Optical polymer and preparation method thereof, optical polymer masterbatch, and optical element

Abstract

The present application relates to the technical field of optical materials, and provides an optical polymer and its preparation method, an optical polymer masterbatch, and an optical element. The optical polymer is formed by polymerizing monomers as shown in the following formula 1: #imgabs0# wherein g and h are selected from integers of 1 to 5, and at least one of g and h is 1; R1 is a cyclic hydrocarbon group or an aromatic structure; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; X is an oxygen atom or a sulfur atom; a, b, m, n, and p are each independently selected from 0, 1, or 2, and when X is an oxygen atom, a and b are not simultaneously 0; and o is 0 or 1. The optical polymer provided in the present application has the advantages of high refractive index and high Abbe number while maintaining good heat resistance and low volume shrinkage.

Description

Technical Field

[0001] The present application belongs to the technical field of optical materials, and in particular relates to an optical polymer and a preparation method thereof, an optical polymer masterbatch, and an optical element. Background Art

[0002] Polymer optical materials are characterized by light weight, impact resistance, easy processing and molding, dyeability, and excellent optical properties. They are gradually replacing inorganic optical materials and are widely used in precision lenses, optical discs, optical fibers, building materials, resin lenses, and other materials. Refractive index and Abbe number are important indicators that reflect the basic performance of optical lenses. Among them, the refractive index determines the thickness and curvature of the optical lens, and the Abbe number determines the imaging quality of the optical lens. However, the refractive index and Abbe number are inversely proportional to a certain extent. Specifically, in optical lenses, the higher the refractive index of the optical material, the lower the Abbe number. Currently, the research and application of optical materials are mainly focused on PC materials with high refractive index and low Abbe number, as well as COC materials and COP materials with low refractive index and high Abbe number.

[0003] To obtain optical materials with both a high refractive index and a high Abbe number, it is necessary to introduce functional groups with both a high refractive index and a high Abbe number into the polymer structure. The S element possesses both a high refractive index and a high Abbe number, and it also has a wide range of functional group selectivity. Therefore, introducing the S element into the polymer structure has become the most effective way to achieve high refractive index and high Abbe number.

[0004] The document Macromolecules 2012, 45, 3402-3408 discloses a method for preparing a series of thermoplastic polymers containing the element S using a Michael addition reaction. The refractive index of the polymers produced by this method increases with increasing S content, and the Abbe number level can be maintained above 35, enabling the preparation of high-refractive-index, high-Abbe-number optical materials (hereinafter referred to as "high-refractive-index, high-Abbe-number materials"). However, because the element S has a large atomic radius, the introduction of S into the polymer backbone greatly increases the flexibility of the polymer chain, making it easier for the material to twist. The resulting thermoplastic polymers containing S have poor thermal properties, which affects their practical applicability. Japanese patent JP2001031675A provides a thermosetting polymer with a cross-linked network structure prepared by copolymerizing a polyfunctional thiol and a difunctional isocyanate monomer. Compared to thermoplastic resins, thermosetting resins have molecular chains directly connected by chemical bonds, which limits chain twisting and thus improves the heat resistance of the material. In Chinese patent CN101495531B, cyclic sulfide ring-opening polymerization is used to prepare thermosetting resin materials. Due to the high sulfur content of the polymerized monomer, the obtained polymer material has a very high refractive index and the Abbe number is also maintained at a high level. In addition, since the cross-linking density can be maintained, the heat resistance of the obtained polymer is better. However, the above-mentioned thermosetting resin materials are all solid polymers with high cross-linking density directly generated using liquid monomers under the action of a catalyst. The density difference between the monomer and the resin material is relatively large, so the volume shrinkage rate during the curing process is relatively large, which is relatively limited for applications in fields with high dimensional accuracy requirements. At the same time, new molding processes need to be developed. Moreover, due to the characteristic of isocyanate monomers containing benzene rings, the obtained isocyanates contain a large amount of benzene ring structures, which causes the Abbe number of the optical material obtained to be difficult to guarantee.

[0005] It is particularly important to obtain an optical material that has a high refractive index and a high Abbe number without reducing the material's heat resistance and increasing its volume shrinkage. Summary of the Invention

[0006] The purpose of this application is to provide an optical polymer and a preparation method thereof, an optical polymer masterbatch, and an optical element, aiming to solve the problem that the existing high-refractive index and high-Abbe material obtained using S element cannot have both good heat resistance and volume shrinkage.

[0007] To achieve the above application objectives, the technical solutions adopted in this application are as follows:

[0008] In a first aspect, the present application provides an optical polymer, wherein the optical polymer is formed by polymerizing a monomer as shown in the following formula 1:

[0009]

[0010] wherein g and h are each selected from integers of 1 to 5, and at least one of g and h is 1;

[0011] R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms;

[0012] R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br;

[0013] X is an oxygen atom or a sulfur atom, and when g is greater than or equal to 2, multiple Xs are each independently selected from an oxygen atom or a sulfur atom;

[0014] a, b, m, n, and p are each independently selected from 0, 1, or 2, and when X is an oxygen atom, a and b are not both 0;

[0015] o is 0 or 1, and when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1.

[0016] The optical polymer provided by the present application contains S elements in the polymerization monomer, which is beneficial to improving the refractive index and Abbe number of the optical polymer, thereby obtaining a high-refractive-index and high-Abbe material. On this basis, two different types of polymerizable functional groups with different activities are introduced into the polymerization monomer structure - X heterocyclopropane (X is S or O) and carbon-carbon double bond. Since the two functional groups have different activities, and the molar ratio of at least one of the two functional groups to the polymerization monomer is 1:1 (at least one of g and h is 1), the polymerization monomer can initiate two polymerization reactions of two different functional groups in succession by selecting a suitable initiator. Specifically, the first polymerization reaction of the polymerizable functional group with a molar ratio of 1:1 to the polymerization monomer is initiated, and the first polymerization reaction does not initiate the polymerization of another polymerizable functional group to obtain a thermoplastic polymer with a linear structure. At this time, since the intermolecular distance becomes smaller and the volume shrinks during the transformation of the polymerization monomer into a thermoplastic polymer, a part of the shrinkage rate is consumed in advance, and therefore, the shrinkage rate of the material after the final thermal curing can be greatly reduced. Furthermore, the remaining polymerizable functional group in the thermoplastic polymer serves as a crosslinking point for the thermoplastic polymer. After a second polymerization reaction, the thermoplastic polymer is crosslinked to form a thermosetting polymer, thereby imparting the heat resistance of a thermosetting material to the optical polymer. In summary, the optical polymer provided herein possesses the advantages of a high refractive index and a high Abbe number while maintaining excellent heat resistance and low volume shrinkage.

[0017] Because the types of X-heterocyclopropane groups and carbon-carbon double bonds in the polymerizable monomers are different, the activity of the polymerization reaction is also different. Therefore, the initiation system or catalytic system for initiating the ring-opening polymerization of the X-heterocyclopropane group is different from the initiation system or catalytic system for initiating the polymerization of the carbon-carbon double bond. On this basis, in the process of polymerizing the polymerizable monomers of the present application to form an optical polymer, by selecting an initiator that initiates a specific polymerizable functional group, the polymerization reaction of the two polymerizable functional groups can be initiated in batches without affecting each other, thereby obtaining the corresponding optical polymer.

[0018] According to the different values of g and h, the structure of the optical polymer of the present application can be divided into two situations. As the first possible implementation scenario of the optical polymer structure of the present application, the g is 1, and the optical polymer includes multiple first polymer chains, which are formed by ring-opening polymerization of the X heterocyclopropane group in the formula 1, and different first polymer chains are cross-linked through the carbon-carbon double bond polymerization in the formula 1. The formation mechanism of this implementation scenario is: the X heterocyclopropane group opens the ring under the action of the initiator to form an X alkyl group containing polymerizable sites at both ends. When g is 1, it means that one molecule of the polymerized monomer contains only one molecule of the X heterocyclopropane group. Therefore, one molecule of the polymerized monomer X heterocyclopropane group only obtains two polymerizable sites after ring opening. The polymerized monomer is sequentially polymerized through the two polymerizable sites during the first polymerization process to form a linear first polymer chain. The first polymer chain retains a complete carbon-carbon double bond structure. By initiating a second polymerization of the carbon-carbon double bond, cross-linking between different first polymer chains is achieved, thereby obtaining a network-like optical polymer. The optical polymer thus formed not only has the advantages of high refractive index and high Abbe number, but also because the thermosetting polymer is not obtained by a single polymerization reaction, but is obtained by first polymerizing the polymer monomer to form a thermoplastic polymer, and then further cross-linking the thermoplastic polymer, the obtained optical polymer has good heat resistance and can significantly reduce volume shrinkage before and after the second polymerization.

[0019] In a possible implementation of the optical polymer of the present application, the structure of the optical polymer contains a repeating unit A as shown below:

[0020]

[0021] In this embodiment, the formation mechanism of the optical polymer structure is as follows: the polymerized monomer first undergoes ring-opening polymerization via the X-heterocyclopropane group to form a linear thermoplastic polymer with a main chain consisting of -X-CH2-CH(Y)- repeating units, which helps to overcome the large volume difference between the polymerized monomer and the optical polymer, wherein Y represents a side chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p Sb (CO) o CH(R2)=C(R3)(R4); different linear polymers covalently polymerize through carbon-carbon double bonds to ultimately form cross-linked optical polymers, which helps overcome the lack of heat resistance of optical polymers. The repeating unit A is rich in sulfur atoms, resulting in optical polymers containing this repeating unit A having the advantages of a high refractive index and a high Abbe number.

[0022] As a second possible implementation scenario of the optical polymer of the present application, the h is 1, and the optical polymer includes a plurality of second polymer chains, which are formed by polymerization of the carbon-carbon double bond in the formula 1, and different second polymer chains are cross-linked by ring-opening polymerization of the X heterocyclopropane group in the formula 1. The formation mechanism of this implementation scenario is: the carbon-carbon double bond is double-bonded under the action of an initiator, and the two carbon atoms form two polymerizable sites in the form of free radicals. When h is 1, it means that a molecule of polymerized monomer contains only one molecule of carbon-carbon double bond. Therefore, a molecule of polymerized monomer contains only two polymerizable sites. During the first polymerization process, adjacent polymerized monomers are sequentially polymerized through the two polymerizable sites to form a linear first polymer chain. The first polymer chain retains a complete X heterocyclopropane structure, and by initiating the ring-opening polymerization of the X heterocyclopropane group (second polymerization), cross-linking between different first polymer chains is achieved, thereby obtaining a network-like optical polymer. The polymer thus formed not only has the advantages of high refractive index and high Abbe number, but also has good heat resistance and no significant volume shrinkage before and after polymerization.

[0023] In a possible implementation of the optical polymer of the present application, the structure of the optical polymer is as follows:

[0024]

[0025] In the repeating unit B, s is selected from an integer greater than 2, and the structure of R5 is as follows:

[0026]

[0027] In this embodiment, the formation mechanism of the optical polymer structure is as follows: the polymerized monomers first polymerize through carbon-carbon double bonds to form a linear thermoplastic polymer with a main chain consisting of -C(R2)(R6)-C(R3R4)- repeating units, which helps overcome the large volume difference between the polymerized monomers and the optical polymer. The different linear polymers then undergo ring-opening polymerization of the X heterocyclopropane groups to ultimately form a cross-linked optical polymer, which helps overcome the problem of insufficient heat resistance of the optical polymer. In -C(R2)(R6)-C(R3R4)-, R6 represents the following structural fragment:

[0028]

[0029] The repeating unit B contains abundant sulfur atoms. Therefore, the optical polymer containing the repeating unit B also has the advantages of high refractive index and high Abbe number.

