A hydrophobic heat-resistant bio-based polycarbonate copolymer, and a preparation method and application thereof

Abstract

The present application belongs to the technical field of polycarbonates, and particularly relates to a polycarbonate copolymer, a preparation method and application thereof. By introducing a fluorine-containing rigid structural unit, the material heat resistance is improved, the surface energy is significantly reduced, the hydrophobic property is improved, and the moisture heat aging resistance of the polycarbonate copolymer is synergistically improved from two dimensions of heat resistance and hydrophobicity. The copolymer has excellent transparency, mechanical property and thermal stability, and is suitable for the field of engineering plastics, and is particularly suitable for application scenarios with high requirements for moisture heat aging resistance.

Description

[0001] This invention relates to a method for preparing and using a bio-based polycarbonate copolymer that combines surface hydrophobicity and good heat resistance. Background Technology

[0002] Polycarbonate is a polymer material containing carbonate groups in its main chain. Thanks to its unique molecular structure, polycarbonate possesses excellent optical transmittance, outstanding impact resistance, and good heat resistance, making it widely used in automotive parts, AI speakers (smart speaker housings), optical sheets, and electronic appliance casings. It is considered one of the five major engineering plastics, along with polyamide, polyoxymethylene, polyphenylene ether, and thermoplastic polyester. Among them, bisphenol A polycarbonate (BPA-PC) is the most common type on the market due to its mature synthesis process and balanced overall performance. However, during long-term use, residual or degraded BPA in BPA-PC gradually leach out. BPA has chronic toxic effects (such as interfering with the endocrine system), posing a potential threat to human health. Therefore, its use in sensitive areas such as food packaging and infant bottles has been prohibited. To overcome this drawback, isosorbide polycarbonate (Iosorbide-based) using biomass resources has emerged. However, isosorbide-based biocarbonate suffers from low toughness and high melt viscosity, making its processing and molding difficult and limiting its practical applications.

[0003] Patents CN101448871A and CN111138650A propose copolymerizing isosorbide (ISB) with a flexible diol to improve the toughness and processing flowability of bio-based polycarbonate (PC). Among them, the bio-based polycarbonate (ISB) prepared by co-polymerizing isosorbide and 1,4-cyclohexanediethanol is... c Compared to BPA-PC, C-PC (C-PC) has the advantage of... c C-PC is not only made from green and renewable raw materials, but also has higher optical transmittance (up to 92% or more) and better heat resistance, while maintaining good mechanical strength. It is regarded as the next generation of high-performance and environmentally friendly polycarbonate material.

[0004] But I c The ether bonds in the ISB difuran ring of C-PC give it strong hygroscopic properties. Furthermore, the use of 1,4-cyclohexanediethanol in toughening bio-based PC leads to... c The glass transition temperature of C-PC ( T g This decrease further accelerates the material's water absorption behavior. After water absorption, I... c C-PC is prone to degradation, brittle transition, and decreased heat resistance, making it difficult to pass damp heat aging tests. Therefore, it is necessary to study I... c C-PC is modified.

[0005] Patent CN 118126304 A improves the heat resistance of the copolymer by copolymerizing it with HBPA, which has good heat resistance, thereby slowing down its hygrothermal aging process. Patent CN 118271588A improves the hydrophobicity of the material by copolymerizing it with a fluorinated polyether with low surface energy and bio-based PC. It should be noted that although the above modifications have made useful explorations into the hygrothermal aging problem of bio-based PC from the perspectives of heat resistance and hydrophobicity, they all adopted a single modification strategy and failed to simultaneously improve the resistance to hygrothermal aging from both dimensions. In humid and hot environments, the resistance of a material to hygrothermal aging depends not only on its heat resistance but also on its hydrophobicity; both are indispensable. Therefore, how to synergistically modify bio-based polycarbonate from both the dimensions of heat resistance and hydrophobicity to comprehensively improve its resistance to hygrothermal aging is a technical problem that urgently needs to be solved. Summary of the Invention

[0006] To address the aforementioned problems, this invention proposes using 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane (HBPAF), a fluorinated derivative of hydrogenated bisphenol A, as a comonomer to address the I... c C-PC was copolymerized and modified. The HBPAF molecular structure contains a hydrogenated bisphenol A backbone, which endows the copolymer with good heat resistance. At the same time, the fluorine element contained in the molecular structure can effectively reduce the surface energy of the material and significantly improve the hydrophobicity. This invention achieves a synergistic improvement in the material's resistance to humid heat aging from both heat resistance and hydrophobicity dimensions, thereby overcoming the shortcomings of single modification strategies in the prior art.

