CN114702655A

CN114702655A - Polycarbonate and preparation method and application thereof

Info

Publication number: CN114702655A
Application number: CN202210357342.3A
Authority: CN
Inventors: 王公应; 王庆印; 邹海良; 陈辰; 邹胜; 孙腾; 李晨
Original assignee: Huawei Technologies Co Ltd; Chengdu Organic Chemicals Co Ltd of CAS
Current assignee: Huawei Technologies Co Ltd; Chengdu Organic Chemicals Co Ltd of CAS
Priority date: 2022-04-06
Filing date: 2022-04-06
Publication date: 2022-07-05
Anticipated expiration: 2042-04-06
Also published as: CN114702655B

Abstract

The embodiment of the application provides a polycarbonate, which comprises a structural unit shown as a formula (I):

in formula (I), X is independently selected from oxygen atom, sulfur atom, sulfuryl or sulfoxide group at each occurrence; ar (Ar)₁、Ar₂Each occurrence is independently selected from

Or

The marked locations represent the attachment locations; r¹、R²、R³、R⁴、R⁵Each occurrence is independently selected from a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, or an atom or atomic group that may substitute for the above groups, R¹‑R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; a. b, c are independently selected from integers between 1 and 4 at each occurrence, and d, e are independently selected from integers between 1 and 3 at each occurrence. The polycarbonate has high refractive index, proper Tg and low internal stress. The embodiment of the application also provides a preparation method and application of the polycarbonate.

Description

Polycarbonate and preparation method and application thereof

Technical Field

The embodiment of the application relates to the technical field of optical materials, in particular to polycarbonate and a preparation method and application thereof.

Background

Polycarbonate (PC) materials are widely used for manufacturing optical products such as optical lenses and optical films because of their advantages such as light weight, impact resistance, and easy processing and molding. With the continuous pursuit of optical products for high optical performance, the demand for PC materials with high refractive index is particularly urgent. However, some existing polycarbonate materials are often accompanied by phenomena such as too high glass transition temperature (Tg) or too large internal stress while the refractive index is increased, which results in increased difficulty in injection molding and poor imaging effect of the obtained optical product. Therefore, there is a need to develop a new PC material that can combine a high refractive index, low internal stress, and a suitable Tg.

Disclosure of Invention

In view of this, embodiments of the present application provide a polycarbonate, and a preparation method and an application thereof, so as to solve the problem that the existing polycarbonate material cannot achieve high refractive index, low internal stress, and appropriately low Tg to some extent.

Specifically, a first aspect of embodiments herein provides a polycarbonate comprising structural units represented by formula (I):

The marked positions represent the attachment positions;

wherein R is¹、R²、R³、R⁴、R⁵Independently at each occurrence, is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, or an atom or atom group that may substitute for the above groups, R¹-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; a. b, c are independently selected from integers between 1 and 4 at each occurrence, and d, e are independently selected from integers between 1 and 3 at each occurrence.

In the polycarbonate provided by the first aspect of the embodiments of the present application, the structural unit represented by formula (I) has two aromatic rings Ar₁The existence of the fluorene rigid aromatic polycyclic structure can improve the refractive index of the polycarbonate; meanwhile, the fluorene structure enables the central aromatic polycyclic structure to be a twisted structure, so that the steric hindrance between polymer molecular chains is increased in the injection molding processing process, the orientation of the material can be reduced, and the birefringence phenomenon of the material can be further reduced; in the main chain of the structural unit, -X-Ar₂The existence of the compound can further improve the refractive index of the material, wherein the bridging group X containing the heteroatom can endow the main chain of the polymer with a certain rotation space, so that the glass transition temperature of the polymer is not high, the polymer can be molded at a lower temperature by injection molding, and the existence of the X can reduce the residual internal stress of the polycarbonate material in the processing process and relieve the birefringence phenomenon of the material.

In an embodiment of the present application, the structural unit represented by formula (I) includes at least one of the following structural units represented by formulae (I-a) and (I-b):

in an embodiment of the present application, the polycarbonate has a total molar ratio of structural units represented by formula (I) of greater than or equal to 10%. The larger the total molar proportion of the structural units of the formula (I) is, the more favorable the internal stress of the polycarbonate material is and the glass transition temperature thereof is reduced to some extent.

In some embodiments of the present disclosure, the polycarbonate further comprises a structural unit represented by formula (II) and/or a structural unit represented by formula (III):

in formula (II), R is selected from alkylene, cycloalkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, or a single bond; each occurrence of Y is independently selected from the group consisting of alkylene groups having 1 to 4 carbon atoms and each occurrence of p is independently selected from the group consisting of integers of 0 to 5; ar is independently selected for each occurrence from substituted or unsubstituted arylene;

in the formula (III), R' is selected from substituted or unsubstituted C₆-C₂₀Cycloalkylene, Z is independently selected for each occurrence from alkylene of 1-4 carbon atoms or a single bond.

The monomers corresponding to the structural units shown in the formulas (II) and (III) are easy to obtain, the preparation cost of the polycarbonate material is reduced, and the structural units can participate in adjusting the refractive index of the polycarbonate material, wherein the structural unit shown in the formula (II) is beneficial to improving the refractive index and the glass transition temperature of the polycarbonate material, and the structural unit shown in the formula (II) is beneficial to improving the Abbe number of the polycarbonate material.

In the present embodiment, in formula (II), the substituent on the substituted arylene group and the substituted heteroarylene group is independently selected from one or more of a deuterium atom, a tritium atom, a halogen atom, a hydroxyl group, a thiol group, an amino group, a cyano group, an ester group, and a substituted or unsubstituted alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, and a heteroaryl group.

In some embodiments of the present application, in formula (II), both Y are ethylene and both p are 1. In this case, monomers corresponding to the structural units of the formula (II) are more readily available.

In some embodiments of the present application, the structural unit represented by formula (II) includes at least one of the structural units described in the following cases:

1) r is a substituted or unsubstituted 9-fluorenyl group, and Ar is independently at each occurrence a substituted or unsubstituted phenylene group;

2) r is substituted or unsubstituted 9-fluorenyl, and Ar is independently at each occurrence substituted or unsubstituted naphthylene;

3) r is a single bond and each occurrence of Ar is independently substituted or unsubstituted naphthylene.

In some embodiments of the present application, in formula (III), R' is selected from the group consisting of substituted or unsubstituted tricyclodecanediyl, pentacyclopentadecanediyl, tetracyclododecanediyl. The polycyclic cycloalkylene R' enables the structural unit shown in the formula (III) to have Tg equivalent to that of the monomer corresponding to the structural unit shown in the formula (III), and can adjust the refractive index of the polycarbonate material to be in a required range.

In some embodiments of the present application, the polycarbonate has a total molar ratio of structural units represented by formula (II) in the range of 10% to 90%. The presence of the structural unit of formula (II) in an appropriate amount helps to increase the refractive index of the polycarbonate material and provides the material with a higher Tg for processing.

In some embodiments of the present application, the polycarbonate has a total molar ratio of structural units represented by formula (III) in the range of 30% to 90%. The presence of a suitable amount of structural units of formula (III) helps to increase the abbe number of the polycarbonate material and adjust its refractive index to the desired range, giving it an easy-to-process Tg.

In the embodiment of the present application, the number average molecular weight of the polycarbonate is 10000-50000. In this case, the polycarbonate material can well balance molding convenience and good mechanical properties.

In the embodiment of the present application, the glass transition temperature of the polycarbonate is 130-160 ℃. In this case, the polycarbonate can be molded at a relatively low molding temperature, and the molded article can have good heat resistance.

In an embodiment of the present application, the polycarbonate has a refractive index of greater than or equal to 1.56. In this case, the molded sheet obtained by molding the polycarbonate material has a small thickness.

In an embodiment of the present application, the abbe number of the polycarbonate is greater than 16. The molded sheet obtained by molding the polycarbonate material has a low dispersion level.

In an embodiment of the present application, the polycarbonate has a visible light transmittance of 87% or more.

In a second aspect, embodiments herein also provide a resin composition comprising a polycarbonate as described in the first aspect of embodiments herein.

The resin composition containing the polycarbonate disclosed by the embodiment of the application has the advantages that the processing and forming temperature is low, the resin composition can be conveniently formed through an injection molding process, the residual internal stress in the injection molding process is less, the internal force birefringence phenomenon is less, and the imaging quality of the obtained forming sheet is high.

In an embodiment of the present application, the resin composition further includes one or more of a filler, a dye, an antioxidant, a light stabilizer, a heat stabilizer, an ultraviolet absorber, a plasticizer, a flame retardant, an antistatic agent, and a mold release agent.

In a third aspect, embodiments also provide an optical article comprising a polycarbonate as described in the first aspect of embodiments herein, or a resin composition as described in the second aspect of embodiments herein.

In embodiments of the present application, the optical article comprises an optical lens, an optical film, an optical disc, a light guide plate, or a display panel.

In an embodiment of the present invention, the optical lens includes a spectacle lens, an image pickup lens, a sensor lens, an illumination lens, and an imaging lens.

The polycarbonate provided by the embodiment of the application has high refractive index, low glass transition temperature and high toughness, is convenient to machine and mold, and the optical product obtained by machining and molding has light weight. When the optical product is an optical lens, the product also has good imaging effect.

Because the polycarbonate has high refractive index, lower glass transition temperature, high convenience of processing and forming and less internal stress residue in the processing process, the thickness of the obtained optical product can be thinner, and the optical performance and the mechanical performance are excellent.

In a fourth aspect, embodiments of the present application further provide an apparatus comprising an optical article as described in the third aspect of embodiments of the present application.

In a fifth aspect, an embodiment of the present application provides an electronic device with a camera module, wherein the camera module includes a camera lens, and the camera lens is prepared by using the polycarbonate according to the first aspect of the embodiment of the present application, or the resin composition according to the second aspect of the embodiment of the present application.

