CN115873226B

CN115873226B - Copolycarbonate and preparation method and application thereof

Info

Publication number: CN115873226B
Application number: CN202211653440.8A
Authority: CN
Inventors: 许泽旺; 靳少华; 邵雪飞; 郭华; 王磊
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2022-12-21
Filing date: 2022-12-21
Publication date: 2024-05-03
Anticipated expiration: 2042-12-21
Also published as: CN115873226A

Abstract

The invention provides a copolycarbonate, a preparation method and application thereof, wherein the copolycarbonate has a high refractive index, and simultaneously the copolycarbonate can achieve relatively low birefringence and relatively low Abbe number. The copolycarbonates comprise structural units A of the following formula (I) and structural units B of the following formula (II): Wherein R ₁ and R ₂ in the structural formula (I) and R ₃ and R ₄ in the structural formula (II) are each independently a hydrogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C5-20 cycloalkyl group, a C5-20 cycloalkoxy group, a C6-20 aryl group, a C6-20 aryloxy group or a halogen atom.

Description

Copolycarbonate and preparation method and application thereof

Technical Field

The invention relates to copolycarbonate, in particular to copolycarbonate and a preparation method and application thereof.

Background

With the development of light and thin electronic digital products, higher requirements are also put on optical lens materials. Common lens materials include optical glass and optical resins. The glass lens has higher technical barriers in the aspects of manufacturing technology, coating technology, precision machining and the like, so that the optical glass has higher manufacturing cost and poor material forming processability, and the large-scale application of the optical glass in the optical lens is limited. The plastic lens is formed by adopting optical resin injection molding, is easy to manufacture into an aspheric surface shape, has the characteristics of strong plasticity, convenience for miniaturization and the like, and is low in preparation cost, so that the plastic lens is widely applied to mobile phone shooting, security protection, VR/AR, vehicle-mounted image, intelligent auxiliary driving, machine vision and the like.

The polycarbonate is used as engineering plastic with excellent performance and has good application in the fields of electronic appliances, automobiles, household appliances and the like. The optical resin has good mechanical property, good impact toughness, creep resistance, good dimensional stability, wide use temperature range, no color and transparency, and is widely used optical resin. Applications of polycarbonate in optical lenses include lenses, vision correction lenses, multilayer diffusion sheets, light reflective films, and the like. The polycarbonate obtained by polymerizing bisphenol A has a refractive index of about 1.58 and has more excellent optical properties than polymethyl methacrylate or polystyrene. Therefore, the development of polycarbonate-based optical resins is a current research hotspot.

According to the Lorentz-Lorenz equation: the introduction of substituents with high values of R/V0 can effectively increase the refractive index n of the polymer. Halogen atoms and sulfur atoms except fluorine have higher [ R ], but the yellowing and the weather resistance of the polymer are easy to be poor, the aromatic ring has higher [ R ] value, and the proper amount of introduced aromatic ring can greatly improve the refractive index of the material. With the rapid iteration of consumer electronics, the miniaturization of optical lenses has become a mainstream trend. In general, when the refractive index of an optical material is high, it is possible to realize lens elements having the same refractive index with a smaller curvature surface, and therefore it is possible to reduce the lens thickness and the number of lenses used by increasing the refractive index of the material, which requires development of an optical resin having a higher refractive index.

Chinese patent CN102471467B discloses a polycarbonate copolymer synthesized from 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene as a monomer, but the refractive index is only 1.644 at the highest, which cannot meet the application requirements. Chinese patent application CN104769007a discloses a polycarbonate containing 2, 2-bis- (2-hydroxyethoxy) -1, 1-binaphthyl and its derivatives, the refractive index of the examples is not more than 1.668, and although the refractive index of the polycarbonate copolymer synthesized by using 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene as a monomer is improved to some extent, there is still room for improvement.

Disclosure of Invention

The invention aims to provide a copolycarbonate with a higher refractive index, and meanwhile, the copolycarbonate can achieve both a relatively low birefringence and a relatively low Abbe number.

The invention provides the following technical scheme for achieving the purpose:

in one aspect, the present invention provides a copolycarbonate comprising structural unit A of formula (I) below and structural unit B of formula (II) below:

Wherein R ₁ and R ₂ in the structural formula (I) and R ₃ and R ₄ in the structural formula (II) are each independently a hydrogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C5-20 cycloalkyl group, a C5-20 cycloalkoxy group, a C6-20 aryl group, a C6-20 aryloxy group or a halogen atom.

The inventors have found that copolycarbonates having structural units A and structural units B described above can maintain a relatively high refractive index while having relatively reduced birefringence and Abbe number.

In some preferred embodiments, the molar ratio of structural unit A to structural unit B is from 1:99 to 99:1, for example from 50:50 to 99:1, for example from 35:65 to 70:30, for example from 55:45 to 60:40, preferably from 50:50 to 99:1.

