Functionalized polycarbonate material and preparation method thereof

Abstract

The invention discloses a functionalized polycarbonate material and a preparation method thereof, and belongs to the field of high polymer materials. The material takes carbon dioxide as a green monomer, double-bond active sites are pre-buried in a polycarbonate main chain through ring-opening copolymerization, and carboxyl, amino or heterocyclic functional side chains are efficiently grafted through thiol-ene click reaction. The preparation method comprises the following steps: under the action of a composite catalyst, copolymerizing a double-bond-containing monomer, propylene oxide and COO to synthesize a precursor; and driving the sulfydryl monomer to carry out click reaction through thermal or photo-initiation. The innovation point lies in that the limitation of traditional protection / deprotection is broken through, multiple functions are integrated, hydrophilic carboxyl, antibacterial amino and conductive thiophene group have a synergistic effect, meanwhile, high mechanical strength and controllable degradability are kept, and the preparation method is suitable for the fields of biomedicine and electronics.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a functionalized polycarbonate material and its preparation method. Background Technology

[0002] With the rapid development of functionalized polymer materials, functionalized polycarbonate has shown broad application prospects in fields such as biomedicine, environmental protection, and engineering plastics due to its excellent biocompatibility, biodegradability, and tunable functional properties. However, there are still some shortcomings in the preparation process and performance optimization of functionalized polycarbonate in the existing technology, which affect its functional diversity and application scope.

[0003] Chinese patent CN115677998B discloses a functionalized polycarbonate. This patent imparts good blood compatibility and anticoagulant properties to the polycarbonate by introducing carboxyl and sulfonic acid groups onto the polycarbonate side chains, while maintaining the mechanical properties and processability of polycarbonate. However, this technical solution does not directly use carbon dioxide as a monomer for polymerization, limiting its potential for carbon dioxide resource utilization. Furthermore, the functionalized polycarbonate has a relatively limited range of side chain functional groups, making it difficult to meet the diverse functional requirements of complex applications.

[0004] Patent CN105754085B describes a carbon dioxide-based functional polycarbonate material and its preparation method. This patent expands the functionalization platform of polycarbonate by controlling the ratio of epoxy groups to cyclic carbonates, significantly increasing the glass transition temperature (Tg). However, the functionalization of this technology mainly relies on the introduction of epoxy groups and cyclic carbonates, lacking in-depth development of other functional side chains such as carboxyl, hydroxyl, and amino groups, thus limiting the further application of the material in the direction of multifunctionalization. Furthermore, its preparation process requires precise control of the raw material molar ratio and reaction conditions, which may lead to increased process complexity and production costs.

[0005] The above problems indicate that existing functionalized polycarbonate materials still have certain shortcomings in terms of monomer selection, diversity of functional side chains, and simplification of preparation processes. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a multifunctional unsaturated polycarbonate and its subsequent polymerization method.

[0007] The technical solution adopted by the present invention to solve its technical problem is: a functionalized polycarbonate material, characterized in that one or more functional side chains (groups) are connected to the polycarbonate main chain, wherein the polycarbonate main chain is composed of random or block polycarbonate segments, polyether segments and arbitrary polyester segments, and the functional side chain contains at least one functional group selected from carboxyl, hydroxyl, amino or heterocyclic groups.

[0008] This invention uses carbon dioxide as a green carbon source. It pre-embeds double-bond active sites in the polycarbonate backbone through copolymerization, and then introduces functional side chains such as carboxyl, hydroxyl, amino, and heterocyclic groups via a highly efficient thiol-olefin click reaction, achieving diversified design and precise control of functional groups. This method overcomes the limitations of cumbersome protection / deprotection steps and the limited range of functional groups in traditional functionalized polycarbonate synthesis, combining environmental friendliness and resource efficiency. The click reaction flexibly introduces hydrophilic carboxyl groups, reactive hydroxyl groups, cationic amino groups, and conductive / degradable heterocyclic groups, meeting the needs of various scenarios such as biomedicine, energy storage, and catalysis. The reaction conditions are mild and the conversion rate is high. By adjusting the ratio of double-bond monomers to thiol reagents, the density of functional side chains can be precisely controlled, enabling the on-demand design of material properties such as hydrophilicity, phase transition enthalpy, degradation rate, and mechanical strength.