In a sixth aspect, embodiments herein provide a method for preparing a polycarbonate, including:

preparing a polycarbonate by carrying out a melt polymerization reaction on raw materials containing a dihydroxy monomer shown in a formula (I) and a carbonic acid diester, wherein the polycarbonate comprises a structural unit shown in a formula (I):

in formula (I) and formula (I), X is independently selected at each occurrence from an oxygen atom, a sulfur atom, a sulfone group, or a sulfoxide group; ar (Ar)₁、Ar₂Each occurrence is independently selected from

The positions marked represent the positions of the linkage to formula (I), formula (I):

wherein R is¹、R²、R³、R⁴、R⁵Each occurrence is independently selected from hydrogenAn atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, or an atom or atom group that may substitute the above groups, R¹-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; a. b, c are independently selected from integers between 1 and 4 at each occurrence, and d, e are independently selected from integers between 1 and 3 at each occurrence.

The preparation method of the polycarbonate material has simple process and easy operation.

In some embodiments of the present application, the starting material further comprises at least one of the dihydroxy monomers of formulas (ii) and (iii):

in formula (iii), R' is selected from substituted or unsubstituted C₆-C₂₀Cycloalkylene, Z is independently selected for each occurrence from alkylene of 1-4 carbon atoms or a single bond.

In some embodiments of the present application, the dihydroxy monomer of formula (i) is prepared by the following method:

reacting a phenolic compound shown in a formula (A) with a fluorene compound shown in a formula (B) under the protection of inert gas to obtain an aromatic diphenol compound shown in a formula (C);

reacting an aromatic diphenol compound shown in a formula (C) with ethylene carbonate under the condition of an alkaline catalyst to obtain a dihydroxy compound shown in a formula (i);

each occurrence of X is independently selected from the group consisting of an oxygen atom, a sulfur atom, a sulfone group, and a sulfoxide group;

ar above₁、Ar₂Each occurrence is independently selected from

Ar₁' Each occurrence is independently selected from

The marked locations represent the attachment locations;

r is as defined above¹、R²、R³、R⁴、R⁵Independently at each occurrence, is selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, or an atom or atom group that may substitute for the above groups, wherein in formula (B), R¹-R²Any adjacent substituent in (a) may be connected to form a cyclic structure; in the formula (A), R³-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; in the formula (C), R¹-R⁵Any adjacent substituent in the formula (I) can be connected into a ring structure; each occurrence of a, b, c, d 'is independently selected from an integer between 1 and 4, each occurrence of d, e is independently selected from an integer between 1 and 3, and each occurrence of c' is independently selected from an integer between 1 and 5.

The preparation method of the dihydroxy monomer shown in the formula (i) is simple in process and easy to operate.

Detailed Description

The refractive index of a conventional Polycarbonate (PC) optical material is not high, and a common technical means for increasing the refractive index of PC generally increases the content of aromatic groups in the material, but this causes the glass transition temperature (Tg) of the PC material to be too high, so that the difficulty of injection molding processing of the PC material becomes large; the introduction of excessive aromatic rings can also cause more internal stress to be remained in the injection molding process, so that the obtained PC material is easy to generate birefringence, interference is easy to occur in the imaging process, and then color fringes are generated, thereby affecting the imaging effect. In addition, excessive aromatic rings also reduce the abbe number of PC materials, increase dispersion, and cause ghost images and color fringes. In view of this, embodiments of the present application provide a novel polycarbonate material that can achieve a compromise between high refractive index, low internal stress, and a suitably low Tg.

The technical solution of the present application is explained in detail below.

Embodiments of the present application provide a polycarbonate comprising a structural unit represented by formula (I):

in formula (I), X is independently selected from oxygen atom (O), sulfur atom (S), sulfuryl (-SO) at each occurrence₂-) or a sulfoxide group (-SO-); ar (Ar)₁、Ar₂Each occurrence is independently selected from

(i.e., substituted or unsubstituted phenylene) or

(i.e., substituted or unsubstituted naphthylene), the marked positions represent the attachment positions to formula (I):

wherein R is¹、R²、R³、R⁴、R⁵Each occurrence is independently selected from a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, a heteroaryl group, or an atom or group of atoms which may substitute for the above groups, R¹-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; a. b, c are independently selected from integers between 1 and 4 at each occurrence, and d, e are independently selected from integers between 1 and 3 at each occurrence.

The polycarbonate provided by the embodiment of the application has a structural unit shown as a formula (I), wherein the structural unit is provided with two aromatic rings Ar₁The existence of fluorene rigid aromatic polycyclic structure, according to the lorentz-lorenz equation, can be mentioned by increasing the number of aromatic rings in the moleculeHigh refractive index of polycarbonate; meanwhile, because the fluorene structure is a twisted structure, the steric hindrance between polymer molecular chains can be increased, the orientation of the material can be reduced, and the birefringence phenomenon of the material can be reduced in the injection molding processing process; in the main chain of the structural unit, -X-Ar₂The existence of the compound can further improve the refractive index of the material, wherein the bridging group X containing the heteroatom can endow a polymer main chain with a certain rotation space, so that the glass transition temperature of the polymer main chain is not high, and the polymer can be molded and formed at a lower temperature; and the existence of X can reduce the residual internal stress of the polycarbonate material in the processing process and relieve the birefringence phenomenon of the material.

Therefore, the polycarbonate provided by the embodiment of the present application can achieve both of optical properties such as a high refractive index, low birefringence, a high abbe number, and a suitably low Tg. For example, the polycarbonate provided by the application can have a higher refractive index under the condition that the Abbe number is basically consistent with that of the existing polycarbonate material; or the polycarbonate provided by the application can have higher Abbe number under the condition that the refractive index is basically consistent with that of the existing polycarbonate material, and the influence of dispersion on material imaging is reduced.

In the formula (I), when X is an oxygen atom, the synthesis process of the aromatic dihydroxy compound monomer used for preparing the polycarbonate is simple, the production efficiency is high, and the cost is relatively low. Compared with the case that X is an O atom and X is a sulfur-containing group such as an S atom, a sulfuryl group or a sulfoxide group, the optical properties such as the refractive index of the polycarbonate can be improved better, but the synthesis difficulty of the monomer corresponding to the structural unit of the formula (I) is slightly high. Further, when X is an S atom, the refractive index of the polycarbonate can be more effectively improved, the internal stress of the material can be reduced, Tg can be reduced, and the like; when X is a sulfone group or a sulfoxide group, the Abbe number is higher under the condition of the same refractive index compared with the polycarbonate/polyester material without the heteroatom, and even under the condition that the polycarbonate of the application has basically the same refractive index, the Abbe number of the X is the sulfone group or the sulfoxide group is higher than that of the X is the S atom.

In the present application, the "atom or atomic group which may substitute for the above-mentioned group" means an atom or atomic group which may substitute for a hydrogen atom, a halogen atom, a hydroxyl group (-OH), a thiol group (-SH), a cyano group (-CN), an amino group, an ester group, an alkyl group, an alkoxy group, an epoxy group, an alkenyl group, an aryl group, an aryloxy group, and specifically, for example, an isotope atom (deuterium atom, tritium atom, etc.) of a hydrogen atom, a thiocyano group (-SCN), an isothiocyanate group (-NCS), an amide group, an imide group, a ketone group, a borane group, a silane group, a siloxane group, an aryl group containing a ring hetero atom (i.e., heteroaryl group), an aryloxy group containing a ring hetero atom (i.e., heteroaryloxy group), and the like.

In the present application, the halogen atom may be a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). In the present embodiment, the alkyl group may be an alkyl group having 1 to 20 carbon atoms. In some embodiments, the number of carbon atoms in the alkyl group is from 1 to 10; in other embodiments, the alkyl group has from 1 to 6 carbon atoms. Wherein the alkyl group may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group may be an unsubstituted alkyl group or a substituted alkyl group. Exemplary alkyl groups can be methyl, ethyl, propyl, butyl, and the like. Similarly, the carbon atom of an alkoxy group herein may be 1 to 20. In some embodiments, the alkoxy group has from 1 to 10 carbon atoms; in other embodiments, the alkoxy group has from 1 to 6 carbon atoms. The alkoxy group may be a linear or branched alkoxy group. The alkoxy group may be an unsubstituted alkoxy group or a substituted alkoxy group. Exemplary alkoxy groups can be methoxy, ethoxy, propoxy, butoxy, and the like. In the embodiment of the present application, the number of carbon atoms of the epoxy group may be 3 to 20, for example, 3 to 15 or 4 to 12. The cycloalkyl group may be a substituted cycloalkyl group, or an unsubstituted cycloalkyl group. The number of carbon atoms of the alkenyl group may be 2 to 20, and for example, 2 to 10 or 2 to 6. The alkenyl group may be a linear alkenyl group or a branched alkenyl group; the alkenyl group may be an unsubstituted alkenyl group or a substituted alkenyl group.

In the embodiments, the number of carbon atoms of the aryl group may be 6 to 30, and further, the number of carbon atoms of the aryl group may be 6 to 20; further, the number of carbon atoms of the aryl group may be 6 to 10. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be an unsubstituted aryl group or a substituted aryl group. Exemplary aryl groups can be phenyl, naphthyl, biphenyl, binaphthyl, fluorenyl, methyl-substituted phenyl, deuterated t-butyl-substituted phenyl, and the like. Similarly, the number of carbon atoms of the aryloxy group in the present application may be 6 to 30, and further, the number of carbon atoms of the aryloxy group may be 6 to 20; further, the number of carbon atoms of the aryloxy group may be 6 to 10. The aryloxy group may be a monocyclic aryloxy group or a polycyclic aryloxy group. The aryloxy group may be a non-substituted aryloxy group or a substituted aryloxy group.