In some preferred embodiments, the weight average molecular weight of the copolycarbonate is 10000-200000, preferably 15000-80000, more preferably 20000-70000. The weight average molecular weight can be determined by volume exclusion gel chromatography after pre-calibration with polystyrene or polycarbonate calibration materials.

In some embodiments, each of R ₁、R₂ is independently a hydrogen atom or a benzene ring, and R ₃ and R ₄ are hydrogen atoms;

further preferably, the structural unit a has the following structural formula (a 1) or (a 2), and the structural unit B has the following structural formula (B1):

The copolycarbonate provided by the invention has a higher refractive index, and in some embodiments, the refractive index of the copolycarbonate is 1.65-1.74; the copolycarbonates of the present invention also have a low Abbe number, and in some embodiments, the Abbe number of the copolycarbonate is from 20 to 30.

In some embodiments, the copolycarbonates provided herein have melt indices MFR of 5-70g/10min, and good flowability and processability.

The present invention also provides a method for producing a copolycarbonate by which the above-described copolycarbonate can be produced; the preparation method comprises the following steps:

Reacting a dihydroxy compound and a carbonic acid diester to produce the copolycarbonate; wherein the dihydroxy compound comprises an intermediate a having the following structural formula (a) and an intermediate B having the following structural formula (B);

Wherein R ₁ and R ₂ in the structural formula (A) and R ₃ and R ₄ in the structural formula (B) are each independently a hydrogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C5-20 cycloalkyl group, a C5-20 cycloalkoxy group, a C6-20 aryl group, a C6-20 aryloxy group or a halogen atom;

In some embodiments, the dihydroxy compound and the carbonate compound are reacted by a melt transesterification process to produce the copolycarbonate.

The inventors have found that copolycarbonates having a relatively high refractive index can be obtained using binary copolymerization systems based on intermediate A and intermediate B in the preparation process. In some embodiments, the refractive index may vary from 1.65 to 1.74, depending on the monomer ratio, for example, the molar ratio of intermediate A to intermediate B is adjusted from 1:99 to 99:1.

In a preferred embodiment, the molar ratio of said intermediate A to said intermediate B is in the range of 1:99 to 99:1, such as 50:50 to 99:1, such as 35:65 to 70:30, such as 55:45 to 60:40, more preferably 50:50 to 99:1.

In some embodiments, exemplified, each of R ₁、R₂ is independently a hydrogen atom or a benzene ring, and R ₃ and R ₄ are hydrogen atoms.

In some embodiments, the intermediate a is selected from compounds represented by the following structural formulas (A1) or (A2), and the intermediate B is selected from compounds represented by the following structural formulas (B1):

In the preparation method of the present invention, the carbonic acid diester used may be a carbonic acid diester compound commonly used in the field of preparation of copolycarbonates, preferably, the carbonic acid diester is selected from one or more of diphenyl carbonate, xylene carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate; more preferably, the carbonic acid diester is diphenyl carbonate.

In the present invention, the amount of the carbonic acid diester may be as required in the conventional art, and preferably, the molar ratio of the carbonic acid diester to the dihydroxy compound is 0.97 to 1.20, and more preferably, 0.98 to 1.15.

In the present invention, the copolycarbonate may be prepared by a melt transesterification method well known to those skilled in the art, and specific process operations may be performed by corresponding reaction process operations conventional in the art, without particular limitation. Specifically, the dihydroxy compound and the carbonic acid diester may be reacted in the presence or absence of a catalyst to prepare the copolycarbonate by melt polycondensation.

When a catalyst is used, the catalyst used may be of the type conventionally used in the art for preparing copolycarbonates by melt transesterification; in some embodiments, the catalyst is selected from one or more of a basic compound catalyst, a transesterification catalyst; preferably, the basic compound catalyst is selected from one or more of alkali metal compounds, alkaline earth metal compounds and nitrogen-containing compounds.

Further, in the case of preparing copolycarbonates by the melt transesterification method, the alkali metal compound as a catalyst may be of a type conventionally used in the art, and for example, the alkali metal compound may be one or more of an organic acid salt, an inorganic salt, an oxide, a hydroxide, a hydride, an alkoxide, and the like of an alkali metal; such as, but not limited to, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium, dipotassium, cesium or dilithium salts of bisphenol a, sodium, potassium, cesium or lithium salts of phenol, and the like.

Further, in the case of preparing copolycarbonates by the melt transesterification method, the alkaline earth metal compound as a catalyst may be of a type conventionally used in the art, and for example, the alkaline earth metal compound is one or more of an organic acid salt, an inorganic salt, an oxide, a hydroxide, a hydride, an alkoxide, and the like of an alkaline earth metal; such as, but not limited to, one or more of magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, magnesium phenylphosphate, and the like.