[0007] To achieve the above objectives, the present invention provides the following technical solutions.

[0008] This invention provides a polycarbonate copolymer comprising repeating units represented by formulas A, B, and C: Formula A; Formula B; Formula C;

[0009] Formula A includes the following A-1, A-2, and A-3: Formula A-1; Formula A-2; Formula A-3;

[0010] In formula B, R1 represents a copolymer structure that is either an aliphatic hydrocarbon group or an alicyclic hydrocarbon group;

[0011] In formula C, R2 represents a copolymer structure as shown in formula 1, containing both a rigid bicyclohexane group and a fluoroalkyl group with a CF group. Formula 1;

[0012] In Formula 1, R3 and R4 each independently represent substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups with 1 to 20 carbon atoms. The molecular structure of X contains at least one hexafluoropropane group or a fluorinated alkyl-substituted quaternary carbon.

[0013] Preferably, R1 is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group with 2 to 8 carbon atoms.

[0014] Preferably, the number of moles of the repeating unit in the structure shown in Formula A is 40% to 60% of the sum of the number of moles of the repeating units in the structures shown in Formulas A, B, and C.

[0015] Preferably, the number of moles of the repeating units in the structure shown in Formula B is 20% to 30% of the sum of the number of moles of the repeating units in the structures shown in Formulas A, B and C.

[0016] Preferably, the number of moles of the repeating units in the structure shown in Formula C is 10% to 30% of the sum of the number of moles of the repeating units in the structures shown in Formulas A, B and C.

[0017] The present invention also provides a method for preparing the polycarbonate copolymer, comprising the following steps:

[0018] Under a protective atmosphere, the carbonate diester and diol monomer are mixed and then subjected to transesterification and polycondensation reactions in sequence under catalytic conditions to obtain the polycarbonate copolymer.

[0019] The diol monomers include 1,4;3,6-didehydrohexanehexanedol, a first alcohol monomer, and a second alcohol monomer;

[0020] The first alcohol monomer includes an aliphatic diol or an alicyclic hydrocarbon diol;

[0021] The second alcohol monomer has the structure shown in Formula 2: Formula 2;

[0022] Preferably, the molar ratio of the carbonate diester to the dihydroxy compound is 0.9 to 1.2:1; the temperature of the transesterification reaction is 160 to 210°C; the pressure of the transesterification is atmospheric pressure; and the transesterification time is 1 to 3 hours.

[0023] Preferably, the temperature of the polycondensation reaction is 210 ~ 250°C, the pressure is gradually reduced from atmospheric pressure to below 50 Pa, and the duration is 0.5 ~ 5 h.

[0024] The present invention also provides the application of the polycarbonate copolymer or the polycarbonate copolymer prepared by the preparation method described above in the field of engineering plastics.

[0025] This invention provides a polycarbonate copolymer comprising repeating units represented by formulas A, B, and C: Formula A; Formula B; Formula C;

[0026] Formula A includes the following A-1, A-2, and A-3: Formula A-1; Formula A-2; Formula A-3.

[0027] In formula B, R1 represents a copolymer structure that is either an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[0028] In formula C, R2 represents a copolymer structure as shown in formula 1, which contains both rigid bicyclohexane and CF groups of fluorocarbon groups. Formula 1;

[0029] In Formula 1, R3 and R4 each independently represent substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups with 1 to 20 carbon atoms. The molecular structure of X contains at least one hexafluoropropane group or a fluorinated alkyl-substituted quaternary carbon. Detailed Implementation

[0030] The following examples are used to illustrate the present invention, but should not be used to limit the scope of the invention.

[0031] This invention provides a polycarbonate copolymer comprising repeating units represented by formulas A, B, and C: Formula A; Formula B; Formula C;

[0032] Formula A includes the following A-1, A-2, and A-3: Formula A-1; Formula A-2; Formula A-3.