The amino group in the present application may be an unsubstituted amino group (i.e., a primary amino group (-NH-))₂) And may be substituted amino groups (including secondary amino groups and tertiary amino groups). Wherein, the substituent in the substituted amino group can comprise one or more of alkyl, aryl and heteroaryl. An exemplary alkyl group can be NH₂Methylamino, dimethylamino, diphenylamino, dimethylphenylamino and the like. The ester group may include carbonate, sulfonate, phosphate. The ester group may be an unsubstituted ester group, or a substituted ester group; the ester group may specifically be an alkyl ester group, an alkenyl ester group, an aryl ester group or the like.

In an embodiment of the present application, the substituent R in the recurring unit of formula (I)¹、R²、R³、R⁴、R⁵The specific selection can be made according to the actual functional requirements. Wherein, the selection of chain alkyl and alkoxy substituent groups is helpful for increasing the toughness of the polycarbonate and reducing internal stress. The polar groups such as hydroxyl, amino, ester and the like are selected, so that the adhesive property of the polycarbonate and the compatibility with other optical resins can be improved; the selection of the substituent group containing a cyclic structure and an aromatic ring can improve the refractive index, heat resistance and rigidity of the material; the choice of a group containing an S atom can increase the refractive index of the material.

In the present application, "formula (I)," R¹-R⁵Wherein any adjacent substituents may be linked to form a cyclic structure "means specifically that R¹、R²、R³、R⁴、R⁵Any two, three or four adjacent in the formula (I) can be connected to form a cyclic structure, the formed cyclic structure can be a saturated or unsaturated carbocyclic ring, a saturated or unsaturated heterocyclic ring, and a heteroatom in the heterocyclic ring can be nitrogen,Sulfur, oxygen, boron, silicon, and the like. Specifically, a plurality of adjacent substituents on the same aromatic ring may be linked to form a ring (for example, adjacent R' s¹Connected in a ring with adjacent ones of the plurality of R²Linked to form a ring, located in the same Ar₁Or Ar₂Upper adjacent R³Adjacent R connected to form a ring⁴Connected to form a ring or adjacent R⁵Linked to form a ring, etc.), or adjacent substituents on different aromatic rings linked to form a ring (e.g., adjacent R's)¹And R²Linked to form a ring, Ar₂Substituent on with Ar₁The substituents on which are linked to form a ring, two Ar₁The substituents on the above are linked to form a ring, etc.). In the formula (I), R not participating in the formation of a cyclic structure¹、R²、R³、R⁴、R⁵Each independently selected from a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, or an atom or atomic group that may substitute for the above group.

In some embodiments of the present application, the polycarbonate may include only the structural unit represented by formula (I), that is, the structural unit represented by formula (I) accounts for 100% of the total mole of the polycarbonate. It is understood that the polycarbonate may be a polycarbonate comprising a structural unit represented by the formula (1) (in this case, the polycarbonate is a homopolymer); or a structure unit containing a plurality of different structures represented by the formula (1) (in this case, the polycarbonate is a copolymer), and for example, the polycarbonate contains two kinds of structure units represented by the following formulas (I-a) and (I-b).

In some embodiments of the present application, the structural unit represented by formula (I) includes at least one of the structural unit represented by formula (I-a) and the structural unit represented by formula (I-b). That is, the polycarbonate in this case contains at least one of the structural unit represented by the following formula (I-a) and the structural unit represented by the following formula (I-b).

In some embodiments, in formula (I-a) aboveR of (A) to (B)¹-R³Are each a hydrogen atom; in another embodiment, R¹、R²Are all hydrogen atoms, in which case R is on the aromatic ring to which the 9-fluorenyl group is bonded³Are all phenyl groups. In some embodiments, R in formula (I-b)¹-R⁵Are all hydrogen atoms.

In other embodiments of the present disclosure, the polycarbonate can also include structural units represented by formula (I) as well as other structural units. In particular, other monomers can be added as required during the preparation of the polycarbonates to obtain corresponding further structural units. When the polycarbonate contains other structural units than the structural unit represented by the formula (I), the total molar ratio of the structural units represented by the formula (I) may be 10% or more, for example, 10% to 90%. Wherein, the larger the total molar ratio of the structural units shown in the formula (I), the more beneficial the internal stress of the polycarbonate material is reduced, and the glass transition temperature is reduced. In some embodiments, the total molar proportion of structural units of formula (I) in the polycarbonate can be greater than 30%, or even greater than 50%, which can better reduce the Tg of the polycarbonate material.

In some embodiments of the present disclosure, the polycarbonate further comprises structural units represented by formula (II):

in formula (II), R is selected from alkylene, cycloalkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, or a single bond; each occurrence of Y is independently selected from the group consisting of alkylene groups having 1 to 4 carbon atoms and each occurrence of p is independently selected from the group consisting of integers of 0 to 5; ar is independently selected for each occurrence from substituted or unsubstituted arylene. The monomer of the structural unit shown in the formula (II) is easy to obtain, the preparation cost of the polycarbonate material can be reduced by a simple commercial monomer, the rigidity of the material can be improved to a certain extent, the mechanical property can be harmonized, and the refractive index of the polycarbonate material can be harmonized in a customized manner, for example, the refractive index can be adjusted within the range of 1.64-1.7.

In the present embodiment, when R is an alkylene group in the formula (II), the number of carbon atoms of the alkylene group is 1 to 10, for example, 1 to 6, further 1 to 4. The alkylene group may be a linear or branched alkylene group; the alkylene group may be a substituted or unsubstituted cycloalkylene group. Exemplary alkylene groups can be methylene, ethylene, t-butylene, and the like. Among them, the straight chain alkylene group is more advantageous in increasing the toughness of the polycarbonate. When R in (II) is a cycloalkylene group, the number of carbon atoms may be 3 to 20, for example, 3 to 15, further 5 to 15, or 6 to 18. Cycloalkylene is a radical obtained by replacing a cycloalkyl group by one hydrogen atom. The cycloalkylene group may be substituted or unsubstituted.

When R in (II) is a substituted or unsubstituted arylene group, it may specifically be a substituted or unsubstituted C₆-C₃₀Arylene radicals, e.g. substituted or unsubstituted C₆-C₂₀Arylene, further e.g. substituted or unsubstituted C₆-C₁₀An arylene group. Wherein the substituted or unsubstituted arylene group may be monocyclic (e.g., phenylene) or polycyclic (e.g., polycyclic)

May be referred to as "fluorenylidene" or "9-fluorenyl"). When R in (II) is a substituted or unsubstituted heteroarylene group, it may specifically be a substituted or unsubstituted C₃-C₃₀Heteroarylene, e.g. substituted or unsubstituted C₅-C₂₀Heteroarylene, further e.g. substituted or unsubstituted C₆-C₁₂A heteroarylene group. The substituted or unsubstituted heteroarylene group may be monocyclic or polycyclic. The ring hetero atom in the heteroarylene group may be one or more of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and the like.

In the present embodiment, in formula (II), the substituent on the substituted arylene group or substituted heteroarylene group is independently selected from one or more of deuterium atom, tritium atom, halogen atom, hydroxyl group, thiol group, cyano group, amino group, ester group, and substituted or unsubstituted alkyl group, alkoxy group, cycloalkyl group, alkenyl group, aryl group, aryloxy group, and heteroaryl group. Among them, the specific selection range of the substituents such as halogen atom, hydroxyl group, thiol group, cyano group, amino group, ester group, alkyl group, alkoxy group, cycloalkyl group, alkenyl group, aryl group, aryloxy group, heteroaryl group and the like may be the same as in the aforementioned formula (I).

In some embodiments of the present application, in formula (II), R is selected from substituted or unsubstituted 9-fluorenyl (unsubstituted 9-fluorenyl is represented by

) Or to a single bond. In some embodiments of the present application, each occurrence of Ar is independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene. Among them, the substituent on the substituted naphthylene group is, for example, phenyl, naphthyl, alkyl, etc.

In some embodiments, the-Ar-R-Ar-group in formula (II) is selected from the group consisting of substituted or unsubstituted:

wherein the substituted or unsubstituted group (1) corresponds to the formula (II) in which R is a substituted or unsubstituted 9-fluorenyl group, Ar is a substituted or unsubstituted phenylene group; the substituted or unsubstituted (2) group corresponds to the formula (II) in which R is a substituted or unsubstituted 9-fluorenyl group, Ar is a substituted or unsubstituted naphthylene group; the substituted or unsubstituted group (3) corresponds to the formula (II) in which R is a single bond and Ar is a substituted or unsubstituted naphthylene group.

In some embodiments of the present application, each occurrence of Y is independently selected from the group consisting of alkylene groups having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, and the like; p is independently at each occurrence an integer selected from 1 to 5, for example 1, 2, 3, 4, 5. In some embodiments, both Y in formula (II) are ethylene and both p are 1. In this case, monomers corresponding to the structural unit represented by the formula (II) are more readily available.

In the present application, when the polycarbonate contains a structural unit represented by the formula (II), it may be a structural unit containing one structure represented by the formula (II), or a structural unit containing a plurality of different structures represented by the formula (II). In some embodiments of the present application, the structural unit represented by formula (II) includes at least one of the following structural units represented by formulae (II-a), (II-b), and (II-c):

r is as defined above⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²Each occurrence is independently selected from one or more of hydrogen atom, deuterium atom, tritium atom, halogen atom, hydroxyl group, thiol group, cyano group, amino group, ester group, and substituted or unsubstituted alkyl, alkoxy, cycloalkyl, alkenyl, aryl, aryloxy, heteroaryl; each occurrence of f, g, h, l is independently selected from integers between 1 and 4, each occurrence of i, j is independently selected from integers between 1 and 3, and each occurrence of k is independently selected from integers between 1 and 2.