Further, in the case of preparing copolycarbonates by melt transesterification, the nitrogen-containing compound as a catalyst may be of a type conventionally used in the art, and examples of the nitrogen-containing compound include quaternary ammonium hydroxides and salts thereof, amines and the like; specific examples thereof include, but are not limited to, quaternary ammonium hydroxides having an alkyl group, an aryl group, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc., and tertiary amine compounds such as, but not limited to, triethylamine, dimethylbenzylamine, triphenylamine, etc.; secondary amine compounds such as, but not limited to, diethylamine, dibutylamine, and the like; primary amine compounds such as, but not limited to, propylamine, butylamine, and the like; imidazole compounds such as, but not limited to, 2-methylimidazole, 2-phenylimidazole, benzimidazole, and the like; and one or more of a base or basic salt such as, but not limited to, ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, and the like.

Further, in the case of preparing copolycarbonates by the melt transesterification method, the transesterification catalyst used as a catalyst may be of a type conventionally used in the art, and salts of zinc, tin, zirconium, lead, etc. are preferably used, and these may be used alone or in combination. More specifically, the transesterification catalyst may be, for example, but not limited to, one or more of zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyldimethoxy tin, zirconium acetylacetonate, zirconium glycolate, zirconium tetrabutoxide, lead acetate, and the like.

Preferably, the ratio of the amount of catalyst to the amount of the dihydroxy compound material is 1 x 10 ^-8～10^-1, preferably 1 x 10 ^-7～10^-3. The preparation of copolycarbonates by melt transesterification methods known to those skilled in the art are well known to those skilled in the art. Preferably, in preparing the copolycarbonate of the present invention by the melt transesterification method, the respective reaction raw materials and the catalyst are subjected to transesterification under heating at normal pressure or reduced pressure, and polycondensation is performed while removing by-products during the reaction; the reaction may be carried out in two or more stages. In some preferred embodiments, the reaction process specifically comprises: the first stage of reaction is carried out at a temperature of 130-210 ℃ (preferably 160-200 ℃) for 0.1-5 hours (preferably 1-3 hours), then the reaction is carried out continuously by reducing the pressure and increasing the temperature in the reaction process, and finally the reaction is carried out continuously for 0.1-2 hours at a temperature of 230-270 ℃ after reducing the pressure to below 133.32 Pa. The first stage reaction may be carried out at atmospheric pressure. The reaction process of reducing pressure and heating can be carried out continuously or intermittently; for example, in some embodiments this is done: after the first stage reaction is completed, the pressure is reduced to 2 to 10KPa for continuous reaction, for example, the reaction is continued for 0.3 to 1 hour; then heating, for example, heating to 230-270 ℃ to continue the reaction for 10-50 minutes; then reducing the pressure again, for example reducing the pressure to 1-2 KPa, and continuing the reaction, for example continuing the reaction for 0.5-2 hours; then reducing the pressure again, for example reducing the pressure to 200-800 Pa, and continuing the reaction (for example, reacting for 10-50 minutes); finally, the pressure is reduced to below 133.32Pa, and the reaction is continued for 0.1 to 2 hours.

When a catalyst is used in the polymerization reaction for producing copolycarbonates, it is preferable to remove the catalyst or deactivate the catalyst after the polymerization reaction is completed. The above catalyst deactivation operation may be performed using a catalyst deactivator conventionally used in the art. As the catalyst deactivator, there may be used some known acidic substances, preferably esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and the catalyst deactivator may be used alone or in combination. The amount of the catalyst deactivator to be used may be 0.1 to 45 times by mol, preferably 1 to 20 times by mol, and more preferably 2 to 10 times by mol based on the amount of the catalyst to be used; the use of the preferable catalyst deactivator amount is advantageous in sufficiently deactivating the catalyst and hardly affecting the heat resistance of the resin, and the resulting molded article is hardly colored.

The reaction apparatus used for producing the copolycarbonate of the present invention is not particularly limited, and may be, for example, a vertical reaction apparatus equipped with an anchor-type stirring blade, MAXBLEND-type stirring blade, ribbon-type stirring blade or the like, a horizontal reaction apparatus equipped with a paddle blade, a lattice blade, a spectacle blade or the like, or an extruder-type apparatus equipped with a screw, and those skilled in the art may use a reaction apparatus in which these apparatuses are appropriately combined depending on the viscosity of the polymer.

In the invention, the intermediate A of the structural formula (A) can be prepared by carrying out Frideel-Crafts alkylation reaction and Scholl reaction on titanium tetrachloride and phenol under the action of a catalyst to obtain a fluorenone structure, condensing with aromatic hydrocarbon to obtain a dihydroxy compound and carrying out etherification with ethylene oxide, and taking the intermediate of the structural formula (A1) as an example, the intermediate A can be prepared by adopting the method comprising the following steps:

1a) Carbon tetrachloride and 1-naphthol are contacted to perform a first-step reaction, for example, the reaction is performed for 8-12 hours at 140-160 ℃, the first-step reaction is preferably performed under a catalyst, for example, sulfuric acid (for example, 80wt% sulfuric acid) and ferric oxide, the dosage ratio of the two is for example, 0.5-2, and the dosage of the catalyst in a reaction system is for example, 5-12 wt%; the molar ratio of carbon tetrachloride to 1-naphthol is, for example, 15-5:1; preferably, after the reaction, the reaction mixture is separated by extraction with water and then the organic phase is distilled to obtain intermediate D.