[0030] R1, serving as a bridge connecting the two sulfur-containing segments, is selected from a cyclic hydrocarbon group or an aryl structure with or without heteroatoms. When R1 is selected from a cyclic hydrocarbon group or an aryl structure with heteroatoms, as a possible implementation of the optical polymer of the present application, the heteroatom is selected from a sulfur atom, a nitrogen atom, or an oxygen atom. In particular, when the heteroatom is a sulfur atom, the S content in the optical polymer increases, further facilitating the production of an optical polymer with a high refractive index and a high Abbe number.

[0031] As a possible implementation scenario for the optical polymer of the present application, the mass percentage of sulfur atoms is 20-70%, based on the total mass of the polymerized monomers being 100%. In this case, the optical polymer obtained after polymerization of the polymerized monomers has a high sulfur content, and the refractive index increases with the increase in the sulfur content, while the Abbe number level can be maintained above 35, ultimately facilitating the production of an optical polymer with a high refractive index and a high Abbe number.

[0032] As a possible implementation scenario of the optical polymer of the present application, the polymerizable monomer is selected from one of the following structures:

[0033]

[0034]

[0035]

[0036]

[0037] The polymerizable monomer shown in the above structure contains two polymerizable functional groups: the first polymerizable functional group is a cyclosulfanyl or epoxyalkyl group, and the second polymerizable functional group is a carbon-carbon double bond. Because the two polymerizable functional groups have different activities, a thermoplastic polymer can be obtained by first polymerizing one of the polymerizable functional groups, and then a thermosetting polymer (i.e., the optical polymer of the present application) can be obtained by polymerization of the other polymerizable functional group. This reduces the volume change difference between the thermosetting polymer and the polymerizable monomer, thereby reducing volume shrinkage. Furthermore, because at least one of the two polymerizable functional groups is present in one molecule of the polymerizable monomer, a linear thermoplastic polymer can be obtained when one of the polymerizable functional groups is polymerized to obtain a thermoplastic polymer. Furthermore, when the other polymerizable functional group is polymerized, the linear thermoplastic polymer is cross-linked via the polymerizable functional groups, thereby reducing the flexibility of the optical polymer molecular chain and improving the heat resistance of the optical polymer.

[0038] A second aspect of the present application provides a method for preparing an optical polymer, comprising the following steps:

[0039] A polymerizable monomer as shown in the following formula 1 is provided, wherein g and h are independently selected from integers of 1 to 5, and at least one of g and h is 1; R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; X is an oxygen atom or a sulfur atom, and when g is greater than or equal to 2, multiple Xs are each independently selected from an oxygen atom or a sulfur atom; a, b, m, n, and p are each independently selected from 0, 1, or 2, and when X is an oxygen atom, a and b are not both 0; o is 0 or 1, and when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1;

[0040]

[0041] Initiating a first polymerization reaction of the first polymerizable functional group in Formula 1 to produce a linear thermoplastic polymer, wherein the first polymerizable functional group is an X heterocyclopropane group or a carbon-carbon double bond having a functionality of 1 in the structure of Formula 1;

[0042] Initiate a second polymerization reaction of the second polymerizable functional group in the thermoplastic polymer to produce an optical polymer, wherein the second polymerizable functional group is the X heterocyclopropane group or the carbon-carbon double bond in the structure of Formula 1, and the second polymerizable functional group is different from the first polymerizable functional group.

[0043] The preparation method of the optical polymer provided in the present application uses an organic matter containing the S element as a polymerization monomer, and initiates a first polymerization reaction through a first polymerizable functional group with a functionality of 1 in the polymerization monomer to obtain a linear thermoplastic polymer; then the linear thermoplastic polymer is cross-linked through a second polymerization reaction of the first polymerizable functional group to obtain a cross-linked thermosetting polymer. By initiating the polymerization reactions of two different polymerizable groups through two polymerization reactions, the volume change difference between the thermosetting polymer and the polymerization monomer can be reduced, and the volume shrinkage rate can be reduced. At the same time, the linear thermoplastic polymer is cross-linked through the polymerization reaction between the second polymerizable functional groups, thereby reducing the flexibility of the optical polymer molecular chain and improving the heat resistance of the optical polymer. The optical polymer prepared by this method has the advantages of high refractive index and high Abbe number while being able to maintain good heat resistance and low volume shrinkage rate.

[0044] As a possible implementation scenario of the method for preparing the optical polymer of the present application, when the first polymerizable functional group or the second polymerizable functional group is the X heterocyclopropane group, the polymerization reaction adopts anionic polymerization or cationic polymerization;

[0045] When the first polymerizable functional group is the carbon-carbon double bond, the polymerization reaction adopts free radical polymerization; when the second polymerizable functional group is the carbon-carbon double bond, the polymerization reaction adopts anionic polymerization, cationic polymerization or free radical polymerization.

[0046] When the first polymerizable functional group is an X heterocyclopropane group and the second polymerizable functional group is a carbon-carbon double bond, the X heterocyclopropane group can be anionically polymerized or cationic polymerized under the action of an initiator to form a ring-opening Structure. The negatively charged sulfur in one monomer electrophilically bonds with the positively charged carbon in another monomer; the positively charged carbon then electrophilically bonds with the negatively charged sulfur in another monomer. Thus, each monomer polymerizes with two monomers via the X-heterocyclopropane group and sequentially connects to form a linear thermoplastic polymer. Furthermore, through anionic polymerization, cationic polymerization, or free radical polymerization at carbon-carbon double bonds, different thermoplastic polymers can be cross-linked to form a network-like thermosetting polymer.

[0047] When the first polymerizable functional group is a carbon-carbon double bond and the second polymerizable functional group is an X-heterocyclopropane group, the carbon-carbon double bond of one molecule can be broken by free radical polymerization to form a carbon-carbon single bond. The broken double bond in one molecule of polymerized monomer then crosslinks with the broken double bonds in two other molecules of polymerized monomer. Specifically, under the action of a free radical initiator, the carbon-carbon double bond breaks into two carbon free radicals. The two carbon free radicals in one molecule of polymerized monomer each combine with one carbon free radical in two other molecules of polymerized monomer. Thus, each molecule of polymerized monomer polymerizes with two molecules of polymerized monomer via the carbon-carbon double bond and sequentially connects to form a linear thermoplastic polymer. Furthermore, the X-heterocyclopropane group undergoes anionic or cationic polymerization to crosslink the different thermoplastic polymers to form a network-like thermosetting polymer.

[0048] As a possible implementation of the method for preparing an optical polymer of the present application, g is 1, and the first polymerization reaction is: using an anionic initiator or a cationic initiator to initiate ring-opening polymerization of the X-heterocyclopropane groups in the polymerizable monomers to produce a linear thermoplastic polymer; the second polymerization reaction is: adding an anionic initiator, a cationic initiator, or a free radical initiator to the linear thermoplastic polymer to initiate polymerization and crosslinking of the carbon-carbon double bonds in the linear thermoplastic polymer under light or heating conditions to produce a crosslinked thermosetting polymer. In this case, the functionality of the X-heterocyclopropane group is 1. Therefore, under the action of the initiator, the polymerizable monomers undergo ring-opening polymerization of the X-heterocyclopropane groups, and the carbon-carbon double bonds in the polymerizable monomers are retained, forming a linear thermoplastic polymer. Furthermore, by initiating polymerization of the carbon-carbon double bonds in the side chains of the thermoplastic polymers, different thermoplastic polymers are crosslinked to form a network-like thermosetting polymer.

[0049] As a possible implementation of the method for preparing an optical polymer of the present application, h is 1. The first polymerization reaction involves adding a free radical initiator to the polymerizable monomers to initiate crosslinking of the carbon-carbon double bonds in the polymerizable monomers under light or heat conditions, thereby producing a linear thermoplastic polymer. The second polymerization reaction involves adding an ionic initiator or a cationic initiator to the linear thermoplastic polymer to initiate ring-opening polymerization of the X-heterocyclopropane groups in the linear thermoplastic polymer, thereby producing a crosslinked thermosetting polymer. In this case, the functionality of the carbon-carbon double bond is 1. Therefore, under the action of the free radical initiator, the polymerizable monomers undergo polymerization reactions between the carbon-carbon double bonds, and the X-heterocyclopropane groups in the polymerizable monomers are retained, forming a linear thermoplastic polymer. Furthermore, by initiating ring-opening polymerization of the X-heterocyclopropane groups on the side chains of the thermoplastic polymers, different thermoplastic polymers are crosslinked to form a network-like thermosetting polymer.

[0050] As a possible implementation scenario of the preparation method of the optical polymer of the present application, the preparation method of the polymerization monomer is:

[0051] Compound 2 of the structure shown in Formula 2 and thiourea are heated to reflux in an organic solvent, and a solid product is collected after the reaction is completed; the solid product is dissolved in water, heated to a high temperature, and ammonia water is added to react to obtain compound 3 of the structure shown in Formula 3;

[0052] Compound 3 of the structure shown in Formula 3, sodium ethoxide, and tetrabutylammonium bromide were added to a reaction flask, stirred at room temperature, and then ethyl carbon-carbon double bond bromine was added. The reaction system was sealed and heated to obtain compound 4 of the structure shown in Formula 4.

[0053] Compound 4 of formula 4, epichlorohydrin, triethylamine, and THF were added to a reaction flask, magnetic stirring was started, and the temperature was raised to react to obtain compound 5 of formula 5;

[0054] Add compound 5 of formula 5, THF, and sodium hydroxide solution into a reaction flask, start magnetic stirring, and heat and keep warm to obtain compound 6 of formula 6;

[0055]

[0056]

[0057] In the above formula 2 and the above formula 5, A represents a halogen atom.

[0058] By the above method, a polymer monomer in which X is an O atom can be synthesized.

[0059] As a possible implementation scenario of the method for preparing the optical polymer of the present application, the method for preparing the polymerized monomer further includes:

[0060] Compound 6 of formula 6, thiourea, methanol, toluene and acetic acid were added to a reaction flask, and heated to obtain compound 7 of formula 7.

[0061]

[0062] By using this method, the O atoms in the oxygen-containing heterocycle can be replaced with sulfur atoms, further increasing the S content in the polymerized monomer. In particular, when the values of m, n, o, and p are large, the sulfur-containing heterocycle is beneficial for increasing the sulfur content in the polymerized monomer, thereby increasing the refractive index and Abbe number of the optical polymer, thereby obtaining high-refractive-index, high-Abbe-number optical materials.

[0063] A third aspect of the present application provides an optical polymer masterbatch, comprising a first polymer or a second polymer, wherein the first polymer and the second polymer are both formed by polymerizing a monomer as shown in Formula 1 below;

[0064] Wherein, the first polymer is a linear polymer formed by the polymerization monomer through X-heterocyclopropane ring-opening polymerization, and the second polymer is a linear polymer formed by the polymerization monomer through carbon-carbon double bond polymerization;

[0065]

[0066] In formula 1, g and h are each selected from integers of 1 to 5, and at least one of g and h is 1;

[0067] R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms;

[0068] R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br;

[0069] X is an oxygen atom or a sulfur atom, and when g is greater than or equal to 2, multiple Xs are each independently selected from an oxygen atom or a sulfur atom;

[0070] a, b, m, n, and p are each independently selected from 0, 1, or 2, and when X is an oxygen atom, a and b are not both 0;

[0071] o is 0 or 1, and when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1.

