistry 1】 (In the formula, m and m' are integers between 1 and 5, respectively; R １ , R ２ , R ３ and R ４ Each of these is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R ７ , R ８ , R ９ , and R １０ Each of the following is selected from a hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, hydroxyl group, cyano group, amino group, or thiol group; s and s' are integers between 0 and 5, and g, h, g', and h' are integers between 0 and 4. It comprises a functional group represented by and a flexible chain segment bonded to the functional group; The polymer material is characterized by having a refractive index of 1.56 to 1.63 and a water absorption rate of 0.1% or less.

2. The polymer material according to claim 1, wherein the flexible chain segment comprises at least one of an alkyl chain segment, a polyethylene glycol chain segment, and a poly(ethanedithiol) chain segment.

3. The polymer material according to claim 1 or 2, wherein the functional group further comprises an alicyclic group.

4. The polymer material according to claim 3, wherein the alicyclic group is a group containing a bridged ring structure, a group containing a helical ring structure, or a group containing a ring structure containing a heteroatom.

5. The polymer material according to claim 3, wherein the structural formula of the alicyclic group is at least one of the following. 【Chemistry 2】 (where m ２１ and m ２２ are each an integer of 0 or more and 5 or less, and m ２３ is an integer of 1 or more and 10 or less)

6. The structural formula of the repeating unit is as follows: 【Transformation 3】 (In the formula, A is the following general structural formula: 【Chemistry 4】 (In the formula, m and m' are integers between 1 and 5, respectively; R1, R2, R3, and R4 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R7, R8, R9, and R10 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group, and s and s' are each integers between 0 and 5, and g, h, g', and h' are each integers between 0 and 4. R Ａ１ and R Ａ２ These each represent a flexible chain segment, and R Ａ３ and R Ａ４ (Each of these is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an ester group, or a cyano group.) The polymer material according to claim 1 or 2, as described above.

7. The structural formula of the repeating unit is as follows: 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 (In the formula, R Ａ９ , R Ａ１０ , R Ａ１１、 R Ａ１ ', R Ａ２ ', R Ｂ１ , and R Ｂ２ Each of these represents a flexible chain segment, and A and A' are represented by the following general structural formula: 【Chemistry 9】 (In the formula, m and m' are integers between 1 and 5, respectively; R1, R2, R3, and R4 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R7, R8, R9, and R10 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; s and s' are each integers between 0 and 5, and g, h, g', and h' are each integers between 0 and 4. This indicates that B is an alicyclic group. A polymer material according to any one of claims 1 to 5, which is one or more selected from the group consisting of the following.

8. The structural formula of the repeating unit is as follows: 【Chemistry 10】 (In the formula, A and A' are the following general structural formulas: 【Chemistry 11】 (In the formula, m and m' are integers between 1 and 5, respectively; R1, R2, R3, and R4 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R7, R8, R9, and R10 are each selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; s and s' are each integers between 0 and 5, and g, h, g', and h' are each integers between 0 and 4. (This indicates that -O- represents the flexible chain segment.) The polymer material according to claim 1 or 2, as described above.

9. The polymer material according to any one of claims 1 to 7, wherein the flexible chain segment is selected from at least one of a polyethylene glycol chain segment having a degree of polymerization of less than 10, a poly(ethanedithiol) chain segment having a degree of polymerization of less than 10, and a substituted or unsubstituted alkylidene group chain segment having fewer than 20 carbon atoms.

10. A composition characterized by comprising the polymer material described in any one of claims 1 to 9.

11. The composition according to claim 10, wherein the composition further comprises at least one of a filler, a dye, an antioxidant, a light stabilizer, a plasticizer, a flame retardant, an antistatic agent, and a mold release agent.

12. An optical component comprising a polymer material according to any one of claims 1 to 9 or a composition according to claim 10 or 11.

13. The optical component according to claim 12, wherein the optical component is an optical lens, an optical film, a light guide plate, or an optical disc.

14. A device comprising the optical component described in claim 12 or 13.

15. The following general structural formula: 【Chemistry 12】 (In the formula, m and m' are integers between 1 and 5, respectively; R １ , R ２ , R ３ and R ４ Each of these is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R ７ , R ８ , R ９ , and R １０ Each of the following is selected from a hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, hydroxyl group, cyano group, amino group, or thiol group; s and s' are integers between 0 and 5, and g, h, g', and h' are integers between 0 and 4. To prepare a diene monomer comprising a functional group represented by and a flexible chain segment bonded to the functional group; The process involves causing a metathesis reaction of the diene monomer to obtain an intermediate product containing a carbon-carbon double bond, and then causing a hydrogenation reaction of the intermediate product to produce a polymer material comprising repeating units including the functional group and the flexible chain segment bonded to the functional group. A method for preparing a polymer material according to any one of claims 1 to 9, including the method described in any one of claims 1 to 9.

16. below 【Chemistry 13】 (In the formula, m and m' are integers between 1 and 5, respectively; R １ , R ２ , R ３ and R ４ Each of these is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R ７ , R ８ , R ９ , and R １０ Each of the following is selected from a hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, hydroxyl group, cyano group, amino group, or thiol group; s and s' are integers between 0 and 5, and g, h, g', and h' are integers between 0 and 4. To prepare a diene monomer comprising a functional group represented by and a flexible chain segment bonded to the functional group; To prepare the dithiol monomer; An addition reaction occurs between the thiol group of the dithiol monomer and the carbon-carbon double bond of the diene monomer to produce a polymer material comprising a repeating unit including the functional group and the flexible chain segment bonded to the functional group. A method for preparing a polymer material according to any one of claims 1 to 9, including the method described in any one of claims 1 to 9.

17. below 【Chemistry 14】 (In the formula, m and m' are integers between 1 and 5, respectively; R １ , R ２ , R ３ and R ４ Each of these is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a cyano group, an amino group, or a thiol group; d, e, d', and e' are each integers between 0 and 4, inclusive; and, In the fluorene group, R ７ , R ８ , R ９ , and R １０ Each of the following is selected from a hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, hydroxyl group, cyano group, amino group, or thiol group; s and s' are integers between 0 and 5, and g, h, g', and h' are integers between 0 and 4. To prepare a monomer comprising a functional group represented by and a phenol group bonded to the functional group; To induce a nucleophilic substitution reaction between the phenol group of the monomer and the halogenated aromatic compound, thereby producing a polymer material comprising repeating units including the functional group and a flexible chain segment bonded to the functional group, A method for preparing a polymer material according to any one of claims 1 to 9, including the method described in any one of claims 1 to 9.

Images