[0009] Specifically, the structural formula is:

[0010] ;

[0011] Wherein, R is hydrogen-based, methyl, ethyl, propyl, butoxymethyl, or long-chain alkoxymethyl; R1 is phenyl or naphthyl; R2 and R3 are alkyl groups; R4 is a functional group containing at least one of carboxyl, hydroxyl, amino, or heterocyclic groups; and 10≤a≤300, 0≤b≤50, 0≤c≤10, and 1≤m+n≤75.

[0012] Preferably, in the above-mentioned functionalized polycarbonate materials, the molar ratio of copolymer segments with functional side chains to all copolymer segments in the polycarbonate backbone is 1% to 25%. This molar ratio ensures that the functional groups such as carboxyl / amino groups provide sufficient hydrophilicity or bioactivity while maintaining the inherent mechanical strength and thermal stability of polycarbonate; at the same time, it avoids phase separation or deterioration of processing performance caused by excessive side chains, thus balancing material uniformity and economy.

[0013] Preferably, in the above-mentioned functionalized polycarbonate materials, the comonomers of the polycarbonate backbone include epoxy compounds, carbon dioxide, and any cyclic anhydride, wherein at least one double-bonded epoxy compound or double-bonded cyclic anhydride is included. By strongly introducing double-bonded monomers, active sites are pre-embedded in the backbone, allowing subsequent mercapto-olefin click reactions to directly graft functional side chains such as carboxyl / amino groups, avoiding the chemical degradation of the backbone caused by traditional post-modification.

[0014] Specifically, the double-bonded epoxy compounds include one or both of allyl glycidyl ether and 1,2-epoxy-4-vinylcyclohexane.

[0015] Specifically, the double-bonded cyclic anhydride is at least one of maleic anhydride, citraconic anhydride, norbornene anhydride, halomaleic anhydride, dimethylmaleic anhydride, dodecenylsuccinic anhydride, itaconic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0016] The aforementioned double-bonded compounds can precisely introduce reactive double bonds into the polycarbonate backbone by participating in copolymerization reactions, providing active sites for subsequent efficient mercapto-olefin click reactions.

[0017] A method for preparing the above-mentioned functionalized polycarbonate material includes the following steps:

[0018] 1) Add ring-opening catalyst, initiator and comonomer to high-pressure reactor, and react for 2h to 18h under carbon dioxide pressure of 1.5MPa~3.5MPa, reaction temperature of 45℃~70℃ and stirring conditions;

[0019] 2) The reaction product was diluted with a solvent and then precipitated in ethanol to obtain a polycarbonate compound containing double bonds;

[0020] 3) Add 2 to 2.4 times the molar number of double bonds to the polycarbonate compound containing double bonds; initiate the reaction and react for 3 to 12 hours; the product is dried to obtain the functionalized polycarbonate material.

[0021] This preparation method directly introduces reactive double bonds through carbon dioxide ring-opening copolymerization, and then precisely grafts functional groups through mercapto-olefin click reaction, which endows the material with various functional properties while maintaining the high mechanical strength and thermal stability of polycarbonate. The single-reactor two-step process simplifies the process, and the reaction conditions are mild and energy consumption is low.

[0022] Specifically, the ring-opening catalyst mentioned in step 1) is a metal catalyst or an organoborane catalyst; the initiator is a saturated or unsaturated onium salt of an organic acid. This catalytic initiation system efficiently catalyzes the alternating copolymerization of carbon dioxide and epoxides under mild conditions, achieving high conversion and high selectivity, and ensuring the precise introduction of double bond sites in the main chain. Simultaneously, this system initiates polymerization through an ionic mechanism, precisely controlling chain growth kinetics, achieving controllable molecular weight and chain segment sequence of the polycarbonate precursor, providing structurally uniform active sites for subsequent click reactions, and directly compatible with monomers containing double bonds participating in copolymerization, avoiding the cumbersome functional group protection / deprotection steps in traditional processes.