[0033] In this invention, the molar number of the repeating unit in the structure shown in Formula A is preferably 30% to 80% of the sum of the molar numbers of the repeating units in the structures shown in Formulas A, B, and C, and more preferably 40% to 70%. When the content is higher than 70%, the water absorption rate is high and the toughness is poor; when the content is lower than 40%, the utilization of biomass resources is insufficient.

[0034] In Formula B, R1 represents a copolymer structure consisting of aliphatic or alicyclic hydrocarbon groups, accounting for 10% to 50% of the total repeating units. When the content is below 10%, the copolymer segments are too rigid, resulting in insufficient polymer toughness. When the content is above 50%, the heat resistance decreases significantly. T g <110℃), which cannot meet the requirements for high-temperature use scenarios.

[0035] In formula C, R2 represents the copolymer structure shown in formula 1, which contains both rigid bicyclohexane and CF groups of fluorocarbons.

[0036] Formula 1.

[0037] In structure R2, R3 and R4 independently represent cycloalkyl groups with fluorine substitution, carbon-fluorine substitution, or no substitution. The X molecule contains at least one hexafluoropropane group or a fluorinated alkyl-substituted quaternary carbon, accounting for 10% to 50% of the total repeating units, preferably 10% to 30%. When the content is below 10%, the hydrophobic effect of the copolymer is not significant; when the content is above 30%, the cost is too high and it is difficult to prepare high molecular weight copolymers.

[0038] The present invention also provides a method for preparing the aforementioned polycarbonate copolymer, comprising the following steps:

[0039] Under a protective atmosphere, the diester and diol monomer are mixed and then subjected to transesterification and polycondensation reactions in sequence under catalytic conditions to obtain the polycarbonate copolymer.

[0040] In this invention, the carbonate diesters include diphenyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, as well as diphenyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate with substituents. These carbonate diesters can be used alone or in combination with two or more. Diphenyl carbonate or substituted diphenyl carbonates are preferred, and diphenyl carbonate is particularly preferred.

[0041] In this invention, the diol monomers include 1,4;3,6-didehydrohexanehexacol, aliphatic diols or alicyclic diols and fluorinated aromatic diol hydrides.

[0042] In this invention, the 1,4;3,6-didehydrohexahexanol is selected from at least one of isosorbide, isomannitol and iso-idole, with isosorbide preferred considering monomer cost and reactivity.

[0043] In this invention, the aliphatic diol is selected from straight-chain aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; and branched aliphatic dihydroxy compounds such as 1,2-butanediol, 1,3-butanediol, neopentanediol, and hexanediol.

[0044] In this invention, the alicyclic diol compound is selected from 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, tricyclodecanediethanol, pentacyclopentadecanedimethanol, 2,6-decanediethanol, 1,5-decanediethanol, 2,3-decanediethanol, 2,3-norbornanediethanol, 2,5-norbornanediethanol, 1,3-adamantanediethanol, limonene, and other dihydroxy compounds derived from terpene compounds, as well as alicyclic dihydroxy compounds containing primary alcohols; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, etc. 1,4-cyclohexanediethanol is preferred.

[0045] In this invention, the fluorinated aromatic diol hydride has the structure shown in Formula 2: Equation 2.

[0046] In this invention, the fluorinated aromatic diol hydrides include: 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 2,2-bis(3-methyl-4-hydroxycyclohexyl)hexafluoropropane, 2,2-bis(4-hydroxy-3,5-dimethylcyclohexyl)hexafluoropropane, 2,2-bis(4-hydroxy-3,5-diethylcyclohexyl)hexafluoropropane, 2,2-bis(4-hydroxy-(3-cyclohexyl)cyclohexyl)hexafluoropropane, 2,2-bis(4-hydroxy-(3,5-dicyclohexyl)cyclohexyl)hexafluoropropane, 2,2-bis(3-fluoro-4-hydroxycyclohexyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-trifluoromethylcyclohexyl)hexafluoropropane, etc. Preferably, 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane is used.

[0047] In this invention, the catalyst preferably includes metal compounds of Group IA or IIA, Group IB or IIB of the periodic table, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, organic amine compounds, and ionic liquid compounds.