2B) The intermediate D is continuously reacted in trifluoroacetic acid for a second step, for example, the reaction is carried out for 10 to 14 hours at the temperature of 150 to 170 ℃, the second step is preferably carried out under the presence of a catalyst, for example, palladium acetate and silver oxide, the dosage ratio of the palladium acetate to the silver oxide is for example, the molar ratio of the palladium acetate to the silver oxide is 1:10 to 20, and the dosage of the catalyst in a reaction system is for example, 5 to 10wt%; preferably, the reaction product is filtered and washed after the reaction. The intermediate P is obtained through the second step of reaction.

3A) The intermediate P is contacted with 1, 1-dinaphthyl methane to carry out a third step of reaction, the reaction temperature is controlled to be not more than 40 ℃, and the reaction time is 1 to 4 hours; the third reaction is preferably carried out under a catalyst such as sulfuric acid (e.g., 80wt% sulfuric acid), and the amount of the catalyst in the reaction system is, for example, 10 to 20wt%; preferably, the reaction product is filtered and washed after the reaction. In some embodiments, the third step reaction is performed in the presence of a solvent such as toluene. In the third reaction step, the intermediate P and 1, 1-dinaphthyl methane are used in a mass ratio of, for example, 1 to 1.2. And obtaining an intermediate product Q through a third step of reaction.

4A) Contacting the intermediate Q with ethylene oxide for a fourth reaction, for example, at 50-80 ℃ for 8-14 hours, preferably under a catalyst, for example, sodium hydroxide, in an amount of 1 x 10 ^-3～10^-5 of the total mass of the reaction system; after the fourth step of reaction is completed, the reaction product is washed by methylene dichloride, and then methanol recrystallization is carried out, so that an intermediate of the structural formula (A1) is obtained.

Intermediate a of formula (a) may be prepared by reference to steps 1 a) -4 a) above, for example by replacing 1, 1-dinaphthyl methane with 1, 1-bis (7-phenyl) naphthyl methane, an intermediate of formula (A2) may be prepared, and in particular, in step 3 a) the corresponding reaction starting materials may be selected depending on the difference in R ₁ and R ₂ groups in intermediate a satisfying formula (a).

In the invention, the intermediate B of the structural formula (B) can be prepared by reacting naphthalene dicarboxaldehyde with aryl magnesium halide to obtain a dihydroxyl compound and then etherifying the dihydroxyl compound with ethylene oxide, and taking the intermediate of the structural formula (B1) as an example, the intermediate can be prepared by adopting a method comprising the following steps:

1b) 2, 7-naphthalene dicarboxaldehyde is contacted with 9-phenanthryl magnesium bromide for reaction, for example, under nitrogen atmosphere at 0 ℃ for 12h to generate an intermediate M, and then a quenching agent (such as ammonium chloride and the like) is added for quenching; extracting, washing and drying the product;

2b) The intermediate M and ethylene oxide are contacted and reacted for example at 50-80 ℃ for 8-14h, the fourth step is preferably carried out under a catalyst, for example sodium hydroxide, the catalyst dosage is for example 1 x 10 ^-3～10^-5 of the mass of the reaction system; preferably, the reaction further comprises washing the reaction product with methylene chloride, and then recrystallizing with methanol to obtain the intermediate of the structural formula (B1).

Intermediate B of formula (B) may be prepared by referring to steps 1B) -2B) above, and specifically, in step 2B), the 9-phenanthryl magnesium bromide may be replaced with the corresponding reaction starting material according to the difference between the R ₃ and R ₄ groups in intermediate B satisfying formula (B), so that the desired target intermediate B may be obtained.

In the above steps 1 a) to 4 a) and 1 b) to 2 b), the amount of each reaction raw material and the amount of the catalyst may be specifically determined according to the final desired target product amount and the reaction yield of each step.

The present invention also provides a product comprising a copolycarbonate as described above or a copolycarbonate prepared by the preparation method described above.

In some embodiments, the product is a composition comprising the copolycarbonate of the invention, such as a solution formulated from the copolycarbonate according to the invention, or the composition is a thermoplastic resin composition, which may optionally contain other additives such as various additives conventionally added to thermoplastic resins. In some embodiments, the proportion of additives is from 0 to 5% by weight, preferably from 0 to 2.5% by weight, particularly preferably from 0 to 2% by weight, relative to the total weight of copolycarbonate. Wherein the additive comprises: one or more of mold release agents, flow aids, heat stabilizers, hydrolysis stabilizers, antioxidants, UV absorbers, flame retardants, antistatic agents, pigments, reinforcing fillers, and the like.