[0072] The optical polymer masterbatch provided herein contains a thermoplastic first polymer or a second polymer. The side chains of the first or second polymer contain polymerizable functional groups. By initiating a polymerization reaction of the polymerizable functional groups in the side chains of the first or second polymer, a thermosetting polymer can be obtained. This method retains the advantages of thermoplastic injection molding, reducing the volume shrinkage between the polymerized monomer and the resulting polymer, while also combining the heat resistance of thermosetting materials, ultimately resulting in a high-refractive index, high-Abbe optical material with practical application value.

[0073] As a possible implementation scenario of the optical polymer masterbatch of the present application, the optical polymer further includes an initiator and an auxiliary agent. The initiator can be used to initiate a polymerization reaction of the polymerizable functional groups in the side chains of the first polymer or the second polymer, thereby forming crosslinks between the first polymer or the second polymer; the auxiliary agent can be used to improve the injection molding performance of the optical polymer masterbatch.

[0074] As one possible implementation of the optical polymer masterbatch of the present application, the additive is selected from at least one of a filler, a dye, an antioxidant, a light stabilizer, a UV absorber, a plasticizer, a flame retardant, an antistatic agent, a release agent, a polymerization regulator, and a crosslinking accelerator. Different additives can enhance different properties of the optical polymer masterbatch. The present application can select appropriate additives based on the pre-prepared optical material to obtain an optical material with corresponding properties.

[0075] In a fourth aspect, the present application provides an optical element, which includes the optical polymer described in the first aspect of the present application or the optical polymer produced by the method described in the second aspect of the present application; or the optical element is made of the optical polymer masterbatch described in the third aspect of the present application.

[0076] Since the optical polymer provided in the first aspect of the present application or the optical polymer prepared by the method described in the second aspect, the optical material made from the optical polymer masterbatch described in the third aspect of the present application has a refractive index greater than 1.60 and an Abbe number greater than 30, the optical polymer has a low volume shrinkage rate during the molding process, and the optical polymer can maintain good heat resistance, and therefore can meet the application requirements of optoelectronic components.

[0077] As a possible implementation scenario of the optical element of the present application, the optical element is an optical lens, an optical film, a light guide plate, an optical disc or a lens. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figure 1 is a flow chart of the preparation process of the optical polymer provided in the embodiments of the present application;

[0079] Figure 2 This is a process flow chart for preparing an optical element provided in an embodiment of the present application;

[0080] Figure 3 is the H-NMR graph of the polymerized monomer provided in Example 1 of the present application;

[0081] Figure 4 This is an infrared spectrum of the cyclic sulfide / double bond functional group content in the polymerized monomer, solid thermoplastic polymer and thermosetting resin material provided in Example 1 of the present application. DETAILED DESCRIPTION

[0082] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0083] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0084] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0085] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a", "an", "the" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0086] The weights of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass described in the examples of this application may be a mass unit known in the chemical industry, such as μg, mg, g, kg, etc.

[0087] The terms "first" and "second" are used solely for descriptive purposes to distinguish objects, such as substances, from one another and should not be understood to indicate or imply relative importance or to implicitly specify the quantity of the technical features being referred to. For example, without departing from the scope of the embodiments of this application, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX. Thus, features defined as "first" or "second" may explicitly or implicitly include one or more of such features.

[0088] The term "COC" is an abbreviation for "Cyclic olefin copolyme", which means cyclic olefin copolymer;

[0089] The term "COP" is an abbreviation for "Cyclic olefin polymer", which means cyclic olefin polymer;

[0090] The term "DCM" is an abbreviation for "Dichloromethane (Methylene chloride)", which means dichloromethane;

[0091] The term "BMMD" is an abbreviation for "1,4-Dithiane-2,5-di(methanethiol)", which means 2,5-dimethylmercapto-1,4-dithiane;

[0092] The term "S" is an abbreviation of "sulfur" and refers to the element S;

[0093] The term "PC" is an abbreviation of "Polycarbonate", which means polycarbonate;

[0094] The term "CMOS" is an abbreviation for "Complementary metal-oxide-semiconductor", which means complementary metal oxide semiconductor;

[0095] The term "degree of polymerization" is expressed in English as Degree of Polymerization, abbreviated as DP or Xn. The degree of polymerization is an indicator used to measure the size of polymer molecules. Based on the number of repeating units, that is, the average number of repeating units contained in the polymer macromolecule chain, represented by n; based on the number of structural units, that is, the number of individual structural units contained in the polymer macromolecule chain. For example, if a molecule of polymer monomer contains only one A group or A functional group, then the degree of polymerization of the A group or A functional group in the polymer monomer is 1;

[0096] The term "X heterocyclopropane" refers to a group formed by replacing one carbon atom of cyclopropane with an X heteroatom, wherein one of the carbon atoms in cyclopropane loses a hydrogen atom.

[0097] Refractive index and Abbe number are important indicators that reflect the basic performance of optical components. Taking optical lenses as an example, generally speaking, the higher the refractive index of an optical lens, the more pixels the optical component has when imaging, and the better the quality of the image formed after imaging; the higher the Abbe number of an optical lens, the lower the degree of dispersion of different colors of light, and the higher the clarity of the image formed after imaging. Because the more mature optical materials in the industry are high-refractive-index, low-Abbe-number materials (high refractive index, low Abbe number) and low-refractive-index, high-Abbe-number materials (low refractive index, high Abbe number), it is currently difficult to prepare optical materials with both a high refractive index and a high Abbe number.

[0098] In view of this, an embodiment of the present application provides an optical element having both a high refractive index and a high Abbe number. The optical element contains an optical material having a high refractive index and a high Abbe number, or the optical element is made of an optical material having a high refractive index and a high Abbe number. The optical element containing an optical material having a high refractive index and a high Abbe number or made of an optical material having a high refractive index and a high Abbe number involved in the embodiments of the present application may be an optical lens, an optical film, a light guide plate, an optical disc, or a lens, or may be other optical elements.

[0099] In the embodiment of the present application, the optical material with high refractive index and high Abbe number refers to an optical polymer with high refractive index and high Abbe number. The optical polymer is a polymer containing the S element. Since the S element has both a high refractive index and a high Abbe number level, by introducing the S element into the optical polymer, the refractive index and Abbe number of the optical polymer can be simultaneously increased to a high level. In addition, the embodiment of the present application solves the problem of the difficulty in balancing heat resistance and volume shrinkage in polymers containing the S element by structurally designing the polymer monomers for synthesizing optical polymers, designing two types of polymerizable functional groups with different activities in the polymer monomers, and sequentially initiating the polymerization reaction of the two types of polymerizable functional groups through targeted initiators. This allows the optical polymer formed by polymerization of the polymer monomers to have both good heat resistance and low volume shrinkage.

[0100] Specifically, the optical polymer provided in the embodiment of the present application is formed by polymerizing the polymerizable monomers shown in Formula 1 below.

[0101]

[0102] The polymerizable monomer provided in the embodiments of the present application includes two sulfur-containing groups bridged by R1. The S element in the sulfur-containing group is used to increase the refractive index and Abbe number of the optical polymer, so that the optical polymer has both a high refractive index and a high Abbe number.

[0103] In Formula 1, R1 is a cyclic hydrocarbon group or an aromatic structure, used to connect the two sulfur-containing groups. Furthermore, when R1 is a cyclic structure, specifically a cyclic hydrocarbon group or an aromatic structure, this structure can rationally arrange the positions and numbers of the two sulfur-containing groups on the cyclic structure, so that the two sulfur-containing groups have an appropriate number and spatial configuration on the polymerizable monomer. This not only facilitates the polymerization reaction of the first polymerizable functional group to form a linear polymer, and allows the unreacted second polymerizable functional group to have an appropriate position in the side chain structure, but also facilitates the polymerization and cross-linking of different linear polymers through the second polymerizable functional group to form a thermosetting polymer, i.e., the optical polymer of the embodiments of the present application. In particular, when the degree of polymerization of one of the two sulfur-containing groups is not 1, the cyclic structure can provide suitable binding sites for the multiple sulfur-containing groups, allowing the multiple sulfur-containing groups to have an appropriate spatial configuration in the polymerizable monomer, thereby improving polymerization efficiency.

[0104] In some embodiments, R1 is a cyclic group that does not contain heteroatoms. The cyclic group that does not contain heteroatoms can be a cycloalkyl group or an aryl group. Exemplarily, R1 is a cyclohexyl group, a cyclopentyl group, a phenyl group, etc. The two sulfur-containing groups are respectively bonded to the carbon atoms of the cyclohexyl group, the cyclopentyl group, and the phenyl group. Among them, when the polymerization degree of the two sulfur-containing groups is 1 at the same time, R1 is preferably a cyclohexyl group or a phenyl group. At this time, the two sulfur-containing groups are respectively located in the para position of the cyclohexyl group or the phenyl group, so that the two polymerizable functional groups in the sulfur-containing group form a state in which the angle between the side chain and the main chain is close to 90° or a state in which the angle between the side chain and the main chain is 90° during the first polymerization process; during the second polymerization process, the polymerizable photoenergy groups in the side chains are cross-linked to form a stable grid-like thermoplastic polymer.

[0105] In some possible embodiments, R1 contains a cyclic group containing a heteroatom. The cyclic group containing a heteroatom can be a cycloalkyl group containing a heteroatom or an aryl group containing a heteroatom. In this case, the two sulfur-containing groups are respectively bonded to different carbon atoms on the cyclic group.

[0106] In some possible embodiments, the heteroatom is selected from a sulfur atom, a nitrogen atom, or an oxygen atom. In particular, when the heteroatom is a sulfur atom, the S element content in the optical polymer increases, which is more conducive to obtaining an optical polymer with a high refractive index and a high Abbe number.

[0107] Exemplarily, R1 is the following structure:

[0108]

[0109] In some embodiments, the heteroatom-containing cyclic group preferably comprises a sulfur atom in the aforementioned group. In this case, R1 increases the S content in the polymerized monomer, thereby increasing the number of methylene groups in the two sulfur-containing groups while maintaining the sulfur content in the polymerized monomer, thereby enriching the types of polymerized monomers.

[0110] The polymerizable monomers provided in the embodiments of the present application contain two sulfur-containing groups. Each of the two sulfur-containing groups contains a polymerizable functional group, and the two polymerizable functional groups have different reactivities. Therefore, the polymerizable monomers provided in the embodiments of the present application can undergo two polymerization reactions on the two polymerizable functional groups, respectively, to produce a linear thermoplastic polymer and a cross-linked thermosetting polymer, respectively. The cross-linked thermosetting polymer is the optical polymer of the embodiments of the present application.

[0111] In the embodiment of the present application, a sulfur-containing group of the polymerized monomer has a structure as shown in the following structure 1-1:

[0112]

[0113] The sulfur-containing group shown in Structure 1-1 contains a sulfur atom and an X heterocyclopropane group, wherein the sulfur atom S is used to increase the sulfur content of the polymerized monomer, thereby improving the refractive index and Abbe number of the optical polymer. The number of sulfur atoms (a) in the sulfur-containing group shown in Structure 1-1 can be 0, 1, or 2. It should be noted that when a is 0, at least one X of the X heterocyclopropane group shown in Structure 1-1 is sulfur, or b in Formula 1 is not 0, or b in Formula 1 is not 0 and X in at least one X heterocyclopropane group shown in Structure 1-1 is sulfur, thereby ensuring the sulfur content of the polymerized monomer.