In this case, the formula (II-a) corresponds to the formula (II) wherein R is a substituted or unsubstituted 9-fluorenyl group and Ar is a substituted or unsubstituted phenylene group. Formula (II-b) corresponds to formula (II) wherein R is substituted or unsubstituted 9-fluorenyl, Ar is substituted or unsubstituted naphthylene; the formula (II-b) corresponds to the formula (II) wherein R is a single bond and Ar is a substituted or unsubstituted naphthylene group.

In the embodiment of the present application, the total molar ratio of the structural unit represented by the formula (II) in the polycarbonate is 10% to 90%, and specifically, the total molar ratio of the structural unit represented by the formula (II) may be 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, or the like. In some embodiments, the total molar proportion of structural units represented by formula (II) is from 20% to 80%. The existence of a proper amount of the structural unit shown in the formula (II) is helpful for improving the refractive index of the polycarbonate material and enabling the material to have a higher glass transition temperature suitable for processing.

In some embodiments of the present disclosure, the polycarbonate further comprises structural units represented by formula (III):

in the formula (III), R' is selected from substituted or unsubstituted C₆-C₂₀Cycloalkylene, Z is independently selected for each occurrence from alkylene of 1-4 carbon atoms or a single bond. The monomer of the structural unit shown in the formula (III) is easy to obtain, the preparation cost of the polycarbonate material can be reduced by a simple commercial monomer, the monomer corresponding to the structural unit shown in the formula (I) has the Tg which is equivalent to that of the monomer, and the monomer can participate in adjusting the refractive index of the polycarbonate material, for example, the refractive index can be adjusted within the range of 1.56-1.63.

In the present embodiment, when Z in formula (III) is an alkylene group, it may be a linear alkylene group or a branched alkylene group. In some embodiments, Z is a single bond, methylene, ethylene, or propylene.

In the present embodiment, in R', the substituent in the substituted cycloalkylene group may be selected from one or more of deuterium atom, tritium atom, halogen atom, hydroxyl group, thiol group, cyano group, amino group, ester group, and substituted or unsubstituted alkyl group, alkoxy group, aryl group, aryloxy group, and heteroaryl group. Wherein, the specific selection range of the substituent can be as described in the application.

In some embodiments of the present application, R' in formula (III) is selected from substituted or unsubstituted C₆-C₁₈Cycloalkylene further selected from substituted or unsubstituted C₁₀-C₁₅A cycloalkylene group. The cycloalkylene group may be a monocyclic or polycyclic cycloalkylene group, and a polycyclic cycloalkylene group is preferable.

In some embodiments, the R' is selected from substituted or unsubstituted tricyclodecanediyl, tetracyclododecanediyl, pentacyclopentadecane diyl. Wherein the unsubstituted tricyclodecanediyl group is represented by

Unsubstituted tetracyclododecanediyl is represented by

Unsubstituted pentacyclopentadecanediyl is represented by

In the present application, when the polycarbonate contains a structural unit represented by the formula (III), it may be a structural unit containing one structure represented by the formula (III), or a structural unit containing a plurality of different structures represented by the formula (III). In an embodiment of the present invention, the polycarbonate may have a total molar ratio of the structural units represented by the formula (III) of 30% to 90%.

In other embodiments of the present application, the polycarbonate further comprises a structural unit represented by formula (II) as described above, and a structural unit represented by formula (III) as described above. In this case, the polycarbonate includes the structural unit represented by the formula (I), the structural unit represented by the formula (II), and the structural unit represented by the formula (III), and may further include other structural units in some cases.

Wherein the sum of the total molar ratio of the structural unit represented by the formula (II) and the structural unit represented by the formula (III) may be 10% to 80%. The two structural units can participate in adjusting the refractive index of the polycarbonate material together with the structural unit shown in the formula (II), and the obtained polycarbonate material is ensured to have glass transition temperature which is easy to process and stable to store.

In an embodiment of the present application, the number average molecular weight (Mn) of the polycarbonate is 10,000-50,000. The larger the molecular weight is, the better the mechanical property of the material is, and the higher the strength is; but the processing difficulty is increased at the same time, which is not beneficial to processing and forming; when the molecular weight is low, the processing of the material is easy and the molding yield is high. In order to balance the mechanical properties and moldability, in the embodiment of the present application, the number average molecular weight of the above polycarbonate is controlled to 10,000-50,000. In some embodiments, the number average molecular weight of the polycarbonate is 15,000-35,000. In this case, the polycarbonate material has high toughness, high strength, and good processability.

In an embodiment of the present application, the polycarbonate has a Polymer Dispersibility Index (PDI) of 3 or less. PDI refers to the ratio of the weight average molecular weight Mw of a material to its number average molecular weight Mn. Smaller PDI means that the polycarbonates provided herein have a narrower molecular weight distribution and a more uniform property distribution. In some embodiments, the PDI is 1.5 to 2.5, such as 1.5 to 1.2.

In the present embodiment, the glass transition temperature (Tg) of the polycarbonate may be in a range of greater than 100 ℃ and less than or equal to 160 ℃. Specifically, the Tg can be 110, 120, 130, 135, 140, 145, 150, 155, 160 ℃, and the like. The polycarbonate has a suitable glass transition temperature, can be processed and molded by an injection molding process, and can be molded into a product having good heat resistance. In some embodiments, the polycarbonate has a Tg of 130-160 ℃. In other embodiments, the polycarbonate has a Tg of 135-150 ℃.

In an embodiment of the present invention, the refractive index of the polycarbonate is 1.56 or more. In some embodiments, the refractive index may be 1.56 to 1.70. The polycarbonate material has higher refractive index, and the optical lens prepared by the polycarbonate material is beneficial to reducing the thickness of the lens and is beneficial to realizing the lightness and thinness of electronic equipment adopting the optical lens. The refractive index of the polycarbonate can be measured according to ASTM D542 test standard.

In an embodiment of the present application, the abbe number of the polycarbonate is more than 16. The abbe number is an index of the dispersive power of the transparent dielectric material, and the dispersion affects the imaging effect. The abbe number of the material can be measured according to ASTM D542 test standard. Generally, the smaller the abbe number of the material, the more severe the dispersion and the lower the visual clarity. The higher Abbe number can control the dispersion phenomenon of the material at a lower level. In order to balance the low dispersion and suitably high refractive index of optical lenses made of polycarbonate materials, in some embodiments of the present application, the abbe number of the polycarbonate may be controlled to be 18 to 40, for example, 19, 20, 21, 22, 25, 3o, 32, 35, 40, and the like.

In an embodiment of the present application, the polycarbonate has a visible light transmittance of 87% or more. In some embodiments, the polycarbonate has a visible light transmission of greater than or equal to 88%; in other embodiments, the polycarbonate has a visible light transmission of greater than or equal to 90%. The visible light transmittance of the polycarbonate is measured according to ASTM D1003 test standard.

From the above description, it is clear that the polycarbonate provided in the examples of the present application can simultaneously achieve good processing moldability and excellent optical properties.

Correspondingly, the embodiment of the application also provides a preparation method of the polycarbonate. Specifically, the preparation method of the polycarbonate comprises the following steps:

The position marked represents the connection position with the formula (I) and the formula (I);

wherein R is¹、R²、R³、R⁴、R⁵Each occurrence is independently selected from a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group, or an atom or atomic group that may substitute for the above groups, R¹-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; a. b, c are independently selected from integers between 1 and 4 at each occurrence, and d, e are independently selected from integers between 1 and 3 at each occurrence.

The above melt polymerization process may specifically include: 1): melting the raw materials; 2): the molten raw materials are subjected to transesterification polymerization in the presence of a catalyst under vacuum to obtain polycarbonate.

In step 1), the raw material, dihydroxy monomer and carbonic acid diester, may be melted by heating in an inert gas atmosphere (e.g., nitrogen atmosphere) at a temperature controlled within the range of 100 ℃ to 300 ℃, wherein the temperature of the heating and melting may be controlled stepwise, for example, by first raising the temperature to a first temperature and holding the temperature for a certain period of time, and then raising the temperature to a second higher temperature and holding the temperature for a certain period of time. Specifically, for example, the temperature is firstly increased to 100-180 ℃ and is preserved for 15-30 min, and then the temperature is increased to 180-300 ℃ and is preserved for 20-60 min. Stirring may be performed simultaneously during the heating and melting.

In the step 2), after the raw materials are completely melted, vacuumizing is carried out, so that the molten raw materials are subjected to ester exchange and polycondensation simultaneously under the conditions of vacuum and a catalyst to obtain polycarbonate; or the raw materials in the molten state are subjected to ester exchange under the conditions of vacuum and catalyst and then subjected to polycondensation to obtain the polycarbonate. Wherein the catalyst can be added and mixed with the dihydroxy monomer and the carbonic acid diester, namely, the catalyst is already in the reaction raw materials during the heating and melting process. The degree of vacuum in the above transesterification polymerization may be 10Pa to 3X 10⁵Pa. Specifically, the degree of vacuum during transesterification may be lower than that during polycondensation. For example, the absolute pressure during transesterification may be from 50Pa to 500Pa, and the absolute pressure during polycondensation may be from 50Pa to 150 Pa. The stirring operation may be maintained during the transesterification polymerization of step 2). The time for the transesterification polymerization is 30min or more, generally 60min or more. After the whole melt polycondensation reaction is finished, the pressure can be restored to normal pressure, the reacted materials are dissolved by a first organic solvent (such as dichloromethane, trichloromethane and the like), and then are reprecipitated by a second organic solvent (such as ethanol, methanol and the like) to obtain the polycarbonate.

In the embodiment of the present invention, the carbonic acid diester used in the above melt polymerization reaction may include one or more of diphenyl carbonate, di-m-tolyl carbonate, di-o-tolyl carbonate, dibenzyl carbonate, di (chlorophenyl) carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. In some embodiments of the present application, the carbonic acid diester may be embodied using a lower cost diphenyl carbonate.