The above composition may be prepared by compounding the copolycarbonate of the present invention and optionally the above additives. In particular, in some embodiments, the composition may be prepared, for example, by: the components of the composition are mixed and melt compounded and melt extruded in common equipment such as internal mixers, extruders and twin screw kneaders at a temperature of 270 ℃ to 330 ℃ and then pelletized by a pelletizer.

Preferably, the product is a shaped article, extrudate or laminate, which may be transparent, translucent or coloured; the shaped parts are, for example, sheets, profiles, extrudates are, for example, tubes, sheets, laminates are, for example, sheets.

Preferably, the product is an optical device, and the copolycarbonate of the present invention can be used in applications where higher refractive index is required, for example, in optical devices such as a mobile phone lens, an AI/VR lens, a security lens, or an optical lens.

The invention also provides the use of the copolycarbonates described above or prepared by the preparation method described above for the preparation of shaped articles, extrudates or laminates, wherein the shaped articles, extrudates or laminates may be transparent, translucent or coloured. For example, the use of the copolycarbonates according to the invention comprises molded parts produced from the copolycarbonates according to the invention or their compositions.

The technical scheme provided by the invention has the following beneficial effects:

The copolycarbonate provided by the invention has the structural unit A and the structural unit B with specific structures, wherein the structural unit A takes an anthracycline as a central group and has a double Cardo ring structure, and the unique conjugated space structure in the structural unit A can inhibit the space rotation of benzene rings and prevent the internal rotation and thermal movement of polymer chain segments, so that the polymer has better thermal stability and light transmittance compared with the polymer formed by fluorene ring structure compounds; the naphthalene structure and the flexible alkoxy chain structure in the main chain of the structural unit B are matched with the unique structural unit A, so that the refractive index can be improved, the double refraction phenomenon of the copolycarbonate can be reduced, and the processability of the polycarbonate can be improved. In the preparation method provided by the invention, the copolycarbonate prepared based on the intermediate A and the intermediate B has a specific structural unit A and a specific structural unit B, and the prepared copolycarbonate has high refractive index and low double refraction and simultaneously has good light transmittance and good processability.

Detailed Description

In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.

Where specific experimental steps or conditions are not noted in the examples, they may be performed according to the operations or conditions of the corresponding conventional experimental steps in the art. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The raw material sources are as follows:

1-naphthol: fangfang City Weomeng chemical Co., ltd;

2, 7-naphthalene dicarboxaldehyde (cas 19800-49-8): porsche chemical industry Co., ltd;

9-phenanthryl magnesium bromide (cas 71112-64-6): beijing carboline technologies Co., ltd;

1, 1-dinaphthyl methane (cas 28515-57-3): chongqing Futeng medicine Co., ltd;

1, 1-bis (7-phenyl) naphthylmethane: chongqing Futeng medicine Co., ltd.

Intermediate preparation example 1:

synthesis of dihydroxy compound A1 of structural formula (A1):

(1) Placing a 3L three-neck flask in a constant temperature oil bath, adding 46.1g of carbon tetrachloride, 432g of 1-naphthol, 15ml of 80wt% sulfuric acid and 30g of ferric oxide, stirring for 10 hours at a reaction temperature of 160 ℃, extracting and separating by water, and distilling an organic phase at 130 ℃ to obtain an intermediate D;

(2) Placing a 3L three-neck flask in a constant temperature oil bath, adding 376.8g of the intermediate D obtained in the step (1), 34.8g of palladium acetate and 52.6g of silver oxide into 1.1L trifluoroacetic acid, stirring for 12 hours at 160 ℃ under nitrogen atmosphere, filtering and washing with dichloromethane to obtain an intermediate P;

(3) A3L three-neck flask was placed in a constant temperature oil bath, 268g of 1, 1-dinaphthyl methane and 600ml of toluene were added, 150ml of 80wt% sulfuric acid was slowly added to the flask, then 312g of intermediate P prepared in step (2) was added under stirring, the reaction temperature was controlled to not exceed 40 ℃, stirring was carried out for 2 hours after the addition was completed, and the product was suction-filtered and washed with methylene chloride to obtain intermediate Q.

(4) 562G of intermediate Q obtained in the step (3), 0.05g of sodium hydroxide and 11g of ethylene oxide are added into a reaction kettle, then 20ml of absolute ethyl alcohol with the temperature of minus 5 ℃ and 1L of dimethylformamide DMF are added into the mixture, the mixture is stirred in a sealing way at the temperature of 70 ℃ and cooled to room temperature after reaction for 12 hours, then white solid is obtained after washing with methylene dichloride, methanol recrystallization is carried out at room temperature, and a target product, namely the dihydroxyl compound A1 with the structural formula (A1) is obtained after suction filtration and drying.