[0048] In this invention, the Group IA metal compounds may include the following compounds: sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium aluminate, potassium aluminate, lithium aluminate, cesium aluminate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride. Lithium borohydride, cesium borohydride, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate; alkoxides and phenolates of sodium, potassium, lithium, and cesium; disodium salts, dipotassium salts, dilithium salts, and dicesium salts of bisphenol A, etc.

[0049] In this invention, the Group IIA metal compounds may include the following compounds: calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium aluminate, barium aluminate, magnesium aluminate, strontium aluminate, calcium chloride, magnesium chloride, zinc chloride, calcium stearate, barium stearate, magnesium stearate, and strontium stearate, etc.

[0050] In this invention, the Group IB metal compounds may include the following compounds: copper hydroxide, copper oxide, copper chloride, copper nitrate, copper stearate, copper sulfate, copper sulfite, copper benzoate, copper carbonate, copper bicarbonate, copper fluoride, copper bromide, copper iodide, copper acetate, copper oxalate, copper acetylacetone, copper phosphate, etc.

[0051] In this invention, the Group IIB metal compounds may include the following compounds: zinc hydroxide, zinc oxide, zinc aluminate, zinc chloride, zinc nitrate, zinc stearate, zinc sulfate, zinc sulfite, zinc benzoate, zinc carbonate, zinc bicarbonate, zinc fluoride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetone, zinc oxalate, zinc phosphate, etc.

[0052] In this invention, the basic phosphorus compound may include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphine salts. From the perspective of reactivity and the color of the resulting polycarbonate resin, quaternary phosphine salts are preferred.

[0053] In this invention, the basic ammonium compound may include the following compounds: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide, etc. Alkyl ammonium hydroxide is preferred from the perspective of reactivity and the color of the resulting polycarbonate resin.

[0054] In this invention, the organic amine compounds may include the following compounds: 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazolium, 2-methoxyimidazolium, imidazole, 2-mercaptoimidazolium, 2-methylimidazolium, aminoquinoline, and guanidine, etc.

[0055] In this invention, the anion of the ionic liquid compound is preferably an amino acid anion or an amide anion. The preferred amino acid anions are lysine anion, threonine anion, valine anion, alanine anion, serine anion, histidine anion, or aspartic acid anion. The preferred amide anions are N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-azhexanecycloone, 1,8-naphthalenediamide, 1,2-cyclopentanediamide, 3,3-pentamethyleneglutamate, 3,3-tetramethyleneglutamate, 1,2,3,6-tetrahydrophthalimide, hexahydrophthalimide, diacetamide, succinimide, glutamate, adipamide, maleimide, succinimide, phthalimide, or bis(trifluoroacetamide).

[0056] The preferred cations for the aforementioned ionic liquid catalysts are quaternary ammonium cations, quaternary phosphine cations, imidazole cations, pyridine cations, or piperidine cations. Quaternary ammonium cations are preferably tetraethylammonium cations, tetrabutylammonium cations, or choline cations; quaternary phosphine cations are preferably tetrabutylphosphine cations or trihexyl(tetradecyl)phosphine cations; imidazole cations are preferably 1-ethyl-3-methylimidazolium cations, 1-propyl-3-methylimidazolium cations, 1-butyl-3-methylimidazolium cations, 1-pentyl-3-methylimidazolium cations, 1-hexyl-3-methylimidazolium cations, 1-benzyl-3-methylimidazolium cations, 1-ethyl acetate-3-methylimidazolium cations, 1-allyl-3-methylimidazolium cations, or 1-2-(hydroxyethyl)-3-methylimidazolium cations; and pyridine cations are preferably N-ethylpyridine cations or N-butyl-N-methylpiperidine cations.

[0057] The catalysts used in the preparation of polycarbonate can be used alone or in combination with two or more. The amount of Group IA or IIA metal compounds and Group IB or IIB metal compound catalysts used per mole of all dihydroxy compounds used in the reaction is preferably 0.1 to 1000 ppm, more preferably 1 to 500 ppm, and even more preferably 10 to 100 ppm; the amount of basic phosphorus compounds, basic ammonium compounds, and organic amine compounds used is preferably 1 to 300 ppm, more preferably 3 to 200 ppm, and even more preferably 5 to 100 ppm; the amount of ionic liquid compounds is preferably 1 to 300 ppm, more preferably 10 to 200 ppm.