The catalyst used in the above melt polymerization reaction is usually a basic substance, and may include nitrogen-containing organic substances (such as organic amines), metal compounds (such as oxides, hydroxides, inorganic salts, sulfides, etc., where the metal may be an alkali metal, an alkaline earth metal, a transition metal element, etc.), and the like. Specifically, the catalyst may include, for example, one or more of triethylamine, tri-N-butylamine, N-dimethylaniline, triethylenediamine, triisopropylamine, tetrabutylammonium fluoride (TBAF), tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide (TBAI), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), pyridine, sodium hydroxide, lithium hydroxide, magnesium oxide, zinc sulfide, cesium carbonate, potassium bicarbonate, sodium carbonate, lithium carbonate, calcium carbonate, and magnesium carbonate.

In some embodiments of the present disclosure, the dihydroxy monomer of formula (i) comprises at least one of a compound of formula (i-a) and a compound of formula (i-b):

the reaction equation for the melt polymerization reaction to synthesize the polycarbonate material, using the dihydroxy monomer represented by formula (i) specifically the compound represented by formula (i-a) and the carbonic diester as an example using diphenyl carbonate, can be as follows:

in some embodiments of the present disclosure, the raw materials in the melt polymerization reaction may further include at least one of the dihydroxy monomers shown in formulas (ii) and (iii):

in formula (iii), R' is selected from substituted or unsubstituted C₆-C₂₀Cycloalkylene, Z is independently selected at each occurrence from alkylene of 1-4 carbon atoms or a single bond.

The meaning of each symbol in formula (II) is the same as that of the corresponding symbol in formula (II) above, and the meaning of each symbol in formula (III) is the same as that of the corresponding symbol in formula (III) above, and thus, the description thereof is omitted.

In some embodiments of the present application, the monomer represented by formula (ii) includes at least one of the following monomers represented by formula (ii-a), formula (ii-b), and formula (ii-c):

among them, examples of the substance corresponding to the formula (ii-a) include 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (abbreviated as BPEF), 9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl ] fluorene (abbreviated as BPPEF "), 9-bis [4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-tert-butylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl ] fluorene, and the like.

Among them, examples of the substance corresponding to the formula (ii-b) include 9, 9-bis [6- (2-hydroxyethoxy) naphthalen-2-yl ] fluorene (abbreviated as BNEF), 9-bis [6- (1-hydroxymethoxy) naphthalen-2-yl ] fluorene, 9-bis [6- (3-hydroxypropoxy) naphthalen-2-yl ] fluorene, and 9, 9-bis [6- (4-hydroxybutoxy) naphthalen-2-yl ] fluorene.

Among them, examples of the substance corresponding to the formula (ii-c) include 2, 2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl (abbreviated as BHEBN), 2 '-bis (1-hydroxymethoxy) -1, 1' -binaphthyl, 2 '-bis (3-hydroxypropoxy) -1, 1' -binaphthyl, and 2, 2 '-bis (4-hydroxybutoxy) -1, 1' -binaphthyl.

In the embodiment of the present invention, in the above melt polymerization reaction, the molar amount of the carbonic acid diester may be 0.98 to 1.2 times of the total molar amount of the dihydroxy monomers, for example, 1 to 1.2 times, preferably 1.01 to 1.2 times of the total molar amount of the dihydroxy monomers, and the excessive addition of the carbonic acid diester is advantageous to increase the conversion rate of the dihydroxy monomers and to improve the yield. In order to increase the reaction rate of the above-mentioned melt polymerization reaction and not to decrease the ratio of the dihydroxy monomer in the reaction material system, in the embodiment of the present application, the molar amount of the catalyst is controlled to be 0.0001 to 0.002 times of the total molar amount of the dihydroxy monomer; for example, 0.0005 to 0.001 times.

It should be noted that the "total molar amount of dihydroxy monomers" in the above paragraph depends on the dihydroxy monomer system used in the synthesis of the polycarbonate described above, and does not merely refer to the sum of the molar amounts of the substances indicated in (i). For example, when the dihydroxy monomer used is only a substance represented by formula (i) above, it means that the total molar amount of the dihydroxy monomers is the sum of the molar amounts of the substances represented by formula (i); when the monomers for synthesizing the polycarbonate include, in addition to the monomer represented by formula (i), a dihydroxy monomer represented by formula (ii) and/or a dihydroxy monomer represented by formula (iii), "the total molar amount of dihydroxy monomers" refers to the sum of the molar amounts of the various types of dihydroxy monomers used.

The preparation method of the polycarbonate provided by the embodiment of the application has the advantages of simple process, easiness in operation and capability of obtaining the polycarbonate with higher purity and high yield.

Any of the polycarbonates having a specific structure described in the examples of the present application can be produced by the above-described production method.

In an embodiment of the present application, the dihydroxy monomer represented by formula (i) above is prepared as follows:

a) reacting a phenolic compound shown in a formula (A) with a fluorene compound shown in a formula (B) under the protection of inert gas to obtain an aromatic diphenol compound shown in a formula (C);

b) reacting an aromatic diphenol compound represented by formula (C) with ethylene carbonate in the presence of an alkaline catalyst to obtain a dihydroxy monomer represented by formula (i);

each occurrence of X is independently selected from the group consisting of an oxygen atom, a sulfur atom, a sulfone group, or a sulfoxide group; ar above₁、Ar₂Each occurrence is independently selected from

Ar₁' Each occurrence is independently selected from

The marked locations represent the attachment locations;

r is as defined above¹、R²、R³、R⁴、R⁵Each occurrence of which is independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amino group, an ester group, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an aryloxy group or an atom or atom group which may substitute for the above group, in formula (B), R¹-R²Any adjacent substituent in (a) may be connected to form a cyclic structure; in the formula (A), R³-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; in the formula (C), R¹-R⁵Any adjacent substituent in (a) may be connected to form a cyclic structure; each occurrence of a, b, c, d 'is independently selected from an integer between 1 and 4, each occurrence of d, e is independently selected from an integer between 1 and 3, and each occurrence of c' is independently selected from an integer between 1 and 5. Wherein Ar is₁' with Ar₁Correspondingly, the difference between the two lies in Ar₁' ratio Ar₁One more hydrogen atom.

The reaction equation for preparing the dihydroxy monomer of formula (i) may be as follows:

the reaction in step a) may be referred to as a Friedel-crafts reaction. In carrying out the reaction of step a), a catalyst will generally be employed, which is typically an acidic catalyst, including a protic acid and/or a lewis acid; exemplary protic acids may be, for example, 3-mercaptopropionic acid, p-toluenesulfonic acid, concentrated sulfuric acid; exemplary lewis acids may be zinc chloride and the like. The reaction in step a) may be carried out at a reaction temperature of from 80 to 120 ℃ and for a reaction time of from 10 to 48 hours, for example from 12 to 24 hours. Adding water into the material reacted in the step a), stirring, extracting by an extracting agent (such as ethyl acetate), concentrating and drying to obtain the aromatic diphenol compound shown in the formula (C).

In the embodiment of the application, ethylene carbonate is used as a hydroxyethylation reagent to carry out the condensation reaction in the step b), the reagent is cheap and easy to obtain, and the reagent is changed into carbon dioxide after participating in the reaction, so that the environment is protected; and can ensure that the terminal hydroxyl group of the compound shown in the formula (C) obtained by the reaction has higher activity so as to facilitate the subsequent reaction with the carbonic diester with high efficiency. Wherein ethylene carbonate may be added in stoichiometric proportions or in excess of the reaction, and the excess of ethylene carbonate is advantageous in increasing the yield of the dihydroxy compound of formula (i). The molar ratio of ethylene carbonate to the compound of formula (C) may be greater than or equal to 2: 1, and in some embodiments is (2.1-5) to 1, and may be, specifically, 2: 1, 2.5: 1, 3: 1, 4: 1, and the like. Further, the basic catalyst used for carrying out the reaction in step b) may be selected within the same range as the catalyst for carrying out the aforementioned melt polymerization reaction.

In an embodiment of the present invention, the step b) of reacting the aromatic diphenol compound represented by formula (C) with ethylene carbonate in the presence of a basic catalyst to obtain the dihydroxy monomer represented by formula (i) may specifically include: mixing an aromatic diphenol compound shown in a formula (C), ethylene carbonate, an alkaline catalyst and a first solvent to obtain a mixed solution, heating the mixed solution to be not more than the boiling point of the first solvent, and reacting to obtain a reaction solution containing a dihydroxy monomer shown in a formula (i); and (3) distilling the reaction solution under reduced pressure, adding water, stirring, filtering, dissolving a filter cake obtained by filtering by using a second solvent, and concentrating and drying to obtain the dihydroxy monomer shown in the formula (i).

Wherein, the reaction temperature in the reaction process of the step b) is not higher than the boiling point of the first solvent, the condition is mild, and the solvent vapor pollution can be avoided. In general, the reaction temperature of step b) may be from 90 to 130 ℃ and the reaction time may be from 2 to 24 h. In particular, the reaction temperature may be 90, 100, 110, 120 or 130 ℃. The time for the condensation reaction may be 2, 5, 6, 8 or 10 h.

Among them, the above first solvent may include, but is not limited to, one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, toluene, benzene, xylene, ethylbenzene, diethylbenzene, cumene, and the like. The second solvent may be the same as or different from the first solvent. The second solvent may include, but is not limited to, one or more of ethyl acetate, N-Dimethylformamide (DMF), N-dimethylacetamide, toluene, xylene, and the like.

The preparation process of the dihydroxy monomer shown in the formula (i) in the embodiment of the application is environment-friendly, mild in reaction conditions, short in reaction time, simple in post-treatment, high in yield, high in purity and low in preparation cost. The process of the melt polymerization reaction of the dihydroxy monomer shown in the formula (i) and the carbonic acid diester is stable, and the yield and the purity of the obtained carbonic acid ester are high.