[0114] The X heterocyclopropane group in structure 1-1 can undergo ring-opening polymerization under the action of an initiator, thereby allowing different polymerizable monomers to form a linear polymer through the ring-opening polymerization of the X heterocyclopropane group. Alternatively, the already formed linear polymer can be formed into a network cross-linked structure through the ring-opening polymerization of the X heterocyclopropane group.

[0115] Where X is an oxygen atom or a sulfur atom. Correspondingly, when X is a sulfur atom, the polymerizable functional group in the corresponding sulfur-containing group is a thiol group (-CH(Y)CH2S), which can also be called a thiol group or a thiol group. When X is an oxygen atom, the polymerizable functional group in the corresponding sulfur-containing group is an oxirane group (-CH(Y)CH2O), where Y represents a side chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) oCH(R2)=C(R3)(R4). In particular, when X in the X heterocyclopropane group is a sulfur atom, the relative content of the S element in the polymerized monomer can be increased, thereby facilitating the improvement of the refractive index and Abbe number of the optical polymer, ultimately yielding a high-refractive-index and high-Abbe number material.

[0116] In some embodiments, in the sulfur-containing group shown in the above structure 1-1, a methylene group may be optionally provided between the sulfur atom S and the X heterocyclopropane group, and between the sulfur atom S and R1. When a methylene group is provided between the sulfur atom S and the X heterocyclopropane group, or between the sulfur atom S and R1, the number of methylene groups is at most two. That is, in the structure of Formula 1, m and n are each independently selected from 0, 1 or 2. In some embodiments, in the sulfur-containing group shown in the above structure, the sulfur atom S a Between the heterocyclopropane group and X, the sulfur atom S a and R1 are provided with one or two methylene groups. In some embodiments, the sulfur-containing group shown in the above structure, the sulfur atom S a and X between heterocyclopropane or sulfur atom S a One or two methylene groups are set between R1 and R2. In some embodiments, the sulfur-containing group shown in the above structure 1-1, the sulfur atom S a and X between heterocyclopropane or sulfur atom S a There may be no methylene group between R1 and S1. In this case, the sulfur atom S a Directly connected to the heterocyclopropane group X, the sulfur atom S a It is also directly connected to R1.

[0117] In some embodiments, when g is greater than or equal to 2, multiple -(CH2) n -S a -n is independently selected from 0, 1 or 2. Exemplarily, when g is 2, two -(CH2) n -S a -n is 0 and 1, or 1 and 2, or 0 and 2; or -(CH2) n -S a - n are all 0; or two -(CH2) n -S a - n is 1; or two -(CH2) n -S a - where n is 2.

[0118] In a polymerizable monomer provided in an embodiment of the present application, the number of sulfur-containing groups containing an X heterocyclopropane group can be 1 to 5, i.e., g in Formula 1 is an integer selected from 1 to 5. For example, the number of sulfur-containing groups containing an X heterocyclopropane group can be 1, 2, 3, 4, or 5. Furthermore, the value of g is correlated with h (i.e., the number of the other sulfur-containing groups), such that at least one of g and h is 1. Thus, during the polymerization reaction, a linear thermoplastic polymer can be prepared by first initiating polymerization of a polymerizable functional group with a degree of polymerization of 1.

[0119] In some embodiments, when g is greater than or equal to 2, each of the X heterocyclopropane groups (-CH(Y)CH2X) is independently selected from an oxygen atom or a sulfur atom, wherein Y represents a branched chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4). Exemplarily, when g is 2, X in the two X heterocyclopropane groups (-CH(Y)CH2X) is an oxygen atom and a sulfur atom, respectively; or X in the two X heterocyclopropane groups (-CH(Y)CH2X) is both an oxygen atom; or X in the two X heterocyclopropane groups (-CH(Y)CH2X) is both a sulfur atom.

[0120] It should be noted that when g is not 1, multiple sulfur-containing groups shown in structure 1-1 are respectively bonded to different carbon atoms of R1. In this case, the degree of polymerization of the X heterocyclopropane group in the polymerized monomer is greater than 1.

[0121] In the embodiment of the present application, another sulfur-containing group of the polymerized monomer has a structure as shown in the following structure 1-2:

[0122]

[0123] The sulfur-containing group shown in Structure 1-2 contains a sulfur atom (S) and a carbon-carbon double bond. Together with the sulfur atom in Structure 1-1, this sulfur atom serves to increase the sulfur content of the polymerized monomer, thereby improving the refractive index and Abbe number of the optical polymer. The number of sulfur atoms (b) in the sulfur-containing group shown in Structure 1-2 can be 0, 1, or 2. It should be noted that when b is 0, the X in the Xheterocyclopropane group in Structure 1-1 is sulfur, or a in Structure 1-1 is not 0, or a in Structure 1-1 is not 0 and the X in the Xheterocyclopropane group in Structure 1-1 is sulfur, thereby ensuring the sulfur content of the polymerized monomer.

[0124] The carbon-carbon double bonds in structure 1-2 can be broken and polymerized under the action of an initiator, thereby allowing different polymerizing monomers to polymerize through the carbon-carbon double bonds to form a linear thermoplastic polymer. Alternatively, the already formed linear thermoplastic polymer can be polymerized through the carbon-carbon double bonds on the side chains to form a cross-linked thermosetting polymer, that is, the optical polymer provided in the embodiments of the present application.

[0125] In some embodiments, the sulfur-containing group shown in Structure 1-2 above may optionally have a carbonyl group between the sulfur atom and the carbon-carbon double bond, and may optionally have a methylene group between the sulfur atom and R1, with a maximum of two methylene groups. That is, in Formula 1, p is independently selected from 0, 1, or 2; and o is 0 or 1.

[0126] In some embodiments, when h is greater than or equal to 2, multiple -(CH2) p -S b -p in each independently selected from 0 or 1 or 2. Exemplarily, when h is 2, two -(CH2) p -S b - in which p is 0 and 1, or 1 and 2, or 0 and 2; or -(CH2) p -S b - in which p is 0; or two -(CH2) p -S b - in which p is 1; or two -(CH2) p -S b -The p in each is 2.

[0127] In a polymerizable monomer provided in an embodiment of the present application, the number of sulfur-containing groups containing carbon-carbon double bonds can be 1 to 5, that is, h in Formula 1 is an integer selected from 1 to 5. For example, the number of sulfur-containing groups containing carbon-carbon double bonds can be 1, 2, 3, 4, or 5. Furthermore, the value of h is also related to g (that is, the number of sulfur-containing groups shown in Structure 1-1), such that at least one of g and h is 1. Thus, during the polymerization reaction, the preparation of a thermoplastic linear polymer can be achieved by first initiating a polymerizable functional group with a degree of polymerization of 1.

[0128] In some embodiments, when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1. Exemplarily, when h is 2, two -(CO) o o in CR2=CR3(R4) is 0 and 1 respectively; or two -(CO) o The o's in CR2=CR3(R4) are all 0; or two -(CO) o All o's in CR2=CR3(R4) are 1.

[0129] In the embodiments of the present application, R2, R3, and R4 in the sulfur-containing group shown in Structure 1-2 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br.

[0130] Because the polymerizable monomers provided in the embodiments of the present application contain the element S, they are beneficial for increasing the refractive index and Abbe number of the optical polymer, thereby obtaining a high-refractive-index, high-Abbe-number material. In particular, when the two sulfur-containing groups each independently contain one or more sulfur atoms, the polymerizable monomer is rich in sulfur atoms. Therefore, the optical polymer formed by polymerizing the polymerizable monomers also has the advantages of a high refractive index and a high Abbe number. When X in the X heterocyclopropane group is a sulfur atom, the refractive index and Abbe number of the optical polymer can be further increased.

[0131] In some possible embodiments, the mass percentage of sulfur atoms is 20-70%, based on the total mass of the polymerized monomers as 100%. In this case, the optical polymer obtained after polymerization of the polymerized monomers has a high S content, and the refractive index increases with the increase in the S content. The Abbe number level can also be maintained above 35, ultimately facilitating the production of an optical polymer with a high refractive index and a high Abbe number. For example, based on the total mass of the polymerized monomers as 100%, the mass percentage of sulfur atoms is 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and so on.

[0132] The optical polymer provided in the embodiment of the present application, the two polymerizable functional groups introduced in the polymerization monomer are respectively X heterocyclopropane and carbon-carbon double bond, and the types of the two polymerizable functional groups are different and the activities are also different. Therefore, the initiation system or catalytic system for initiating the ring-opening polymerization of X heterocyclopropane and the initiation system or catalytic system for initiating the polymerization of carbon-carbon double bond also show certain differences. Specifically, when anionic polymerization or cationic polymerization is used to initiate the ring-opening polymerization of X heterocyclopropane, the carbon-carbon double bond will not be affected. Therefore, the polymer formed after the ring-opening polymerization of X heterocyclopropane can retain the complete carbon-carbon double bond structure; similarly, when free radical polymerization is used to initiate the polymerization reaction between carbon-carbon double bonds, X heterocyclopropane will not be affected. Therefore, the polymer formed after the polymerization of carbon-carbon double bond can retain the complete X heterocyclopropane structure. Therefore, the polymerization monomer of the embodiment of the present application can initiate the polymerization reaction of two polymerizable functional groups in batches without affecting each other.

[0133] Furthermore, the molar ratio of at least one of the two polymerizable functional groups to the polymerizable monomer is 1:1. Therefore, by first initiating polymerization of the polymerizable functional groups with a functionality of 1, the polymerizable functional groups with a functionality of 1 in the monomer polymerize with the same polymerizable functional groups in adjacent units, sequentially linking the monomers to form a linear thermoplastic polymer. Meanwhile, the other polymerizable functional groups remain intact in the side chains of the thermoplastic polymer. Since the intermolecular distance decreases and the volume shrinks during the conversion of the monomer to the thermoplastic polymer, a portion of the shrinkage is pre-consumed. This significantly reduces the shrinkage of the material after final thermal curing. Therefore, the optical polymer produced after the secondary polymerization of the thermoplastic polymer exhibits a volumetric shrinkage advantage. Subsequently, polymerization between the polymerizable functional groups in the thermoplastic polymer side chains is initiated, crosslinking the different linear thermoplastic polymers to form a thermoset polymer, endowing the optical polymer with the heat resistance of a thermoset material.

[0134] In the embodiments of the present application, the structure of the optical polymer can be divided into two situations according to the different values of g and h.

[0135] As a first possible implementation scenario, in the polymerized monomer, g is 1, that is, the degree of polymerization of the X heterocyclopropane group in the polymerized monomer is 1. The corresponding optical polymer includes multiple first polymer chains formed by ring-opening polymerization of the X heterocyclopropane group, and different first polymer chains are cross-linked through carbon-carbon double bonds. The formation mechanism of this implementation scenario is: when g is 1, one molecule of the polymerized monomer contains only one molecule of the X heterocyclopropane group. At this time, the X heterocyclopropane group is ring-opened under the action of an initiator to form an X alkyl group (-X-CH2-CH(Y)-) with polymerizable sites at both ends, wherein Y represents a side chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4)). The polymerizable monomer is sequentially polymerized through two polymerizable sites during the first polymerization process to form a linear first polymer chain. The first polymer chain obtained after the first polymerization retains a complete carbon-carbon double bond structure. By initiating a second polymerization of the carbon-carbon double bond, crosslinking between different first polymer chains is achieved, thereby obtaining a cross-linked thermosetting polymer, that is, the optical polymer provided by the embodiment of the present application. The optical polymer thus formed not only has the advantages of a high refractive index and a high Abbe number, but also has good heat resistance because a thermoplastic polymer and a thermosetting polymer are obtained successively through two polymerization reactions. The volume shrinkage before and after the second polymerization can be significantly reduced, thereby improving the practical application effect of the optical polymer containing the S element.