The nuclear magnetic resonance result of the target product is as follows ：¹H-NMR(400MHz,CDCl₃)δ/×10^-6：8.28(m,2H),8.15-8.17(m,4H),8.06(m,2H),7.86(m,2H),7.48-7.58(m,8H),6.95(d,4H),6.18(s,4H),3.91(s,2H),3.65(s,2H).

Intermediate preparation example 2:

synthesis of dihydroxy compound A2 of structural formula (A2):

Reference is made to the aforementioned "intermediate preparation 1" except that: 420.5g of 1, 1-di (7-phenyl) naphthylmethane is adopted to replace 1, 1-dinaphthyl methane in the step (3), and an intermediate R is prepared in the step (3); in the step (4), the intermediate R is adopted to replace the intermediate Q, and finally the target product, namely the dihydroxyl compound A2 of the structural formula (A2) is prepared.

The nuclear magnetic resonance result of the target product is as follows ：¹H-NMR(400MHz,CDCl₃)δ/×10^-6：8.28(m,2H),8.12-8.17(m,4H),7.96(s,2H),7.88-8.17(m,4H),7.41-7.58(m,14H),6.95(s,4H),4.33(d,4H),3.91(s,2H),3.65-3.69(s,6H).

Intermediate preparation example 3:

synthesis of dihydroxy compound B1 of structural formula (B1):

(1) Putting a 5L three-neck flask into an ice-water bath, dissolving 365 g of 2, 7-naphthalene dicarboxaldehyde (4.95 mmol) into 2.5L of dry diethyl ether, adding 1152g of 9-phenanthryl magnesium bromide into the solution, stirring for 12h at the reaction temperature of 0 ℃ under a nitrogen atmosphere, adding 1.25L of 0.1mol/L ammonium chloride aqueous solution to quench the mixed solution, extracting with water, washing an organic phase with dichloromethane, and drying to obtain an intermediate M;

(2) 540g of intermediate M obtained in the step (1), 0.05g of sodium hydroxide and 11g of ethylene oxide are added into a reaction kettle, then 20ml of absolute ethyl alcohol with the temperature of minus 5 ℃ and 1L of dimethylformamide DMF are added into the mixture, the mixture is stirred in a sealing way at the temperature of 70 ℃ and cooled to room temperature after reaction for 12 hours, then white solid is obtained after washing with methylene dichloride, methanol recrystallization is carried out at room temperature, and the target product, namely the dihydroxyl compound B1 with the structural formula (B1) is obtained after suction filtration and drying.

The nuclear magnetic resonance result of the target product is as follows ：¹H-NMR(400MHz,CDCl₃)δ/×10^-6：8.93(m,4H),8.12(m,4H),7.82-7.95(s,10H),7.64(s,2H),7.43(s,2H),7.14(m,2H),5.41(s,2H),3.56-3.7(m,10H).

Example 1

Copolycarbonates prepared on the basis of dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 99:1.

64.425G (0.099 mol) of dihydroxy compound A1, 0.629g (0.001 mol) of dihydroxy compound B1, 22.278 (0.104 mol) of diphenyl carbonate and 0.0002g (5X 10 ^-6 mol) of sodium hydroxide were charged into a reactor equipped with a stirring and distilling apparatus, and heated to 160℃for 1 hour under normal pressure to melt them. Thereafter, the temperature was raised to 200℃over 0.5 hour, and stirring was carried out. Then, the pressure was adjusted to 2KPa for 10 minutes, and the reaction was kept at 200℃for 30 minutes under 2KPa to carry out transesterification. Then the temperature is raised to 260 ℃ at the speed of 50 ℃/hour, and the mixture is kept at 260 ℃ for 20 minutes at 2 KPa. Then, the temperature was adjusted to 1KPa for 10 minutes, and the temperature was maintained at 260℃for 1 hour at 1 KPa. Then adjusted to 500Pa for 10 minutes, and maintained at 260℃for 20 minutes at 500 Pa. The pressure was reduced to 133Pa or lower for 30 minutes, and the mixture was stirred at 260℃for 15 minutes under 133Pa or lower to carry out polymerization. After the reaction, butyl benzoate was added in an amount 2 times the amount of the catalyst (sodium hydroxide) to deactivate the catalyst, the reaction product was discharged from the bottom of the reaction tank under nitrogen pressure, and the mixture was cooled in the tank and cut with a granulator to obtain granules. The physical properties of the obtained copolycarbonate resin, no. C1, are shown in table 1.

Example 2

Copolycarbonates prepared on the basis of the dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 90:10.

Physical properties of the resulting copolycarbonates were as shown in Table 1, except that 58.57g (0.09 mol) of the dihydroxy compound A1 and 6.29g (0.01 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1.

Example 3

Copolycarbonates prepared on the basis of the dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 70:30.

The physical properties of the resulting copolycarbonates were as shown in Table 1, except that 45.55g (0.07 mol) of the dihydroxy compound A1 and 18.86g (0.03 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1, with the exception of the number C3.