[0023] Preferably, the ring-opening catalyst is an organoborane catalyst. More preferably, the organoborane catalyst is a composite catalytic system of tris(pentafluorophenyl)borane (B(C6F5)3) and triethylboron (TEB) in a molar ratio of 1:7~9. This composite catalytic system can ensure the copolymerization of polycarbonate chains, avoid the self-polymerization and cross-linking of double bonds, and promote the addition reaction of thiol functional monomers. When B(C6F5)3 and triethylboron (TEB) are combined in this ratio, the strong Lewis acidity of B(C6F5)3 dominates the alternating copolymerization of epoxide / CO2 to form highly selective polycarbonate chains (carbonate units > 99%), while TEB shields the self-polymerization and cross-linking of double bonds through steric hindrance. At the same time, TEB can generate ethyl radicals in situ during the reaction, triggering the rapid addition of thiol functional monomers. It and B(C6F5)3 synergistically lower the energy barrier of the thiol-alkene click reaction, achieving a double bond conversion rate > 98%. This composite system, through dual regulation of electrons and steric hindrance, ensures efficient copolymerization of the main chain while also possessing the ability to resist side reactions and promote post-functionalization.

[0024] Preferably, the initiator is an unsaturated organic acid onium salt, more preferably.

[0025] Specifically, the thiol functional monomers mentioned in step 3) include one or more combinations of thiol propionic acid, mercaptoethanol, 2-aminoethanethiol, 2-mercaptothiophene, and furfuryl mercaptan. Choosing thiol monomers in the preparation of functionalized polycarbonates has unique advantages: the high reactivity of thiols, with selectivity for olefins at pH 6.5–7.5 nearly a thousand times higher than that of amino groups, allows for precise grafting of functional groups while avoiding side reactions; multifunctional expansion enables modular integration of hydrophilicity, antibacterial properties, and conductivity / degradability through carboxyl, amino, and heterocyclic groups, while the mild reaction conditions ensure precise control of functions such as bioactive molecule compatibility and degradation rate. This makes thiol a core functional group in this invention that combines precision, stability, and programmable functionality.

[0026] Preferably, the initiation reaction described in step 3) is initiated under heating conditions of 80℃ to 105℃. Performing the mercapto-olefin click reaction at 80℃ to 105℃ offers both high efficiency and safety: this temperature range is well-suited to the effective decomposition window of the thermal initiator, significantly increasing the reaction rate and ensuring stable free radical generation, while precisely avoiding the glass transition temperature of the polycarbonate backbone, preventing material softening and double bond self-polymerization side reactions, thus achieving high conversion rate and controllable molecular weight.

[0027] Preferably, the initiation reaction described in step 3) can also be initiated by ultraviolet light (wavelength 365~405nm), operated at room temperature, using TPO or 1173 high-efficiency photoinitiator, and the reaction is completed within 5~30 minutes, which can effectively avoid heat risks and save energy.

[0028] The drying described in step 3) is vacuum drying. The vacuum drying conditions are: temperature 110℃~140℃, preferably 120℃~130℃; vacuum pressure: 200Pa~500Pa, preferably 200Pa~300Pa; residence time: 3h~5h, preferably 3h~4h. Vacuum drying lowers the boiling point of water through a low-pressure environment, efficiently removes residual dichloromethane and moisture, avoids high-temperature hydrolysis side reactions, significantly improves optical purity, and shortens the drying cycle while achieving solvent recovery.

[0029] Compared with existing technologies, this invention has the following advantages: This invention precisely pre-embeds double bonds through carbon dioxide ring-opening copolymerization, followed by efficient grafting of carboxyl, amino, and other functional groups via a mercapto-olefin click reaction, overcoming the limitations of cumbersome protection / deprotection steps in traditional functionalized polycarbonates; it achieves synergistic effects of highly selective alternating copolymerization and double bond self-polymerization inhibition using a composite catalyst, combined with mild reaction conditions, ensuring narrow molecular weight distribution and precise control of functional side chain density; the single-reactor two-step process simplifies the process, combining carbon dioxide resource utilization with multifunctional integration, significantly enhancing the application potential and economic efficiency of materials in biomedicine, flexible electronics, and other fields. Detailed Implementation

[0030] The present invention will now be described in detail through examples. Unless otherwise stated, all raw materials used are commercially available.