[0136] In some embodiments, the structure of the optical polymer contains a repeating unit A as shown below:

[0137]

[0138] In this embodiment, the formation mechanism of the optical polymer structure is as follows: the polymerized monomer first undergoes ring-opening polymerization via the X-heterocyclopropane group to form a linear thermoplastic polymer with a main chain consisting of -X-CH2-CH(Y)- repeating units, which helps to overcome the large volume difference between the polymerized monomer and the optical polymer, wherein Y represents a side chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4); different linear polymers covalently polymerize through carbon-carbon double bonds to ultimately form cross-linked optical polymers, which helps overcome the lack of heat resistance of optical polymers. The repeating unit A is rich in sulfur atoms, resulting in optical polymers containing this repeating unit A having the advantages of a high refractive index and a high Abbe number.

[0139] As a second possible implementation scenario, in the polymerized monomer, h is 1, that is, the degree of polymerization of the carbon-carbon double bond in the polymerized monomer is 1. The corresponding optical polymer includes a plurality of second polymer chains formed by polymerization of the carbon-carbon double bond in Formula 1, and different second polymer chains are cross-linked by ring-opening polymerization of the X heterocyclopropane group. The formation mechanism of this implementation scenario is: when h is 1, one molecule of polymerized monomer contains only one molecule of carbon-carbon double bond. At this time, after the carbon-carbon double bond is broken under the action of the initiator, the two carbon atoms form two polymerizable sites in the form of free radicals. The polymerized monomer is sequentially polymerized through the two polymerizable sites during the first polymerization process to form a linear first polymer chain. The first polymer chain obtained after the first polymerization retains a complete X heterocyclopropane structure, and by initiating the ring-opening polymerization of the X heterocyclopropane group (second polymerization), cross-linking between different first polymer chains is achieved, thereby obtaining a cross-linked thermosetting polymer, that is, the optical polymer provided in the embodiment of the present application. The optical polymer thus formed not only has the advantages of high refractive index and high Abbe number, but also has good heat resistance and no significant volume shrinkage before and after polymerization, thereby improving the practical application effect of the optical polymer containing S element.

[0140] In some embodiments, the structure of the optical polymer is as follows:

[0141]

[0142] In the repeating unit B, s is selected from an integer greater than 2, and the structure of R5 is as follows:

[0143]

[0144] In this embodiment, the formation mechanism of the optical polymer structure is as follows: the polymerized monomers first polymerize through carbon-carbon double bonds to form a linear thermoplastic polymer with a main chain consisting of -C(R2)(R6)-C(R3R4)- repeating units, which helps overcome the large volume difference between the polymerized monomers and the optical polymer. The different linear polymers then undergo ring-opening polymerization of the X heterocyclopropane groups to ultimately form a cross-linked optical polymer, which helps overcome the problem of insufficient heat resistance of the optical polymer. In -C(R2)(R6)-C(R3R4)-, R6 represents the following structural fragment:

[0145]

[0146] Based on the above embodiment, in some embodiments, the polymerizable monomer is selected from one of the following structures:

[0147]

[0148]

[0149]

[0150]

[0151] The polymerizable monomers provided in the above embodiments are all polymerizable monomers in which the heteroatom is selected from S atoms. The optical polymer obtained by selecting a polymerizable monomer rich in S atoms is beneficial for obtaining the effects of high refractive index and high Abbe number. It should be understood that the above polymerizable monomers are only some of the monomers listed in the embodiments of the present application, not all monomers. One or more of the heteroatoms in the above polymerizable monomers can be replaced by O atoms or N atoms to obtain more types of polymerizable monomers.

[0152] The structure of the aforementioned polymerizable monomer contains two polymerizable functional groups: the first polymerizable functional group is a cyclosulfanyl or epoxyalkyl group, and the second polymerizable functional group is a carbon-carbon double bond. Because the two polymerizable functional groups have different activities, a thermoplastic polymer can be obtained by first polymerizing one of the polymerizable functional groups, and then a thermosetting polymer (i.e., the optical polymer of the present application) can be obtained through polymerization of the other polymerizable functional group. This reduces the difference in volume change between the thermosetting polymer and the polymerizable monomer, thereby reducing volume shrinkage. Furthermore, because at least one of the two polymerizable functional groups is present in one molecule of the polymerizable monomer, a linear thermoplastic polymer can be obtained when one of the polymerizable functional groups is polymerized to obtain a thermoplastic polymer. Furthermore, when the other polymerizable functional group is polymerized, the linear thermoplastic polymer is cross-linked through the polymerizable functional groups, thereby reducing the flexibility of the optical polymer molecular chain and improving the heat resistance of the optical polymer.

[0153] In summary, the optical polymers provided in the embodiments of the present application can be prepared by polymerizing a polymerizable functional group with a degree of polymerization of 1 in the polymerizable monomer through a first polymerization reaction to prepare a linear thermoplastic polymer with a reactive functional group in the side chain, thereby reducing the overall volume shrinkage and improving the shrinkage problem of the thermosetting material. This can then be triggered by another polymerizable functional group to form a cross-linked polymer system, solving the problem of poor heat resistance of sulfur-containing thermoplastic materials. When the polymerizable monomer is directly prepared to form an optical component, due to the thermal fluidity of the thermoplastic material, the linear polymer can be formed and then a polymerization reaction of another polymerizable functional group can be triggered to directly obtain the optical component.

[0154] Correspondingly, such as Figure 1 As shown, the embodiment of the present application provides a method for preparing the above-mentioned optical polymer, comprising the following steps:

[0155] S01. Provide a polymerizable monomer as shown in the following formula 1, wherein g and h are independently selected from integers of 1 to 5, and at least one of g and h is 1; R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; X is an oxygen atom or a sulfur atom, and when g is greater than or equal to 2, multiple Xs are each independently selected from an oxygen atom or a sulfur atom; a, b, m, n, and p are each independently selected from 0, 1, or 2, and when X is an oxygen atom, a and b are not both 0; o is 0 or 1, and when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1.

[0156]

[0157] In this step, the polymerizable monomer shown in Formula 1 is used as the only polymerizable monomer of the optical polymer. The functionality of the polymerizable functional group, the selection of R1, the number of sulfur atoms in the two sulfur-containing groups, and the structure of some polymerizable monomers can be found above. In order to save space, they are not repeated here.

[0158] In one possible embodiment, when X is an oxygen atom, the preparation method of the polymerizable monomer is:

[0159] (1) Compound 2 of Formula 2 and thiourea are heated to reflux in an organic solvent, and after the reaction is completed, a solid product is collected; the solid product is dissolved in water, heated to a high temperature, and ammonia water is added to react to obtain Compound 3 of Formula 3, wherein A in Formula 2 represents a halogen atom.

[0160]

[0161] In this step, compound 2 of Formula 2 is heated under reflux with thiourea in an organic solvent to replace the halogen atom A in Formula 2 with a thiol group. Here, R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms; a, b, n, and p are each independently selected from 0, 1, or 2; g and h are each selected from integers between 1 and 5, and at least one of g and h is 1.

[0162] (2) Compound 3 of formula 3, sodium ethoxide, and tetrabutylammonium bromide were added to a reaction flask, stirred at room temperature, and then ethyl carbon-carbon double bond bromine was added. The reaction system was sealed and heated to obtain compound 4 of formula 4.

[0163]

[0164] In this step, under the action of sodium ethoxide and tetrabutylammonium bromide, ethyl carbon-carbon double bond bromine reacts with compound 3 to introduce a carbon-carbon double bond. Here, R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; X is an oxygen atom or a sulfur atom; and R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br.

[0165] (3) Compound 4 of Formula 4, epichlorohydrin, triethylamine, and THF were added to a reaction flask, magnetic stirring was started, and the temperature was raised to react to obtain Compound 5 of Formula 5. Wherein, A in Formula 5 represents a halogen atom.

[0166]

[0167] In this step, under the action of triethylamine, epichlorohydrin reacts with compound 4 under heating conditions to generate compound 5 having a structure shown in formula 5.

[0168] (4) Compound 5 of Formula 5, THF, and sodium hydroxide solution were added to a reaction flask, magnetic stirring was started, and heating and heat preservation were performed to obtain Compound 6 of Formula 6.

[0169]

[0170] In this step, under heating conditions, compound 5 reacts with sodium hydroxide to obtain compound 6 having a structure shown in formula 6.

[0171] The preparation method of the polymerizable monomer provided in the above embodiment can synthesize a polymerizable monomer in which X is an O atom.

[0172] In one possible embodiment, when X is a sulfur atom, the method for preparing the polymerizable monomer comprises: preparing compound 6 having a structure shown in formula 6 by the above method;

[0173] Furthermore, compound 6 with the structure shown in formula 6, thiourea, methanol, toluene and acetic acid are added to a reaction flask, and the mixture is heated and kept warm to react, thereby obtaining compound 7 with the structure shown in formula 7.

[0174]

[0175] By using this method, the O atoms in the oxygen-containing heterocycle can be replaced with sulfur atoms, further increasing the S content in the polymerized monomer. In particular, when the values of m, n, o, and p are large, the relative molecular weight of the polymerized monomer increases. Therefore, sulfur-containing heterocycles are beneficial for increasing the sulfur content in the polymerized monomer, thereby increasing the refractive index and Abbe number of the optical polymer, and thus achieving high-refractive-index, high-Abbe-number optical materials.

[0176] When g is greater than or equal to 2, n, p, and o in multiple sulfur-containing groups are not necessarily the same. Similarly, multiple X heterocyclopropane groups (-CH(Y)CH2X, where Y represents a branched chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o The X in CH(R2)=C(R3)(R4)) is not necessarily the same. Therefore, the preparation method of the polymer monomer is not limited to the above method, but the corresponding polymer monomer can be prepared by referring to the above method, which will not be listed here one by one.

[0177] S02. Initiating a first polymerization reaction of the first polymerizable functional group in Formula 1 to produce a linear thermoplastic polymer, wherein the first polymerizable functional group is an X heterocyclopropane group or a carbon-carbon double bond having a functionality of 1 in the structure of Formula 1.

[0178] In the embodiment of the present application, the polymerizable monomer contains two types of polymerizable functional groups, namely: X heterocyclopropane (-XCH(Y)CH2) and carbon-carbon double bond, wherein Y represents a branched chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4). Due to the different reactivities of the two types of polymerizable functional groups, the polymerizable monomers provided in the embodiments of the present application can initiate polymerization reactions of the two types of polymerizable functional groups separately through two polymerization reactions without affecting each other.

[0179] In this step, a first polymerization reaction is first performed on one type of polymerizable functional group in the polymerizable monomer, namely, the first polymerizable functional group in this step. It should be understood that the first polymerizable functional group undergoing the first polymerization reaction is a polymerizable functional group with a functionality of 1, so as to obtain a linear thermoplastic polymer. The polymerizable functional group with a functionality of 1 may be an X-heterocyclopropane group (-XCH(Y)CH2) or a carbon-carbon double bond.