Example 4

Copolycarbonates prepared on the basis of the dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 50:50.

Physical properties of the resulting copolycarbonates were as shown in Table 1, except that 32.54g (0.05 mol) of the dihydroxy compound A1 and 31.44g (0.05 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1, with the exception of the number C4.

Example 5

Copolycarbonates prepared on the basis of the dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 30:70.

The physical properties of the resulting copolycarbonates were as shown in Table 1, except that 19.52g (0.03 mol) of the dihydroxy compound A1 and 44.01g (0.07 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1.

Example 6

Copolycarbonates prepared on the basis of the dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 10:90.

The physical properties of the resulting copolycarbonates were as shown in Table 1, except that 6.51g (0.01 mol) of the dihydroxy compound A1 and 56.59g (0.09 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1.

Example 7

Copolycarbonates prepared on the basis of the dihydroxy compounds A1, B1 were synthesized in which the molar ratio of structural units A to structural units B was 1:99.

The physical properties of the resulting copolycarbonates were as shown in Table 1, except that 0.651g (0.001 mol) of the dihydroxy compound A1 and 62.25g (0.099 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1, with the exception of the number C7.

Example 8

Copolycarbonates prepared on the basis of the dihydroxy compounds A2, B1 were synthesized in which the molar ratio of structural units A to structural units B was 70:30.

The physical properties of the resulting copolycarbonate were as shown in Table 1, except that 56.21g (0.07 mol) of the dihydroxy compound A2 and 18.86g (0.03 mol) of the dihydroxy compound B1 were used, and the resulting copolycarbonate was synthesized as described in example 1, with the number C8.

Comparative example 1

Copolycarbonates were prepared from dihydroxy compound A1 and bisphenol A in a molar ratio of 30:70.

The main difference between the present invention and example 1 is that the dihydroxy compounds A1 and B1 used in example 1 were replaced with 19.52g (0.03 mol) of the dihydroxy compounds A1 and 15.981g (0.07 mol) of bisphenol A, and the remainder was the same as in example 1. The physical properties of the obtained copolycarbonate resin, no. D1, are shown in table 1.

Comparative example 2

Copolycarbonates were prepared from dihydroxy compound A2 and bisphenol A in a molar ratio of 30:70.

The main difference between the present invention and example 1 is that the dihydroxy compounds A1 and B1 used in example 1 were replaced with 24.09g (0.03 mol) of dihydroxy compounds A2 and 15.981g (0.07 mol) of bisphenol A. The physical properties of the copolycarbonate resin obtained, number D2, are shown in Table 1

Comparative example 3

Copolycarbonates prepared from dihydroxy compound B1 and bisphenol A in a molar ratio of 30:70.

The main difference between the present invention and example 1 is that the dihydroxy compounds A1 and B1 in example 1 were replaced with 18.86g (0.03 mol) of the dihydroxy compounds B1 and 15.981g (0.07 mol) of bisphenol A. The physical properties of the obtained copolycarbonate resin, no. D3, are shown in table 1.

After the reaction of the above examples and comparative examples is finished, the reaction monomers in the reaction system are detected to be completely reacted by liquid chromatography, and the content of residual monomers is less than 100ppm.

Performance testing

The copolycarbonates prepared in the above examples and comparative examples were characterized by means of refractive index, abbe number, orientation birefringence, light transmittance, melt index tests. Refractive index, abbe number, light transmittance were obtained by measuring copolycarbonate films, refractive index, abbe number were measured according to ASTM D542, light transmittance was measured according to ASTM D1003; the copolycarbonate film was prepared by dissolving a copolycarbonate resin in methylene chloride to prepare a 10wt% solution, and then spin-coating the solution to a thickness of 50. Mu.m.

Orientation birefringence measurement

After cutting a casting film having a thickness of 100 μm into a casting direction of 7cm and a direction perpendicular to the casting direction (width direction) of 1.5cm, both ends in the longitudinal direction were clamped to chucks (chuck spacing 4.5 cm), and the film was stretched 2 times in the casting direction at Tg+10deg.C of the copolycarbonate resin, and the retardation (Re) at 589nm was measured by using a polarization ellipsometer M-220 manufactured by Japan spectroscopy, and the orientation birefringence (Deltan) was determined by the following formula.

Δn＝Re/d

An: orientation birefringence

Re: phase difference

D: thickness of (L)

Fluidity: melt flow rate MFR is measured by ASTM D1238. The filled material was placed in a vertical cylinder with a small die of 2mm at the bottom, measured at 260 ℃, then a specified load was applied to the molten material and the material extruded through the die was collected, then the amount of material extruded after a given time was normalized to g/10min.

The characterization results of each copolycarbonate resin are shown in Table 1.