The embodiment of the application also provides a resin composition, which comprises the polycarbonate in the embodiment of the application.

The polycarbonate resin composition is low in processing and forming temperature, can be formed conveniently through an injection molding process, and is low in residual internal stress and internal force birefringence in the injection molding process, so that the obtained molded sheet is high in imaging quality.

In the embodiment, the resin composition may further include an additive, and the additive may include one or more of a filler, a dye, an antioxidant, a light stabilizer, a heat stabilizer, an ultraviolet absorber, a plasticizer, a flame retardant, an antistatic agent, and a mold release agent. Of course, the resin composition may further include other polymers, the other polymers may be other optical resins different from the polycarbonate of the embodiments of the present application, the other optical resins may specifically be other polycarbonates different from the embodiments of the present application, and may also be non-polycarbonate optical resins, and the other optical resins may specifically be added in appropriate amounts as needed.

In an embodiment of the present invention, the polycarbonate resin composition of the examples of the present invention contains 80% by mass or more of the polycarbonate resin. In some embodiments, the polycarbonate of the examples herein is present in the resin composition in an amount of 80%, 85%, 90%, 95%, 98% by mass.

Embodiments also provide an optical article including the polycarbonate of an embodiment, or the resin composition of an embodiment. The above polycarbonate or resin composition can be processed into an optical article by various known molding methods. The optical article may be partially processed from the polycarbonate or the resin composition, or may be entirely processed from the polycarbonate or the resin composition.

The processing method of the optical article includes, but is not limited to, injection molding, extrusion molding, solution casting, foam molding, blow molding, compression molding, calendering, rotational molding, and the like. In the present embodiment, the polycarbonate or the resin composition may be processed into an optical article by injection molding, based on the fact that the polycarbonate is a thermoplastic resin. Because the polycarbonate has high refractive index, lower glass transition temperature, high processing and forming convenience and less internal stress residue in the processing process, the optical property and the mechanical property of the obtained optical product are excellent, and the thickness can be thinner.

In embodiments of the present application, the optical article may specifically include an optical lens, an optical film, an optical disc, a light guide plate, or a display panel.

In the embodiments of the present application, the optical lens may specifically include, but is not limited to, a spectacle lens, a sensor lens, an image pickup lens, an illumination lens, an imaging lens, and the like. The spectacle lenses may include, among others, myopic lenses, presbyopic lenses, sunglass lenses, contact lens corrective lenses, goggle lenses, and the like. The sensor lens may be a motion detector lens, a proximity sensor lens, an attitude control lens, an infrared sensor lens, or the like. The camera lens may be a mobile phone camera lens, a notebook computer camera lens, a desktop camera lens, an automobile camera lens, or the like. Among them, the illumination lens may be an indoor illumination lens, an outdoor illumination lens, a vehicle headlamp lens, a vehicle fog lens, a vehicle backlight lens, a vehicle running light lens, a vehicle fog lens, a vehicle interior lens, a Light Emitting Diode (LED) lens, an Organic Light Emitting Diode (OLED) lens, or the like. The imaging lens may be a scanner lens, a projector lens, a telescope lens, a microscope lens, a magnifier lens, or the like.

In the embodiments of the present disclosure, the optical film may include a light guide film, a reflective film, an antireflection film, a diffusion film, a light filter film, a polarizing film, a light splitting film, a phase film, and the like. The optical film can be used in the display field, the illumination field, and the like, and can be used, for example, as a film for a substrate of a liquid crystal display panel.

Embodiments of the present application also provide an apparatus including an optical article as described above in embodiments of the present application. The device may specifically be a mobile terminal, glasses, a camera, a vehicle (e.g. car, motorcycle, train, etc.), a lighting device (e.g. table lamp, ceiling lamp, street lamp, etc.), an imaging device (e.g. microscope, telescope, projector, scanner, etc.), etc. The mobile terminal may specifically include various handheld devices (e.g., mobile phones, tablet computers, mobile notebooks, netbooks, etc.) with wireless communication functions, wearable devices (e.g., smart watches, etc.), or other processing devices connected to a wireless modem, as well as various forms of User Equipment (UE), Mobile Stations (MS), terminal equipment (terminal device), and the like.

In some embodiments, the present disclosure provides an electronic device comprising an electronic device body and a camera module mounted on the electronic device body, wherein the camera module comprises a camera lens, and the camera lens is prepared by using the polycarbonate or the resin composition described in the examples of the present disclosure.

In some embodiments, the electronic device is a mobile terminal, such as a smartphone. In other embodiments, the electronic device is a vehicle.

The examples of the present application are further illustrated below in the context of several examples.

Example 1

(1) Preparation of monomeric BOF for the Synthesis of polycarbonate:

the reaction equation involved in synthesizing the BOF monomer is:

sequentially adding 9-fluorenone (20g, 0.11mol), a raw material A-1 (namely 4-phenoxyphenol) (82.7g, 0.44mol) and a catalyst 3-mercaptopropionic acid (1.2g, 0.011mol) into a 250mL three-necked flask, slowly heating to 95 ℃, adding zinc chloride (15.3g, 0.11mol), and reacting for 12 h; then, 80mL of water was added to the obtained reaction solution, and the mixture was stirred for 10min, extracted twice with 150mL of ethyl acetate, and the organic phases were combined, dried, concentrated and purified to obtain 42.75g of a white solid with a yield of 72%. The structure of this white solid was known by characterization to conform to the aforementioned formula (C), which was designated compound C-1. Wherein, the characterization data of the nuclear magnetic resonance image of the compound C-1 are as follows:¹H NMR(300MHz，CDCl₃) Delta 8.51(s, 2H), 7.62-7.60(m, 2H), 7.25-7.18(m, 4H), 7.15-7.12(m, 2H), 6.96-6.93(m, 4H), 6.72-6.64(m, 8H), 6.62-6.59(m, 4H). The nuclear magnetic junctionThe results show successful preparation of compound C-1.

Adding the reaction product C-1(22.1g) in the previous step, 110mL of DMF, ethylene carbonate (10.9g, 0.124mol) and anhydrous potassium carbonate (2.86g, 0.021mol) into a 250mL single-neck flask, stirring, slowly heating to 110 ℃ and reacting for 12 hours; naturally cooling to 70 ℃, removing most DMF in the reaction solution by reduced pressure distillation, adding 200mL of water for dilution, stirring for 10min, filtering, dissolving a filter cake obtained by filtering by using 100mL of ethyl acetate, drying, concentrating and purifying to obtain 17.5g of white powdery solid BOF.

The characterization data of the nuclear magnetic resonance image of the BOF monomer are as follows:¹H NMR(300MHz，CDCl₃) δ 7.78 to 7.75(m, 2H), 7.39 to 7.37(m, 4H), 7.36 to 7.27(m, 2H), 7.15 to 7.12(m, 4H), 6.97 to 6.95(m, 4H), 6.89 to 6.86(m, 4H), 6.80 to 6.77(m, 4H), 4.07 to 4.04(m, 4H), 3.99 to 3.95(m, 4H), 2.1(s, 2H).

(2) Preparation of polycarbonate-BOF homopolymerization:

the BOF monomer (1 molar equivalent, abbreviated as 1eq), diphenyl carbonate (DPC, 1.03eq) and MgO catalyst (0.0007eq) were charged in this order in a single-neck flask, heated to raise the temperature, and N was added₂Stirring at constant speed under atmosphere, heating to 160 deg.C, and maintaining for 20min to melt the raw materials; heating to 200 deg.C, and maintaining at 200 deg.C for 60min to completely melt the monomers; then, vacuum was started to provide a reduced pressure atmosphere, and N was slowly turned off₂Performing ester exchange reaction at the pressure of 100-120Pa for 30-60 min, and carrying out vacuum extraction of phenol generated by ester exchange; then heating to 220 ℃, increasing the vacuum degree to the absolute pressure of 100-105Pa, then heating to 240 ℃, increasing the vacuum degree to the absolute pressure of 90-100Pa, entering the polycondensation stage, continuing for more than 30min, and terminating the polymerization according to the phenomenon of pole climbing (namely, the phenomenon that the polymerization product is tangled upwards along the stirring slurry in the polymerization reaction). After the reaction was terminated, the pressure in the flask was returned to normal pressure, and after the reaction mixture was dissolved in methylene chloride, the solution was reprecipitated in ethanol to obtain polycarbonate represented by the reference numeral P1.

The preparation of the polycarbonate of example 1 involves, among other things, the reaction equation:

it was found by testing that the polycarbonate P1 from example 1 had a number-average molecular weight Mn of 22kg/mol, a Polymer Dispersity Index (PDI) of 1.80 and a glass transition temperature (Tg) of 145 ℃. The visible light transmittance of this P1 was 89%.

Example 2

Preparation of polycarbonate-BOF and BPEF copolymerization

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer from example 1 was replaced with 0.5eq of BOF monomer and 0.5eq of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF, structure shown below).

The preparation of the polycarbonate of example 2 involves, among other things, the reaction equation:

the polycarbonate obtained in example 2 was designated by the reference numeral P2. The polycarbonate P2 had a number-average molecular weight Mn of 24kg/mol and a PDI of 1.78.

Example 3

Preparation of polycarbonate-BOF and BHEBN copolymerization

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer in example 1 was replaced with 0.5eq of BOF monomer and 0.5eq of 2, 2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl (BHEBN, structure shown below).

The polycarbonate of preparation example 3 is prepared according to the reaction equation:

the polycarbonate obtained in example 3 was designated by the reference numeral P3. The polycarbonate P3 was found to have a number average molecular weight Mn of 28kg/mol and a PDI of 1.69.

Example 4

Preparation of polycarbonate-copolymerization of BOF, BHEBN and BNEF

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer in example 1 was replaced with 0.4eq of BOF monomer, 0.3eq of 2, 2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl (BHEBN), and 0.3eq of 9, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene (BNEF, structure shown below).