[0180] In some embodiments, g is 1 and h is an integer from 2 to 5. In this case, the polymerizable functional group with a functionality of 1 is an X-heterocyclopropane group, that is, the first polymerizable functional group is an X-heterocyclopropane group (-XCH2CH(Y)). In this case, under the action of an initiator, the polymerizable monomer first undergoes ring-opening polymerization through the X-heterocyclopropane group to form a linear thermoplastic polymer with a main chain consisting of repeating units of -X-CH2-CH(Y)-, wherein Y represents a side chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4). The side chain of the repeating unit of the resulting linear thermoplastic polymer includes a carbon-carbon double bond. It should be understood that in this embodiment, the initiator that initiates the first polymerization reaction of the first polymerizable functional group in Formula 1 is an initiator that can initiate ring-opening polymerization of the X-heterocyclopropane group (-XCH2CH(Y)) but does not initiate polymerization of the carbon-carbon double bond. The type of initiator is not limited and can be an anionic initiator or a cationic initiator; it can also be a photoinitiator or a thermal initiator.

[0181] In some embodiments, g is an integer from 2 to 5, and h is 1. In this case, the polymerizable functional group with a functionality of 1 is a carbon-carbon double bond, i.e., the first polymerizable functional group is a carbon-carbon double bond. Under the action of an initiator, the monomers polymerize first through the carbon-carbon double bond to form a linear thermoplastic polymer with a main chain consisting of repeating units of -C(R2)(R6)-C(R3R4)-. In -C(R2)(R6)-C(R3R4)-, R6 represents the following structural fragment. The side chains of the repeating units of the resulting linear thermoplastic polymer include heterocyclopropane groups.

[0182]

[0183] It should be understood that in this embodiment, the initiator that initiates the first polymerization reaction of the first polymerizable functional group in Formula 1 is an initiator that can initiate a polymerization reaction of a carbon-carbon double bond but does not initiate a ring-opening polymerization of the X heterocyclopropane group (-XCH2CHY), such as a free radical initiator, wherein Y represents a side chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4). However, the type of initiator is not strictly limited, and the initiator that initiates the first polymerization reaction of the first polymerizable functional group in Formula 1 can be a photoinitiator or a thermal initiator.

[0184] In some embodiments, g is 1 and h is 1. In this case, the functionality of the X heterocyclopropane group (-XCH2CH(Y)) or the carbon-carbon double bond in the polymerizable monomer is 1. In this case, the first polymerizable functional group that undergoes the first polymerization reaction can be an X heterocyclopropane group (-XCH2CH(Y)) or a carbon-carbon double bond, wherein Y represents a branched chain containing a carbon-carbon double bond: -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4). The principle of initiating X heterocyclopropane (-XCH2CH(Y)) or carbon-carbon double bond can be referred to the above two embodiments.

[0185] S03. Initiating a second polymerization reaction of a second polymerizable functional group in the thermoplastic polymer to produce an optical polymer, wherein the second polymerizable functional group is the X heterocyclopropane group or the carbon-carbon double bond in the structure of Formula 1, and the second polymerizable functional group is different from the first polymerizable functional group.

[0186] In this step, the linear thermoplastic polymer obtained by the first polymerization reaction is subjected to a second polymerization reaction, so that the second polymerizable functional groups on the side chains of the linear thermoplastic polymer undergo a polymerization reaction, and different linear thermoplastic polymers are cross-linked to obtain a cross-linked thermosetting polymer.

[0187] In the embodiment of the present application, the second polymerizable functional group is a polymerizable functional group different from the first polymerizable functional group among the two polymerizable functional groups of the polymerizable monomer.

[0188] In some embodiments, when the first polymerizable functional group is a heterocyclopropane group, the second polymerizable functional group is a carbon-carbon double bond. In this case, the second polymerization reaction involves a polymerization reaction at the carbon-carbon double bonds in the side chains of the linear thermoplastic polymer under the action of an initiator, crosslinking the different linear thermoplastic polymers to form a crosslinked thermosetting polymer. It should be understood that in this embodiment, the initiator that initiates the second polymerization reaction at the second polymerizable functional group in the linear thermoplastic polymer is an initiator capable of initiating polymerization of carbon-carbon double bonds. The type of initiator is not limited and can be an anionic initiator, a cationic initiator, or a free radical initiator; it can also be a photoinitiator or a thermal initiator.

[0189] In some embodiments, when the first polymerizable functional group is a carbon-carbon double bond, the second polymerizable functional group is a X-heterocyclopropane group. In this case, the second polymerization reaction involves ring-opening polymerization of the X-heterocyclopropane groups in the side chains of the linear thermoplastic polymer under the action of an initiator, crosslinking the different linear thermoplastic polymers to form a crosslinked thermosetting polymer. It should be understood that in this embodiment, the initiator that initiates the second polymerization reaction of the second polymerizable functional group in the linear thermoplastic polymer is an initiator capable of initiating ring-opening polymerization of the X-heterocyclopropane groups. The type of initiator is not limited and can be an anionic or cationic initiator, a photoinitiator, or a thermal initiator.

[0190] In step S02 and step S03, the first polymerizable functional group or the second polymerizable functional group may undergo polymerization in a variety of ways. Exemplarily, the polymerization reaction may be anionic polymerization, cationic polymerization, or free radical polymerization. Free radical polymerization is suitable for polymerization of carbon-carbon double bonds, but is not suitable for polymerization of heterocyclopropane groups.

[0191] In one possible embodiment, when the first polymerizable functional group or the second polymerizable functional group is an X heterocyclopropane group, the polymerization reaction adopts anionic polymerization or cationic polymerization. Specifically, when the polymerization is carried out by anionic polymerization or cationic polymerization, under the action of an initiator, the X heterocyclopropane group first opens the ring to form Structure. The negatively charged sulfur in one polymeric monomer electrophilically bonds with the positively charged carbon in another polymeric monomer; the positively charged carbon then electrophilically bonds with the negatively charged sulfur in another molecule, thus forming a cross-linked polymer between each polymeric monomer and two other monomers via the X heterocyclopropane group.

[0192] In one possible embodiment, when the first polymerizable functional group is a carbon-carbon double bond, the polymerization reaction is free radical polymerization. When the carbon-carbon double bond is polymerized by free radical polymerization, under the action of a free radical initiator, the carbon-carbon double bond is broken into two carbon free radicals, and the two carbon free radicals in one polymerizing monomer molecule are respectively combined with one carbon free radical in two other polymerizing monomer molecules; thus, each polymerizing monomer molecule is cross-linked with two polymerizing monomer molecules via the carbon-carbon double bond.

[0193] In one possible embodiment, when the second polymerizable functional group is a carbon-carbon double bond, the polymerization reaction is anionic polymerization, cationic polymerization, or free radical polymerization. When the carbon-carbon double bond is polymerized by anionic polymerization or cationic polymerization, after the carbon-carbon double bond is broken, the two carbon atoms carry positive and negative charges, respectively. The negatively charged carbon in one polymerizing monomer electrophilically bonds with the positively charged carbon in another polymerizing monomer; and the positively charged carbon then electrophilically bonds with the negatively charged carbon in another polymerizing monomer. Thus, each polymerizing monomer molecule is sequentially connected to two polymerizing monomer molecules via the carbon-carbon double bond to form a polymer.

[0194] In some embodiments, the first polymerizable functional group is a X heterocyclopropane group, and the second polymerizable functional group is a carbon-carbon double bond. The X heterocyclopropane group can be anionic polymerized or cationic polymerized under the action of an initiator to form a ring-opening Structure. The negatively charged sulfur in one monomer electrophilically bonds with the positively charged carbon in another monomer; the positively charged carbon then electrophilically bonds with the negatively charged sulfur in another monomer. Thus, each monomer polymerizes with two monomers via the X-heterocyclopropane group and sequentially connects to form a linear thermoplastic polymer. Furthermore, through anionic polymerization, cationic polymerization, or free radical polymerization at carbon-carbon double bonds, different thermoplastic polymers can be cross-linked to form a network-like thermosetting polymer.

[0195] In some embodiments, the first polymerizable functional group is a carbon-carbon double bond, and the second polymerizable functional group is an X heterocyclopropane group. The carbon-carbon double bond of one molecule can be broken by free radical polymerization to form a carbon-carbon single bond. The broken double bond in one molecule of polymerized monomer then combines with the broken double bonds in two other molecules of polymerized monomer to form a crosslink. Specifically, under the action of a free radical initiator, the carbon-carbon double bond breaks into two carbon free radicals, and the two carbon free radicals in one molecule of polymerized monomer respectively combine with one carbon free radical in two other molecules of polymerized monomer; thus, each molecule of polymerized monomer polymerizes with two molecules of polymerized monomer through the carbon-carbon double bond and connects sequentially to form a linear thermoplastic polymer. Furthermore, anionic polymerization or cationic polymerization occurs through the X heterocyclopropane group, crosslinking different thermoplastic polymers to form a network-like thermosetting polymer.

[0196] The preparation method of the optical polymer provided in the embodiment of the present application uses an organic matter containing the S element as a polymerization monomer, and initiates a first polymerization reaction through a first polymerizable functional group with a functionality of 1 in the polymerization monomer to obtain a linear thermoplastic polymer; then the linear thermoplastic polymer is cross-linked through a second polymerization reaction of the first polymerizable functional group to obtain a cross-linked thermosetting polymer. By initiating the polymerization reactions of two different polymerizable groups through two polymerization reactions, the volume change difference between the thermosetting polymer and the polymerization monomer can be reduced, and the volume shrinkage rate can be reduced. At the same time, the linear thermoplastic polymer is cross-linked through the polymerization reaction between the second polymerizable functional groups, thereby reducing the flexibility of the optical polymer molecular chain and improving the heat resistance of the optical polymer. The optical polymer prepared by this method has the advantages of high refractive index and high Abbe number while being able to maintain good heat resistance and low volume shrinkage rate.

[0197] In one specific embodiment, in the polymerizable monomer represented by Formula 1, g is 1. The first polymerization reaction method involves initiating ring-opening polymerization of the X-heterocyclopropane groups in the polymerizable monomers using an anionic or cationic initiator to produce a linear thermoplastic polymer. The second polymerization reaction method involves adding an anionic or cationic initiator or free radicals to the linear thermoplastic polymer and initiating crosslinking of the carbon-carbon double bonds in the linear thermoplastic polymer under light or heat conditions to produce a crosslinked thermosetting polymer. In this case, the functionality of the X-heterocyclopropane groups is 1. Therefore, under the action of the initiator, the polymerizable monomers undergo ring-opening polymerization of the X-heterocyclopropane groups, while retaining the carbon-carbon double bonds in the polymerizable monomers, forming a linear thermoplastic polymer. Furthermore, by initiating polymerization of the carbon-carbon double bonds in the side chains of the thermoplastic polymers, different thermoplastic polymers are crosslinked to form a network-like thermosetting polymer.