Weight average molecular weight (Mw): using Gel Permeation Chromatography (GPC), a standard curve was prepared using standard polystyrene of known molecular weight (molecular weight distribution=1) with dichloromethane as a solvent. Based on the standard curve, mw was calculated from the retention time of GPC.

TABLE 1

As can be seen from the experimental results, the copolycarbonates obtained in the examples using the scheme of the present invention have relatively high refractive indexes as compared with the comparative examples, and although the Abbe numbers of the examples and the comparative examples are in the range of 20 to 30, the Abbe numbers of the examples are relatively lower and the orientation birefringence is relatively lower; meanwhile, the copolycarbonate provided by the invention has good light transmittance; the copolycarbonates obtained also have good flowability (MFR in the art from 5 to 70g/10min, considered to have good flowability) compared with the comparative examples, and good processability.

It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims

1. A copolycarbonate comprising structural unit a of formula (I) and structural unit B of formula (II):

2. The copolycarbonate of claim 1, wherein the molar ratio of structural unit a to structural unit B is from 1:99 to 99:1.

3. The copolycarbonate according to claim 2, wherein the molar ratio of structural unit a to structural unit B is 50:50 to 99:1.

4. The copolycarbonate according to claim 1, wherein the weight average molecular weight of the copolycarbonate is 10000-200000.

5. The copolycarbonate according to claim 4, wherein the copolycarbonate has a weight average molecular weight of 15000 to 80000.

6. The copolycarbonate according to claim 5, wherein the weight average molecular weight of the copolycarbonate is 20000 to 70000.

7. The copolycarbonate according to any one of claims 1-6, wherein each R ₁、R₂ is independently a hydrogen atom or a benzene ring, and R ₃ and R ₄ are hydrogen atoms.

8. The copolycarbonate according to claim 7, wherein the structural unit a has the following structural formula (a 1) or (a 2), and the structural unit B has the following structural formula (B1):

9. The copolycarbonate according to any one of claims 1-6, wherein the copolycarbonate has a refractive index of 1.65 to 1.74;

And/or, the abbe number of the copolycarbonate is 20-30;

And/or the melt index MFR of the copolycarbonate is 5-70g/10min.

10. A method for preparing copolycarbonate, comprising the steps of:

Wherein R ₁ and R ₂ in the structural formula (A) and R ₃ and R ₄ in the structural formula (B) are each independently a hydrogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C5-20 cycloalkyl group, a C5-20 cycloalkoxy group, a C6-20 aryl group, a C6-20 aryloxy group or a halogen atom.

11. The process of claim 10, wherein the molar ratio of intermediate a to intermediate B is from 1:99 to 99:1.

12. The process of claim 11, wherein the molar ratio of intermediate a to intermediate B is from 50:50 to 99:1.

13. The production method according to claim 10, wherein the dihydroxy compound and the carbonic acid diester are reacted by a melt transesterification method to produce the copolycarbonate.

14. The production method according to any one of claims 10 to 13, wherein each of R ₁、R₂ is independently a hydrogen atom or a benzene ring, and R ₃ and R ₄ are hydrogen atoms;

And/or the carbonic diester is selected from one or more of diphenyl carbonate, dimethylbenzene carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate;

and/or the molar ratio of the carbonic acid diester to the dihydroxy compound is 0.97 to 1.20;

and/or reacting the dihydroxy compound and the carbonic acid diester in the presence or absence of a catalyst to produce the copolycarbonate.

15. The production method according to claim 14, wherein the intermediate a is selected from compounds represented by the following structural formula (A1) or (A2), and the intermediate B is selected from compounds represented by the following structural formula (B1):

16. The method according to claim 14, wherein the molar ratio of the carbonic acid diester to the dihydroxy compound is 0.98 to 1.15.

17. The method according to claim 14, wherein the catalyst is one or more selected from the group consisting of a basic compound catalyst and a transesterification catalyst.

18. The method according to claim 17, wherein the basic compound catalyst is one or more selected from the group consisting of an alkali metal compound, an alkaline earth metal compound, and a nitrogen-containing compound.

19. The method according to claim 14, wherein the ratio of the amount of the catalyst to the amount of the substance of the dihydroxy compound is 1x10 ^-8～10^-1.

20. The method according to claim 19, wherein the ratio of the amount of the catalyst to the amount of the substance of the dihydroxy compound is 1x10 ^-7～10^-3.

21. The method of any one of claims 10 to 13, wherein the copolycarbonate of any one of claims 1 to 9 is produced by the method of production.

22. A product comprising the copolycarbonate of any one of claims 1-9 or the copolycarbonate produced by the method of any one of claims 10-21.

23. The product of claim 22, wherein the product is a shaped piece, extrudate, or laminate.

24. The product of claim 22, wherein the product is an optical device.

25. Use of the copolycarbonate according to any one of claims 1 to 9 or the copolycarbonate produced by the production method according to any one of claims 10 to 24 for producing shaped parts, extrudates or laminates.