The preparation of the polycarbonate of example 4 involves, among other things, the reaction equation:

the polycarbonate obtained in example 4 was designated by the reference numeral P4. The polycarbonate P4 was found to have a number average molecular weight Mn of 21kg/mol and a PDI of 1.90.

Example 5

Preparation of polycarbonate-BOF and TCDDM copolymerization

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer in example 1 was replaced with 0.5eq of BOF monomer and 0.5eq of tricyclodecane dimethanol (TCDDM, structure shown below).

The preparation of the polycarbonate of example 5 involves, among other things, the reaction equation:

the polycarbonate obtained in example 5 was designated by the reference numeral P5. The polycarbonate P5 was found to have a number average molecular weight Mn of 32kg/mol and a PDI of 1.72.

Example 6

Preparation of polycarbonate-BOF and PCPDM copolymerization

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer in example 1 was replaced with 0.5eq of BOF monomer and 0.5eq of pentacyclopentadecane dimethanol (PCPDM, structure shown below).

The preparation of the polycarbonate of example 6 involves, among other things, the reaction equation:

the polycarbonate obtained in example 6 was designated by the reference numeral P6. The polycarbonate P6 was found to have a number average molecular weight Mn of 27kg/mol and a PDI of 1.88.

Example 7

Preparation of polycarbonate-BOF and TeCDDM copolymerization

The polycarbonate was prepared by a procedure different from that of example 1: 1eq of BOF monomer in example 1 was replaced with 0.5eq of BOF monomer and 0.5eq of cyclododecanedimethanol (TeCDDM, structure shown below).

The preparation of the polycarbonate of example 7 involves, among other things, the reaction equation:

the polycarbonate obtained in example 7 was designated by the reference numeral P7. The polycarbonate P7 was found to have a number average molecular weight Mn of 29kg/mol and a PDI of 1.86.

Example 8

Preparation of polycarbonate-BOF and BPEF, TeCDDM copolymerization

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer in example 1 was replaced with 0.25eq of BOF monomer, 0.25eq of BPEF, and 0.5eq of TeCDDM.

The polycarbonate of example 8 was prepared according to the reaction equation:

the polycarbonate obtained in example 8 is denoted by the reference numeral P8. The polycarbonate P8 was found to have a number average molecular weight Mn of 25kg/mol and a PDI of 1.88.

Example 9

(1) Preparation of monomeric BSF for synthetic polycarbonate:

the reaction equation involved in synthesizing the BSF monomer is:

in a 500mL three-necked bottle, raw materials of 25.2g of p-hydroxybenzothiaol, 41.6g of iodobenzene, 1.9g of cuprous iodide and PEG are added in sequence₁₀₀₀200g and 106.5g of potassium phosphate trihydrate, slowly heating the three-neck flask to 110 ℃ through an oil bath, starting stirring after most of reaction raw materials are molten, and keeping the temperature and stirring at 110 ℃ for 12 hours to ensure that the materials are basically completely reacted. Then, 100mL of water was added to the reaction mass at 45 ℃ and stirred for 20min, and extraction was performed with 200mL of ethyl acetate, which was repeated four times, and the organic phases were combined and dried to remove the solvent to obtain a pale yellow oil with a yield of 85%. The structure of the light yellow oil is known to accord with the formula (A) through characterization, the light yellow oil is marked as A-2, and the structure is shown as above. Wherein the data of the nuclear magnetic resonance image of the compound A-2 are as follows:¹H NMR(300MHz，CDCl₃)δ7.39-7.36(m，2H)，7.28-7.14(m，5H)，6.85-6.82(m，2H)，4.98(s，1H)。

adding 9-fluorenone (1g, 5.6mmol), the product A-2(4.49g, 22mmol) of the previous step, the catalyst 3-mercaptopropionic acid (0.06g, 0.565mmol) and zinc chloride (0.76g, 5.58mmol) in sequence into a 250mL three-necked flask, stirring and heating to 90 ℃ for reaction for 12 h; then, water is added into the obtained reaction liquid for dilution, the reaction liquid is extracted twice by ethyl acetate, organic phases are combined, and the organic phases are dried, concentrated and purified to obtain light yellow solid. The structure of this pale yellow solid is known by characterization to conform to the aforementioned formula (C), which is designated compound C-2. Wherein the data of the nuclear magnetic resonance image of the compound C-2 are as follows:¹H NMR(300MHz，CDCl₃)δ7.75-7.71(m，2H)，7.35-7.31(m，7H)，7.27-7.24(m，2H)，7.07-6.80(m，7H)，6.80-6.77(m，2H)，6.67-6.64(m，2H)，4.98(s，2H)。

in a 250mL single-neck flask, the above-mentioned compound C-2(1.13g), ethylene carbonate (0.528g, 6mmol), 110mL of toluene and anhydrous potassium carbonate (0.208g, 1.5mmol) were added, and the mixture was slowly heated to 110 ℃ and reacted for 20 hours. To the obtained reaction solution, 50mL of water was added, and the mixture was extracted twice with 100mL of ethyl acetate, dried, concentrated and purified to obtain BSF as a pale yellow foamy solid.

The characterization data of the nuclear magnetic resonance image of the BSF are as follows:¹H NMR(300MHz，CDCl₃) δ 7.75-7.72(m, 2H), 7.39-7.31(m, 6H), 7.25-7.24(m, 4H), 7.10-6.97(m, 8H), 6.89-6.86(m, 2H), 6.76-6.73(m, 2H), 4.98(s, 2H), 4.07-3.96(m, 4H), 3.95-3.89(m, 4H). The nuclear magnetic results show that the dihydroxy compound monomer having the structure according to the general formula (i) was successfully prepared.

(2) Preparation of polycarbonate-copolymerization of BSF with BPEF:

the BSF monomer (0.5eq) and 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] were added in sequence to a single-neck bottle]Fluorene (BPEF, 0.5eq), diphenyl carbonate (DPC, 1.03eq) and MgO catalyst (0.0007eq), heated to raise the temperature, N₂Stirring at constant speed under atmosphere, heating to 160 deg.C, and maintaining for 20min to melt the raw materials; heating to 200 deg.C, and maintaining at 200 deg.C for 60min to completely melt the monomers; then, vacuum pumping is started to increase the reduced pressure environment, and N is slowly closed₂Carrying out ester exchange reaction at the pressure of 100-120Pa for 30-60 min, and carrying out vacuum extraction of phenol generated by ester exchange; then heating to 220 ℃, regulating the vacuum to 100-105Pa, heating to 240 ℃, increasing the vacuum to 90-100Pa, entering a polycondensation stage, continuing for more than 30min, and terminating the polymerization according to the pole climbing phenomenon. After the reaction was terminated, the pressure in the flask was returned to normal pressure, and after the reaction mixture was dissolved in methylene chloride, the solution was reprecipitated in ethanol to obtain polycarbonate represented by the reference numeral P9.

Wherein the reaction equation involved in the preparation of the polycarbonate P9 is:

tests have shown that the polycarbonate P9 from example 9 has a number-average molecular weight Mn of 30kg/mol and a PDI of 1.73.

Example 10

Preparation of polycarbonate-BSF homopolymerization

The polycarbonate preparation differs from example 8 in that: 0.5eq of BOF monomer and 0.5eq of BSF monomer from example 8 were replaced with 1eq of BSF monomer.

The reaction equation involved in preparing the polycarbonate of example 10 is:

the polycarbonate obtained in example 10 was designated by the reference numeral P10. The polycarbonate P10 was found to have a number average molecular weight Mn of 21kg/mol and a PDI of 1.78.

Example 11

(1) Monomer BNOF for preparing synthetic polycarbonate

The reaction equation involved in preparing monomeric BNOF is:

2-naphthol (17.3g, 0.12mol), 4-iodophenoxyethanol (26.4g, 0.1mol), cuprous iodide (0.01mol, 1.9g), 1-pyridin-2-yl-2-propanone (2.0g, 0.015mol), DMSO (200 mL), and cesium carbonate (65g, 0.2mol) as raw materials were sequentially added to a 500mL three-necked flask, and the atmosphere in the three-necked flask was replaced with argon gas, followed by heating and stirring at 80 ℃ for 8 hours to complete the reaction. After cooling, diluting with 500mL of ethyl acetate, filtering with silica gel to remove the catalyst, performing rotary evaporation on the obtained filtrate, and separating by column chromatography to obtain a product 4- (2-naphthoxy) -phenoxyethanol (NOPE), wherein the yield is 82%;

sequentially adding 9-fluorenone (20g, 0.11mol), NOPE (123.3g, 0.44mol) serving as a raw material and 3-mercaptopropionic acid (1.2g, 0.011mol) serving as a catalyst into a 250mL three-necked flask, slowly heating to 95 ℃, adding zinc chloride (15.3g, 0.11mol), and reacting for 12 hours; then, 80mL of water was added to the obtained reaction solution, and the mixture was stirred for 10min, extracted twice with 150mL of ethyl acetate, and the organic phases were combined, dried, concentrated and purified to obtain 59.6g of a white solid with a yield of 75%. The white solid is BNOF with the structural formula shown above.

(2) Preparation of polycarbonate-BNOF and BHEBN copolymerization

The polycarbonate preparation differs from example 1 in that: 1eq of BOF monomer in example 1 was replaced with 0.3eq of BNOF monomer and 0.7eq of BHEBN monomer.

The reaction equation involved in preparing the polycarbonate of example 11 is:

the polycarbonate obtained in example 11 was designated by the reference numeral P11. The polycarbonate P11 was found to have a number average molecular weight Mn of 19kg/mol and a PDI of 1.94.