[0198] In another specific embodiment, in the polymerizable monomers represented by Formula 1, h is 1. The first polymerization reaction involves adding a free radical initiator to the polymerizable monomers to initiate crosslinking of the carbon-carbon double bonds in the polymerizable monomers under light or heat conditions, thereby producing a linear thermoplastic polymer. The second polymerization reaction involves adding an ionic initiator or a cationic initiator to the linear thermoplastic polymer to initiate ring-opening polymerization of the X-heterocyclopropane groups in the linear thermoplastic polymer, thereby producing a crosslinked thermosetting polymer. In this case, the functionality of the carbon-carbon double bond is 1. Therefore, under the action of the free radical initiator, polymerization between the carbon-carbon double bonds occurs between the polymerizable monomers, and the X-heterocyclopropane groups in the polymerizable monomers are retained, forming a linear thermoplastic polymer. Furthermore, by initiating ring-opening polymerization of the X-heterocyclopropane groups on the side chains of the thermoplastic polymers, different thermoplastic polymers are crosslinked to form a network-like thermosetting polymer, namely, an optical polymer.

[0199] In the above embodiment, the anionic initiator can be a Lewis base. In some embodiments, the anionic initiator is a N-containing compound. Exemplarily, the N-containing compound is an aliphatic amine, such as triethylamine, diisopropylethylamine, or ethylenediamine; exemplary, the N-containing compound is an aromatic polyamine, such as p-phenylenediamine, m-phenylenediamine, or m-phenylenediamine; exemplary, the N-containing compound is an imidazole or other N-containing oligomer or polymer. In some embodiments, the anionic initiator contains a halide anion, exemplary, n-tetrabutylammonium bromide, n-tetrabutylphosphonium bromide, or the like.

[0200] In the above embodiment, the cationic initiator may be a Lewis acid, for example, a complex of BF3, AlCl3, SnCl4, or BF3, such as BF3.THF.

[0201] In the first polymerization reaction and the second polymerization reaction of the embodiment of the present application, there is no strict restriction on the polymerization mode, which can be solution polymerization, bulk polymerization, or a mixture of solution polymerization and bulk polymerization; the catalyst used in the polymerization reaction can be a photocatalyst or a thermal catalyst, and it only needs to be able to catalyze the polymerization of one type of polymerizable functional groups and have no effect on the other type of polymerizable functional groups.

[0202] Since the optical polymer provided in the embodiments of the present application or the optical polymer obtained by the method provided in the embodiments of the present application has the advantages of high refractive index and high Abbe number (refractive index greater than 1.60, Abbe number greater than 30), and the optical polymer has a low volume shrinkage rate during the molding process, and the optical polymer can maintain good heat resistance, it can meet the application requirements of optoelectronic components.

[0203] In one possible embodiment, the optical element can be prepared by optical polymer masterbatch.

[0204] In accordance with the requirements of optical components for high refractive index, high Abbe's degree, heat resistance, and low volume shrinkage, the present invention also provides an optical polymer masterbatch. The optical polymer masterbatch includes a first polymer or a second polymer, wherein the first polymer and the second polymer are both formed by polymerizing monomers as shown in Formula 1 below:

[0205] Wherein, the first polymer is a linear polymer formed by polymerization of monomers through X-heterocyclopropane ring-opening polymerization, and the second polymer is a linear polymer formed by polymerization of monomers through carbon-carbon double bonds;

[0206]

[0207] In Formula 1, R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; and X is an oxygen atom or a sulfur atom.

[0208] a, b, m, n, and p are each independently selected from 0, 1, or 2, and when X is an oxygen atom, a and b are not both 0; o is 0 or 1; g and h are each selected from an integer between 1 and 5, and at least one of g and h is 1.

[0209] In an embodiment of the present application, the optical polymer masterbatch comprises a linear thermoplastic polymer (i.e., the first polymer or the second polymer) obtained by polymerizing a polymerizable functional group with a degree of polymerization of 1 in a polymerizable monomer. This method allows the thermoplastic polymer to retain the advantages of thermoplastic injection molding, reducing the volume shrinkage between the polymerized monomer and the resulting optical polymer. Furthermore, due to the crosslinking of the different linear thermoplastic polymers, the resulting thermosetting polymer exhibits excellent heat resistance, ultimately resulting in a high-refractive index, high-Abbe optical material or component with practical application value.

[0210] In one possible embodiment, the optical polymer further includes an initiator and an auxiliary agent. The initiator can be used to initiate a polymerization reaction of the polymerizable functional groups in the side chains of the first polymer or the second polymer, thereby forming crosslinks between the first polymer or the second polymer; the auxiliary agent can be used to improve the injection molding performance of the optical polymer masterbatch.

[0211] In one possible embodiment, the additive is selected from at least one of a filler, a dye, an antioxidant, a light stabilizer, a UV absorber, a plasticizer, a flame retardant, an antistatic agent, a release agent, a polymerization regulator, and a crosslinking accelerator. Different additives can improve different properties of the optical polymer masterbatch. The present application can select appropriate additives based on the pre-prepared optical material to obtain an optical material with corresponding properties.

[0212] Specifically, in one embodiment, the first polymer is a linear polymer formed by polymerization of monomers through ring-opening polymerization of heterocyclopropane. In this case, the structure of the first polymer is shown below.

[0213]

[0214] The first polymer thus formed has a main chain of -X-CH2-CH(Y)- repeating units, and the side chains retain a complete carbon-carbon double bond structure. It is a thermoplastic polymer that is solid at room temperature, wherein Y represents a side chain containing a carbon-carbon double bond:

[0215] -(CH2) m S a (CH2) n R1(CH2) p S b (CO) o CH(R2)=C(R3)(R4). Using the first polymer prepared in this embodiment, after initiating polymerization of the carbon-carbon double bonds in the side chains, different first polymers can be cross-linked to form a cross-linked thermosetting polymer. The resulting thermosetting polymer not only has excellent heat resistance but also, because it is further polymerized with a thermoplastic polymer, exhibits low volume shrinkage, making it suitable for the preparation of optical components with precise volume requirements.

[0216] Correspondingly, such as Figure 2 As shown, the optical element can be made by the following steps:

[0217] Mixing the first polymer with a photoinitiator and an auxiliary agent to prepare an optical polymer masterbatch;

[0218] Molding the optical polymer masterbatch into an optical element blank of corresponding shape; wherein the molding method is not strictly limited and can be injection molding, lamination, solvent coating, scraping, etc.;

[0219] The side chain polymerizable functional groups of the first polymer in the optical element embryo are polymerized by light triggering, so that the first polymer is cross-linked to form a thermosetting polymer, thereby obtaining the optical element.

[0220] In another embodiment, the second polymer is a linear polymer formed by polymerization of monomers through carbon-carbon double bonds.

[0221] At this time, the structure of the second polymer is as shown below.

[0222]

[0223] In the repeating unit B, s is selected from an integer greater than 2, and the structure of R5 is as follows:

[0224]

[0225] The first polymer thus formed has a main chain consisting of repeating units of -C(R2)(R6)-C(R3R4)-, with intact X-heterocyclopropane groups remaining on the side chains, and is a thermoplastic polymer that is solid at room temperature. In -C(R2)(R6)-C(R3R4)-, R6 represents the following structural fragment.

[0226]

[0227] The second polymer prepared in this embodiment can be cross-linked to form a cross-linked thermosetting polymer after initiating ring-opening polymerization of the X-heterocyclopropane group in the side chain. The resulting thermosetting polymer not only has excellent heat resistance but also, because it is further polymerized with a thermoplastic polymer, exhibits low volume shrinkage, making it suitable for the production of optical components with precise volume requirements.

[0228] Correspondingly, the optical element can be manufactured by the following steps:

[0229] The second polymer is mixed with an initiator and an auxiliary agent to prepare an optical polymer masterbatch; in this step, the initiator can be a photoinitiator or a thermal initiator;

[0230] Molding the optical polymer masterbatch into an optical element blank of corresponding shape; wherein the molding method is not strictly limited and can be injection molding, etc.;

[0231] The side chain polymerizable functional groups of the second polymer in the optical element embryo are initiated to polymerize, so that the second polymer is cross-linked to form a thermosetting polymer, thereby obtaining the optical element.

[0232] The following describes the details in conjunction with specific embodiments.

[0233] An optical polymer is prepared by the following method:

[0234] (1) Preparation of polymerization monomers

[0235] Preparation of Intermediate 1: Calcium carbonate (0.84 g, 8.4 mmol), DCM (700 mL), and diallyl disulfide (72.28 g, 420 mmol) were weighed and added sequentially to a 2 L four-necked flask. The flask was placed in a low-temperature tank, secured, and stirred. After the reaction solution temperature dropped to -30°C, sulfonyl chloride (60.60 g, 440 mmol) was slowly added dropwise. The reaction temperature was maintained between -30°C and -35°C. The reaction was stirred for 6 h, filtered, and the filtrate was subjected to rotary evaporation to remove the solvent to obtain 103 g of a colorless to pale yellow viscous transparent liquid (Intermediate 1).

[0236] Preparation of Intermediate 2 (BMMD): Intermediate 1 (103 g), thiourea (79.42 g), and ethanol (320 mL) were weighed sequentially and added to a 500 mL four-necked flask. The mixture was heated to 80°C–90°C and refluxed for 3.5 h. Heating was stopped and the mixture was allowed to cool to room temperature. Filtered under reduced pressure to obtain a white solid. The resulting solid was added to ethanol (200 mL), stirred for 1 h, and filtered. The filter cake was further added to dichloromethane (200 mL), stirred for 1 h, filtered, and a white solid was obtained. The solid was then air-dried. The white solid (130 g) and deionized water (300 mL) were added to a 500 mL four-necked flask. Stirring was initiated and the mixture was heated to 50°C. Ammonia (63 g) was added dropwise over 1 h and the mixture was kept at this temperature for 3–4 h. The mixture was cooled to room temperature, allowed to stand for stratification, and separated. 100 mL of dichloromethane was added to the aqueous phase for extraction. The organic phases were combined, 100 mL of deionized water was added, and stirred for 10 min. The mixture was allowed to stand for stratification, and the washing operation was repeated once. Magnesium sulfate (10 g) was added to the organic phase and dried for 30 min. The mixture was filtered and the solvent was removed by rotary evaporation to obtain a colorless to light yellow viscous liquid (73 g). The obtained liquid was subjected to reduced pressure distillation to obtain 60 g of a colorless, viscous, transparent liquid (Intermediate 2).

[0237] Preparation of Intermediate 3: Intermediate 2 (35.45 g), sodium ethoxide (105.64 g), and tetrabutylammonium bromide (1.77 g) were weighed in sequence and added to a pressure-resistant glass bottle. The mixture was stirred at room temperature for 1 hour, and then ethyl carbon-carbon double bond bromine (248.15 mL) was added. The mixture was sealed and the reaction system was heated to 50° C. for 12 hours. After the reaction was completed, the mixture was filtered and the collected filtrate was evaporated to remove the solvent. The resulting viscous liquid was added to 100 mL of dichloromethane, followed by addition of 150 mL of aqueous hydrochloric acid solution (2 wt%) and stirred at room temperature for 30 minutes. The mixture was separated and extracted with 20 mL of dichloromethane. The organic phases were collected and combined, washed with 150 mL of deionized water for 15 minutes, and the organic phase was separated again and collected. The washing step was repeated twice. The resulting organic phase was evaporated to obtain a viscous liquid (Intermediate 3).

[0238] Preparation of Intermediate 4: Intermediate 3 (30 g), epichlorohydrin (17.94 g), triethylamine (19.62 g), and THF (130 mL) were weighed and added to a 250 mL single-necked flask. The mixture was stirred magnetically and heated to 50°C for 5-6 h. The reaction mixture was evaporated to remove the solvent, and column chromatography was performed to obtain 2.4 g of a viscous liquid (90% liquid content, Intermediate 4).