[0058] In this invention, the dicarbonate is preferably used in a molar ratio of 0.90-1.20 relative to all dihydroxy compounds used in the reaction, more preferably in a molar ratio of 0.95-1.05. If this molar ratio is less than 0.9 or greater than 1.20, the transesterification reaction rate decreases under the same conditions, or the desired molecular weight of polycarbonate is not obtained, and the residual amount of diphenyl carbonate in the produced polycarbonate increases.

[0059] In this invention, the temperature of the transesterification reaction is preferably 160-210°C, more preferably 180-200°C, and the holding time is preferably 1-3 hours, more preferably 2 hours.

[0060] After obtaining the polycarbonate prepolymer, the present invention performs a polycondensation reaction on the polycarbonate prepolymer to obtain the polycarbonate copolymer.

[0061] In this invention, the temperature of the polycondensation reaction is preferably 210 ~ 250°C, the pressure is gradually reduced from atmospheric pressure to below 50 Pa, and the duration is 0.5 ~ 5 h.

[0062] In manufacturing the polycarbonate of this invention, to prevent yellowing and thermal degradation, hindered phenols, phosphites, and other antioxidant stabilizers can be added during or at the end of polymerization. Catalytically active quenchers can also be added, and if necessary, UV absorbers, light stabilizers, release agents, color modifiers, and other additives can be added. Preferably, the additives are added after the polymerization reaction is complete, using a twin-screw extruder or similar equipment.

[0063] In this invention, heat stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and their esters, specifically triphenyl phosphate, tris(nonylphenyl) phosphate, tridecyl phosphonate, trioctyl phosphonate, trioctadecyl phosphonate, didecyl phosphate, monophenyl phosphate, dioctyl monophenyl phosphate, diisopropyl monophenyl phosphate, monobutyl diphenyl phosphate, monodecyl diphenyl phosphate, monooctyl diphenyl phosphate, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphate, bis(nonylphenyl)pentaerythritol diphosphate, bis(2... (4-Di-tert-butylphenyl) pentaerythritol diphosphite, distearate pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, trimethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenyl phosphate, diethyl phenyl phosphate, dipropyl phenyl phosphate, etc. These heat stabilizers can be used alone or in combination of two or more.

[0064] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0065] Example 1

[0066] At room temperature, 7.583 g of diphenyl carbonate, 3.073 g of isosorbide, 1.221 g of 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 1.516 g of 1,4-cyclohexanediethanol, and 0.001 mol% sodium aluminate catalyst (based on the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. The system was heated to 180 °C for transesterification for 1 h, followed by gradient heating and reduced pressure, and finally reacted at 250 °C and below 50 Pa for 10 min. The reaction yielded a copolymer with an intrinsic viscosity of 58.2. The properties of the reaction product were characterized, and the results are shown in Table 1.

[0067] Example 2

[0068] Adjusting the feed ratio, at room temperature, 7.583 g of diphenyl carbonate, 2.561 g of isosorbide, 2.442 g of 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 1.516 g of 1,4-cyclohexanediethanol, and 0.001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other steps remained consistent with Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 51.2 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 1.

[0069] Example 3

[0070] Adjusting the feed ratio, at room temperature, 7.583 g of diphenyl carbonate, 2.049 g of isosorbide, 3.663 g of 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 1.516 g of 1,4-cyclohexanediethanol, and 0.001 mol% sodium aluminate catalyst (based on the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other steps remained consistent with Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 51.7 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 1.

[0071] Example 4

[0072] The feed ratio was adjusted, and at room temperature, 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, 1.221 g of 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 1.011 g of 1,4-cyclohexanediethanol, and 0.001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other steps remained the same as in Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 61.0 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 1.

[0073] Example 5

[0074] Adjusting the feed ratio, at room temperature, 7.583 g of diphenyl carbonate, 3.073 g of isosorbide, 2.442 g of 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 1.011 g of 1,4-cyclohexanediethanol, and 0.001 mol% sodium aluminate catalyst (based on the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other steps remained consistent with Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 52.6 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 1.

[0075] Example 6

[0076] Adjusting the feed ratio, at room temperature, 7.583 g of diphenyl carbonate, 2.561 g of isosorbide, 3.663 g of 2,2-bis(4-hydroxycyclohexyl)hexafluoropropane, 1.011 g of 1,4-cyclohexanediethanol, and 0.001 mol% sodium aluminate catalyst (based on the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other steps remained consistent with Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 51.9 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 1.