Example 12

(1) Preparation of synthetic polycarbonate monomer BSO 2F:

the reaction equation involved in preparing the monomeric BSO2F is as follows:

BSF (6.55g, 0.01mol) and m-chloroperoxybenzoic acid (8.63g, 0.05mol) are dissolved in 50Ml of dichloromethane, the mixture is heated and stirred at 40 ℃ for 12 hours until the reaction is completed, the mixture is cooled to room temperature after the reaction is finished, 50mL of water is used for washing the reaction liquid for three times, and after an organic phase is dried and concentrated, the product BSO2F (4.52g) is obtained through separation and purification by column chromatography, and the yield is 63%.

(2) Preparation of polycarbonate-BSO 2 homopolymer

The polycarbonate preparation process differs from example 8 in that: 0.5eq of BOF monomer and 0.5eq of BSF monomer from example 8 were replaced by 1eq of BSO2F monomer.

The reaction equation involved in preparing the polycarbonate of example 12 is:

the polycarbonate obtained in example 12 was designated by the reference numeral P12. The polycarbonate P12 was found to have a number average molecular weight Mn of 21kg/mol and a PDI of 1.85.

To highlight the advantageous effects of the examples of the present application, the following comparative examples 1 to 3 are now provided.

Comparative example 1

A polycarbonate S1 was prepared in substantially the same manner as in example 1, except that the only monomer used was BPEF as described above.

Comparative example 2

A polycarbonate S2 was prepared in substantially the same manner as in example 1, except that the monomer used was 9, 9-bis [ 3-phenyl-4- (2-hydroxyethoxy) -phenyl ] fluorene (BPPEF for short, having the formula shown below).

Comparative example 3

A polycarbonate S3 was prepared in substantially the same manner as in example 11, except that the monomers used were BNEF and BHEBN (molar ratio 3: 7) as described above.

To strongly support the beneficial effects of the technical solutions of the embodiments of the present application, the test results of the thermal and optical properties of the polycarbonate materials of the embodiments 1, 2, 9-12 and the comparative examples 1-3 of the present application are summarized in the following table 1.

Wherein the glass transition temperature (Tg) of the polycarbonate is measured using a Differential Scanning Calorimeter (DSC). The refractive index was measured according to ASTM D542. The injection-molded articles of the respective polycarbonate materials were tested for stress residual using a birefringence stress tester (StrainScope Flex, Ilis, germany): injection molding each polycarbonate material to a diameter of

Has a thickness of10mm disks, each 5mm from the center of each disk (i.e., from the center of the disk)

Circle) in nm, the larger the result, the larger the residual internal stress of the material.

TABLE 1

Resin numbering	Tg(℃)	Refractive index	Abbe number	Double refraction stress (nm)
					P1	145	1.651	21.0	35nm
P2	150	1.640	23.3	47nm
					P9	143	1.673	20.3	42nm
P10	144	1.696	18.0	27nm
					P11	135	1.672	19.2	60nm
P12	145	1.691	20.3	55nm
					S1	148	1.639	23.5	64nm
S2	160	1.655	21.5	75nm
					S3	142	1.651	21.0	73nm

Based on table 1, by introducing novel monomers corresponding to the structural unit of formula (I) of the present application, the residual internal stress in the injection molded part can be significantly reduced. Comparing the polycarbonate materials S1, S2 prepared in comparative examples 1, 2 using monomers similar to the monomer BOF used in example 1, the monomer BPEF used in comparative example 1 contains a dibenzofluorene backbone similar to BOF (but lacks phenoxy between the phenyl and hydroxyethoxy groups of BPEF), the monomer BPPEF used in comparative example 2 contains the same number of benzene rings as the BOF monomer, but the results of testing the polymerization product show that P1 obtained by homopolymerization of the monomer BOF has lower residual internal stress than the comparative S1, S2 materials. Meanwhile, P2 obtained by copolymerizing BOF and BPEF also has the effect of reducing the residual stress in the material. Similarly, the polymers P10 and P12 prepared by homopolymerizing the monomers BSF and BSO2F have lower internal stress residue and higher refractive index than S1 and S2. The polymer P9 prepared by copolymerizing BSF and BPEF can simultaneously realize the improvement of the refractive index and the reduction of residual internal stress. In addition, the monomers BOF, BSF and BSO2F of the present example, which have the same number of benzene rings as BPPEF, and the Tg of the polycarbonate materials (such as P1, P10 and P12) obtained by homopolymerization of the monomers are also obviously lower than that of the homopolymer S2 of BPPEF, and the Tg of the polycarbonate materials is similar to that of the monomers adopting the monomers and having less-X-Ar in the formula (I)₂The partial monomer homopolymerization of polycarbonate S1 was substantially comparable (even lower). Furthermore, as can be seen from the comparison of the data of examples P10 and P12, when the refractive index of the polycarbonate material of the examples is comparable, the polycarbonate obtained by homopolymerizing the corresponding monomer in which X is a sulfone group in the structural unit of formula (I) has a higher abbe number than the polycarbonate obtained by homopolymerizing the corresponding monomer in which X is a sulfur atom, and therefore has better optical properties.

The other monomers of similar but more complex structure (BNOF for example 11 of the present application, BNEF for comparative example 3) were compared, under the same copolymerization conditions (copolymerization with monomer BHEBN in a molar ratio of 3: 7), and the resulting polymer P11 also had lower residual internal stress, and lower Tg, than the polymer S3 of comparative example 3.

After verifying that the birefringence stress of the polycarbonate provided in the examples of the present application is low, a polycarbonate is further prepared by copolymerizing a monomer corresponding to the structural unit of formula (I) of the present application with other disclosed monomers, and information on the glass transition temperature, visible light transmittance, refractive index, abbe number, and the like of the obtained polycarbonate is summarized in table 2 below. Wherein the refractive index and Abbe number are measured according to ASTM D542, and the transmittance (%) in the visible light wavelength range is measured according to ASTM D1003.

TABLE 2

Resin numbering	Tg(℃)	Transmittance of visible light	Refractive index	Abbe number
					P1	145	89％	1.651	21.0
P2	150	89％	1.640	23.3
					P3	133	89％	1.655	20.8
P4	150	88％	1.672	19.1
					P5	137	90％	1.603	29.4
P6	146	91％	1.587	33.1
					P7	142	91％	1.595	31.5
P8	144	90％	1.601	29.6
					P9	143	88％	1.673	20.3
P10	144	88％	1.696	18.0
					P11	145	88％	1.672	19.2
P12	145	88％	1.691	20.3

As can be seen from table 2, the monomer corresponding to the structural unit of formula (I) of the present application can be homopolymerized or copolymerized with other disclosed monomers to control the refractive index, abbe number, visible light transmittance, etc. of the polycarbonate material, and can be applied to various scenes with different requirements on the refractive index.

Claims

1. A polycarbonate comprising a structural unit represented by formula (I):

The marked locations represent the attachment locations;

2. The polycarbonate of claim 1, wherein the structural unit of formula (I) comprises at least one of the following structural units of formulae (I-a) and (I-b):

3. the polycarbonate of claim 1 or 2, wherein the polycarbonate has a total molar proportion of structural units represented by formula (I) of greater than or equal to 10%.

4. The polycarbonate of any of claims 1-3, wherein the polycarbonate further comprises structural units according to formula (II) and/or structural units according to formula (III):

5. The polycarbonate of claim 4, wherein in formula (II), the substituents on the substituted arylene group and the substituted heteroarylene group are independently selected from one or more of deuterium atom, tritium atom, halogen atom, hydroxyl group, thiol group, amino group, cyano group, ester group, and substituted or unsubstituted alkyl group, alkoxy group, cycloalkyl group, alkenyl group, aryl group, aryloxy group, and heteroaryl group.

6. The polycarbonate of any of claims 4-5, wherein in formula (II), both Y are ethylene and both p are 1.

7. The polycarbonate of any of claims 4-6, wherein the structural unit of formula (II) comprises at least one of the following:

8. The polycarbonate of any of claims 4-7, wherein the total molar proportion of structural units represented by formula (II) in the polycarbonate is from 10% to 90%.

9. The polycarbonate of claim 4, wherein in formula (III), R' is selected from the group consisting of substituted or unsubstituted tricyclodecanediyl, pentacyclopentadecanediyl, tetracyclododecanediyl.

10. The polycarbonate of claim 4 or 9, wherein the total molar proportion of structural units represented by formula (III) in the polycarbonate is from 30% to 90%.

11. The polycarbonate of any of claims 1-10, wherein the polycarbonate has a number average molecular weight of 10000-50000.

12. The polycarbonate of any of claims 1-11, wherein the polycarbonate has a glass transition temperature of 130-160 ℃.

13. The polycarbonate of any of claims 1-12, wherein the polycarbonate has a refractive index of greater than or equal to 1.56.

14. The polycarbonate of any of claims 1-13, wherein the polycarbonate has an abbe number greater than 16.

15. The polycarbonate of any of claims 1-14, wherein the polycarbonate has a visible light transmission of 87% or greater.

16. A resin composition comprising the polycarbonate of any one of claims 1-15.

17. The resin composition of claim 16, further comprising one or more of fillers, dyes, antioxidants, light stabilizers, heat stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, mold release agents.

18. An optical article comprising the polycarbonate of any of claims 1-15, or comprising the resin composition of any of claims 16-17.

19. The optical article of claim 18, wherein the optical article comprises an optical lens, an optical film, an optical disc, a light guide plate, or a display panel.

20. The optical article of claim 19, wherein the optical lens comprises an eyeglass lens, a camera lens, a sensor lens, an illumination lens, an imaging lens.

21. A device comprising the optical article of any one of claims 18-20.

22. An electronic device having a camera module, wherein the camera module comprises a camera lens, and the camera lens is prepared from the polycarbonate of any one of claims 1-15 or the resin composition of any one of claims 16-17.

23. A method of producing a polycarbonate, comprising:

24. The method of claim 23, wherein the starting materials further comprise at least one of dihydroxy monomers of the formulae (ii) and (iii):