[0239] Preparation of Intermediate 5: Intermediate 4 (6.00 g), THF (15 mL), and sodium hydroxide solution (2.90 g) were weighed sequentially into a 50 mL single-necked flask. Magnetic stirring was initiated and the mixture was incubated at 50°C for 3-4 h. The reaction solution was filtered, the filtrate was collected, and the filtrate was allowed to stand for separation. The organic phase was collected and the solvent was removed by rotary evaporation to yield 5 g of a viscous liquid (Intermediate 5).

[0240] Example 1 Preparation of Polymer Monomer: Intermediate 5 (5.00 g), thiourea (1.68 g), methanol (6 mL), toluene (15 mL), and acetic acid (0.25 mL) were weighed in sequence and added to a 50 mL single-necked flask. The mixture was kept at 40°C for 3 h. After the reaction was complete, 15 mL of toluene and 30 mL of hydrochloric acid solution (1 wt%) were added to the reaction system, and the mixture was stirred for 10 min. The mixture was allowed to stand for stratification, and the organic phase was collected. The organic phase was washed twice with water (30 mL each time), filtered, and the organic solvent was removed by rotary evaporation to obtain a viscous liquid (TBDS).

[0241] The chemical reaction formula for preparing the polymer monomer of Example 1 by sequentially reacting diallyl disulfide in step (1) is as follows:

[0242]

[0243] The H-NMR spectrum of the polymerized monomer of Example 1 prepared in the present application is as follows: Figure 3 shown.

[0244] (2) Stepwise polymerization of monomers in Example 1

[0245] The asymmetric polysulfide monomer TBDS (5 g) was dissolved in NMP (20 g), and diethylene glycol thiol (0.3 g) and triethylamine (0.2 g) were added. The polymerization temperature was controlled to 120°C and the reaction was carried out for 1 h. The mixture was then washed with ethanol (100 g) and dried to obtain 3 g of a semi-solid thermoplastic polymer.

[0246] After mixing a thermoplastic polymer (3 g) and TPO (0.06 g), the mixture is extruded into granules and then injection molded to obtain a semi-polymerized transparent material with uniform transparency. The semi-polymerized transparent material is placed under UV light to induce a double bond cross-linking reaction to obtain a thermosetting resin material.

[0247] In step (2), the chemical reaction formula for polymerizing the asymmetric polysulfide monomer, i.e., the polymerization monomer of Example 1, twice in two steps is as follows:

[0248]

[0249] The thermoplastic polymer obtained by ring-opening polymerization of cyclic sulfide in Example 1 of the present application is a linear polymer containing a carbon-carbon double bond in the side chain, which is solid at room temperature and can be processed by injection molding; by further initiating a polymerization reaction of the carbon-carbon double bond in the side chain of the thermoplastic polymer, cross-linking between the thermoplastic polymers can be achieved to prepare a thermosetting polymer with good thermal properties, namely an optical polymer.

[0250] In Example 1, the infrared spectra of the cyclic sulfide / double bond functional group content in the polymerized monomer, solid thermoplastic polymer and thermosetting resin material are as follows: Figure 4 As shown. Figure 4 It can be seen that compared with the polymer monomer, the solid thermoplastic polymer is - The signal intensity of the nearby CS bond decreases, but the 1580cm - The signal intensity of the nearby C=C bond did not change. It can be seen that in the first polymerization reaction, the S heterocyclopropane ring-opening polymerization occurred, and the corresponding CS bond signal disappeared, but the carbon-carbon double bond was retained in the obtained polymer. Compared with the solid thermoplastic polymer, the thermosetting polymer has a strong affinity for the alkyl group at 600 cm - There is still no infrared signal of CS button nearby, and at the same time 1580cm - The signal of the nearby C=C bond disappears, indicating that polymerization occurs on the carbon-carbon double bond in the second polymerization reaction.

[0251] The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. An optical polymer, characterized in that The optical polymer is formed by polymerizing the monomers shown in the following formula 1: wherein g and h are each selected from integers of 1 to 5, and at least one of g and h is 1; R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; X is an oxygen atom or a sulfur atom, and when g is greater than or equal to 2, multiple Xs are each independently selected from an oxygen atom or a sulfur atom; a, b, m, n, and p are each independently selected from 0, 1, or 2, and a and b are not simultaneously 0; o is 0 or 1, and when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1.

2. The optical polymer according to claim 1, wherein The g is 1, the optical polymer includes a plurality of first polymer chains, the first polymer chains are formed by ring-opening polymerization of the X heterocyclopropane group in Formula 1, and different first polymer chains are cross-linked through the carbon-carbon double bonds in Formula 1.

3. The optical polymer according to claim 2, wherein The structure of the optical polymer contains a repeating unit A as shown below:

4. The optical polymer according to claim 1, wherein The h is 1, the optical polymer includes a plurality of second polymer chains, the second polymer chains are formed by polymerization of the carbon-carbon double bonds in Formula 1, and different second polymer chains are cross-linked by ring-opening polymerization of the X heterocyclopropane group in Formula 1.

5. The optical polymer according to claim 4, wherein The structure of the optical polymer contains a repeating unit B as shown below: In the repeating unit B, s is selected from an integer greater than 2, and the structure of R5 is as follows:

6. The optical polymer according to any one of claims 1 to 5, wherein The heteroatom is selected from a sulfur atom, a nitrogen atom or an oxygen atom.

7. The optical polymer according to claim 1, wherein Based on the total mass of the polymerized monomers being 100%, the mass percentage of sulfur atoms is 20-70%.

8. The optical polymer according to claim 7, wherein The polymerizable monomer is selected from one of the following structures:

9. A method for preparing an optical polymer according to any one of claims 1 to 8, characterized in that: The steps include: A polymerizable monomer as shown in the following formula 1 is provided, wherein g and h are independently selected from integers of 1 to 5, and at least one of g and h is 1; R1 is a cyclic hydrocarbon group containing or not containing heteroatoms, or an aromatic structure; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; X is an oxygen atom or a sulfur atom, and when g is greater than or equal to 2, multiple Xs are each independently selected from an oxygen atom or a sulfur atom; a, b, m, n, and p are each independently selected from 0, 1, or 2, and a and b are not both 0; o is 0 or 1, and when h is greater than or equal to 2, multiple -(CO) o o in CR2=CR3(R4) is independently selected from 0 or 1; Initiating a first polymerization reaction of the first polymerizable functional group in Formula 1 to produce a linear thermoplastic polymer, wherein the first polymerizable functional group is an X heterocyclopropane group or a carbon-carbon double bond having a functionality of 1 in the structure of Formula 1; Initiating a second polymerization reaction of a second polymerizable functional group in the thermoplastic polymer to produce the optical polymer, wherein the second polymerizable functional group is the X heterocyclopropane group or the carbon-carbon double bond in the structure of Formula 1, and the second polymerizable functional group is different from the first polymerizable functional group.

10. The method for preparing an optical polymer according to claim 9, wherein: When the first polymerizable functional group or the second polymerizable functional group is the X heterocyclopropane group, the polymerization reaction adopts anionic polymerization or cationic polymerization; When the first polymerizable functional group is the carbon-carbon double bond, the polymerization reaction adopts free radical polymerization; when the second polymerizable functional group is the carbon-carbon double bond, the polymerization reaction adopts anionic polymerization, cationic polymerization or free radical polymerization.

11. The method for preparing an optical polymer according to claim 9 or 10, wherein: The g is 1, and the first polymerization reaction is: using an anionic initiator or a cationic initiator to initiate the ring-opening polymerization of the X heterocyclopropane group in the polymerizable monomer to produce a linear thermoplastic polymer; the second polymerization reaction is: adding an anionic initiator, a cationic initiator or a free radical initiator to the linear thermoplastic polymer, and initiating the polymerization and crosslinking of the carbon-carbon double bonds in the linear thermoplastic polymer under light or heating conditions to produce a crosslinked thermosetting polymer.

12. The method for preparing an optical polymer according to claim 9 or 10, wherein: The h is 1, and the first polymerization reaction is: adding a free radical initiator to the polymerizable monomer to initiate polymerization and crosslinking of carbon-carbon double bonds in the polymerizable monomer under light or heating conditions to produce a linear thermoplastic polymer; the second polymerization reaction is: adding an anionic initiator or a cationic initiator to the linear thermoplastic polymer to initiate ring-opening polymerization of the X heterocyclopropane groups in the linear thermoplastic polymer to produce a crosslinked thermosetting polymer.

13. The method for preparing an optical polymer according to claim 9, wherein: The preparation method of the polymerizable monomer is as follows: Compound 2 of the structure shown in Formula 2 and thiourea are heated to reflux in an organic solvent, and a solid product is collected after the reaction is completed; the solid product is dissolved in water, heated to a high temperature, and ammonia water is added to react to obtain compound 3 of the structure shown in Formula 3; Compound 3 of the structure shown in Formula 3, sodium ethoxide, and tetrabutylammonium bromide were added to a reaction flask, stirred at room temperature, and then ethyl carbon-carbon double bond bromine was added. The reaction system was sealed and heated to obtain compound 4 of the structure shown in Formula 4. Compound 4 of formula 4, epichlorohydrin, triethylamine, and THF were added to a reaction flask, magnetic stirring was started, and the temperature was raised to react to obtain compound 5 of formula 5; Add compound 5 of formula 5, THF, and sodium hydroxide solution into a reaction flask, start magnetic stirring, and heat and keep warm to obtain compound 6 of formula 6; In the above formula 2 and the above formula 5, A represents a halogen atom.

14. The method for preparing an optical polymer according to claim 13, wherein: The preparation method of the polymerizable monomer further comprises: Compound 6 of formula 6, thiourea, methanol, toluene and acetic acid were added to a reaction flask, and heated to obtain compound 7 of formula 7.

15. An optical polymer masterbatch, characterized in that: The first polymer or the second polymer is formed by polymerizing a monomer as shown in the following formula 1; Wherein, the first polymer is a linear polymer formed by the polymerization monomer through X-heterocyclopropane ring-opening polymerization, and the second polymer is a linear polymer formed by the polymerization monomer through carbon-carbon double bond polymerization; In Formula 1, R1 is a cyclic hydrocarbon group or an aromatic structure containing or not containing heteroatoms; R2, R3, and R4 are each independently selected from one of H, -CH3, -CH2CH3, Cl, I, and Br; and X is an oxygen atom or a sulfur atom. a, b, m, n, and p are each independently selected from 0, 1, or 2, and a and b are not both 0; o is 0 or 1; g and h are each selected from integers between 1 and 5, and at least one of g and h is 1.

16. The optical polymer masterbatch according to claim 15, wherein The optical polymer further comprises an initiator and an auxiliary agent.

17. The optical polymer masterbatch according to claim 16, wherein The auxiliary agent is selected from at least one of fillers, dyes, antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, release agents, polymerization regulators, and cross-linking accelerators.

18. An optical element, characterized in that: The optical element comprises the optical polymer according to any one of claims 1 to 8 or the optical polymer produced by the method according to any one of claims 9 to 14; or the optical element is made of the optical polymer masterbatch according to any one of claims 15 to 17.

19. The optical element according to claim 18, wherein The optical element is an optical lens, an optical film, a light guide plate, an optical disc or a lens.

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