[0077] Table 1. Properties of the polycarbonate copolymers prepared in the examples;

[0078] Comparative Example 1

[0079] At room temperature, 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, and 1.516 g of 1,4-cyclohexanediethanol were added to a 100 ml three-necked flask containing 0.001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound). The system was heated to 180 °C for transesterification for 1 h, followed by a gradient increase in temperature and reduced pressure. Finally, the reaction was carried out at 250 °C and below 50 Pa for 10 min. The reaction yielded a copolymer with an intrinsic viscosity of 52.3. The properties of the reaction product were characterized, and the results are shown in Table 2.

[0080] Comparative Example 2

[0081] The catalyst dosage was adjusted by adding 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, and 1.516 g of 1,4-cyclohexanediethanol to a 100 ml three-necked flask containing 0.0001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound). All other parameters remained the same as in Comparative Example 1. The reaction yielded a polycarbonate copolymer with an intrinsic viscosity of 49.9. The properties of the reaction product were characterized, and the results are shown in Table 2.

[0082] Comparative Example 3

[0083] The catalyst type was adjusted by adding 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, and 1.516 g of 1,4-cyclohexanediethanol to a 100 ml three-necked flask containing 0.0001 mol% cesium carbonate catalyst (the amount of the dihydroxy compound). All other parameters remained the same as in Comparative Example 1. The reaction yielded a polycarbonate copolymer with an intrinsic viscosity of 53.6. The properties of the reaction product were characterized, and the results are shown in Table 2.

[0084] Comparative Example 4

[0085] The feed ratio was adjusted, and 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, 0.421 g of 2,2-bis(4-hydroxycyclohexyl)propane, 1.264 g of 1,4-cyclohexanediethanol, and 0.0001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other parameters remained the same as in Comparative Example 1. After the reaction was completed, a polycarbonate copolymer with an intrinsic viscosity of 50.3 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 2.

[0086] Comparative Example 5

[0087] The feed ratio was adjusted, and at room temperature, 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, 0.842 g of 2,2-bis(4-hydroxycyclohexyl)propane, 1.011 g of 1,4-cyclohexanediethanol, and 0.0001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other parameters remained consistent with Comparative Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 47.0 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 2.

[0088] Comparative Example 6

[0089] The feed ratio was adjusted, and at room temperature, 7.583 g of diphenyl carbonate, 3.586 g of isosorbide, 1.264 g of 2,2-bis(4-hydroxycyclohexyl)propane, 0.758 g of 1,4-cyclohexanediethanol, and 0.0001 mol% sodium aluminate catalyst (the amount of the dihydroxy compound) were added to a 100 ml three-necked flask. Other parameters remained consistent with Comparative Example 1. After the reaction was complete, a polycarbonate copolymer with an intrinsic viscosity of 45.3 was obtained. The properties of the reaction product were characterized, and the results are shown in Table 2.

[0090] Table 2. Properties of the polycarbonate copolymers prepared in the examples;

[0091] The performance testing methods in the embodiments and comparative examples of this invention are as follows.

[0092] (1) Characteristic viscosity.

[0093] The above polycarbonate copolymer was dissolved in chloroform to a concentration c of 0.01 g / mL, and the concentration was measured using an Ubbelohde viscometer at a temperature of 25 °C ± 0.5. The intrinsic viscosity [η] was calculated using the following formula.

[0094]

[0095]

[0096]

[0097] Where t is the flow time of the solution and t0 is the flow time of the solvent alone.

[0098] (2) Mechanical performance testing

[0099] The stress-strain curves under tensile conditions were determined using an INSTRON 3365 universal testing machine. The specimens were dumbbell-shaped strips (length × width × thickness) of 50 mm × 2.5 mm × 0.40 mm, obtained by cutting. The tensile rate was 10 mm / min. Each group of samples was tested 5 times, and the average value was taken as the final result.

[0100] (3) Thermal performance test

[0101] Differential scanning calorimetry was used to test the polycarbonate copolymer to obtain the copolymer's... T g value.

[0102] (4) Saturated water absorption rate.

[0103] The water absorption of a 100 μm polycarbonate copolymer film was tested at 85°C, and its saturated water absorption rate after water absorption equilibrium was recorded using the following formula:

[0104]

[0105] Where m1 and m2 are the weights of the sample before and after immersion treatment, respectively. Each group of samples was tested 3 times, and the average value was taken as the final result.

[0106] (5) Water contact angle

[0107] The surface hydrophobicity of the copolymer film was evaluated using a contact angle meter. 20 μL of deionized water was dropped onto the film surface using a micro-injection needle. Five independent tests were performed at different locations on the same film sample surface, and the arithmetic mean was taken as the final contact angle data.

[0108] (6) Light transmittance test

[0109] The transmittance of a 0.1 mm thick polycarbonate copolymer molded body was measured using a UV / Vis spectrophotometer (UV1900, Youke Instrument) in the range of 300–800 nm. The transmittance at 580 nm (T) was recorded. 580 To compare the transparency of different polycarbonate copolymers.

[0110] (7) Color difference test.

[0111] Dissolve 1 gram of polycarbonate copolymer completely in 10 ml of chloroform. Measure the solution using a UV / Vis spectrophotometer (UV1900, Youke Instrument) and calculate the color difference according to the following formula.

[0112]

[0113] Among them, T 600 T 555 and T 445 These represent the transmittance of the solution at 600, 555, and 445 nm, respectively.

[0114] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A polycarbonate, characterized in that, Including the repeating units of the following equations A, B, and C: Formula A; Formula B; Formula C; Formula A includes the following A-1, A-2, and A-3: Formula A-1; Formula A-2; Formula A-2; In formula B, R1 represents a copolymer structure that is either an aliphatic hydrocarbon group or an alicyclic hydrocarbon group; In formula C, R2 represents a copolymer structure as shown in formula 1, which contains both rigid bicyclohexane and fluoroalkyl groups of the CF group. Formula 1; In Formula 1, R3 and R4 each independently represent substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups with 1 to 20 carbon atoms. The molecular structure of X contains at least one hexafluoropropane group or a fluorinated alkyl-substituted quaternary carbon.

2. The polycarbonate copolymer according to claim 1, characterized in that, R1 is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group with 2 to 8 carbon atoms.

3. The polycarbonate copolymer according to claim 1, characterized in that, The number of moles of the repeating unit in the structure shown in Formula A is 40% to 60% of the sum of the number of moles of the repeating units in the structures shown in Formulas A, B, and C.

4. The polycarbonate copolymer according to claim 1, characterized in that, The number of moles of the repeating unit in the structure shown in Formula B is 20% to 30% of the sum of the number of moles of the repeating units in the structures shown in Formulas A, B, and C.

5. The polycarbonate copolymer according to claim 1, characterized in that, The number of moles of the repeating units in the structure shown in Formula C is 10% to 30% of the sum of the number of moles of the repeating units in the structures shown in Formulas A, B and C.

6. The method for preparing the polycarbonate copolymer according to any one of claims 1 to 5, characterized in that, Includes the following steps: Under a protective atmosphere, diester and diol monomers are mixed and then subjected to transesterification and polycondensation reactions sequentially under catalytic conditions to obtain the polycarbonate copolymer. The diol monomers include 1,4;3,6-didehydrohexanehexanedol, a first alcohol monomer, and a second alcohol monomer; The first alcohol monomer includes an aliphatic diol or an alicyclic hydrocarbon diol; The second alcohol monomer has the structure shown in Formula 2: Formula 2.

7. The preparation method according to claim 6, characterized in that, The molar ratio of the carbonate diester to the dihydroxy compound is 0.9 to 1.2:1; the temperature of the transesterification reaction is 160 to 210°C; the pressure of the transesterification is atmospheric pressure; and the transesterification time is 1 to 3 hours.

8. The preparation method according to claim 7, characterized in that, The polycondensation reaction is carried out at a temperature of 210 to 250°C, with the pressure gradually decreasing from atmospheric pressure to below 50 Pa for a duration of 0.5 to 5 hours.

9. The application of the polycarbonate copolymer according to any one of claims 1 to 6 or the polycarbonate copolymer prepared by any one of claims 7 to 8 in the field of engineering plastics.

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