[0031] Example 1

[0032] 1. Preparation of polycarbonate backbone containing double bonds

[0033] Raw materials and proportions: propylene oxide to allyl glycidyl ether molar ratio 90:10, catalyst is a composite catalyst of B(C6F5)3 and triethylboron in a molar ratio of 1:8, the amount of which is 0.003% of the total mass of monomers, and initiator is used at a amount of 0.2% of the total molar mass of monomers.

[0034] Add the monomer, catalyst and initiator in the specified proportions to the high-pressure reactor; introduce CO2 to a pressure of 2.0 MPa, and heat to 60°C for 12 h; after the reaction is completed, dilute the product with dichloromethane, precipitate it in ethanol, and dry it under vacuum at 120°C and 300 Pa for 4 h to obtain a polycarbonate compound containing double bonds, with a double bond retention rate of >95%, Mn=30,000 g / mol, and Ð=1.25.

[0035] 2. Click functionalization reaction of thiol-alkene

[0036] Mercaptopropionic acid (2.2 eq / double bond) was added to polycarbonate containing double bonds (double bond content 1.2 mmol / g); the mixture was heated to 80℃~105℃ and reacted for 6 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate, filtered, and then dried under vacuum at 130℃ and 200Pa for 3 h to obtain carboxyl-functionalized polycarbonate with a double bond grafting rate of 98% and an intrinsic viscosity η=0.72 dL / g.

[0037] Example 2

[0038] 1. Preparation of polycarbonate backbone containing double bonds

[0039] Raw materials and proportions: propylene oxide to allyl glycidyl ether molar ratio 90:10, catalyst is triethylboron, amount is 0.003% of the total mass of monomers, initiator is, amount is 0.2% of the total molar mass of monomers.

[0040] The monomer, catalyst, and initiator were added to a high-pressure reactor in the specified proportions; CO2 was introduced to a pressure of 2.0 MPa, and the temperature was raised to 60 °C for 12 h; after the reaction was completed, the product was diluted with dichloromethane, precipitated in ethanol, and dried under vacuum at 120 °C and 300 Pa for 4 h to obtain a polycarbonate compound containing double bonds. The double bond retention rate was >95%, Mn = 30,000 g / mol, and γ = 1.25.

[0041] 2. Click functionalization reaction of thiol-alkene

[0042] Mercaptopropionic acid (2.2 eq / double bond) was added to a polycarbonate compound containing double bonds; the mixture was reacted at 80℃~105℃ for 6 h under nitrogen protection; the reaction solution was then precipitated by adding it dropwise into methanol, filtered, and dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate. The double bond grafting rate was 97%, and the intrinsic viscosity η = 0.70 dL / g.

[0043] Example 3

[0044] 1. Preparation of polycarbonate backbone containing double bonds

[0045] Raw materials and proportions: propylene oxide to allyl glycidyl ether molar ratio 90:10, catalyst B(C6F5)3, dosage 0.003% of total monomer mass, initiator... The dosage is 0.2% of the total moles of monomers.

[0046] The monomer, catalyst, and initiator were added to a high-pressure reactor in the specified proportions; CO2 was introduced to a pressure of 2.0 MPa, and the temperature was raised to 60 °C for 12 h; after the reaction was completed, the product was diluted with dichloromethane, precipitated in ethanol, and dried under vacuum at 120 °C and 300 Pa for 4 h to obtain a polycarbonate compound containing double bonds. The double bond retention rate was >95%, Mn = 30,000 g / mol, and γ = 1.25.

[0047] 2. Click functionalization reaction of thiol-alkene

[0048] Mercaptopropionic acid (2.2 eq / double bond) was added to a polycarbonate compound containing double bonds; the mixture was reacted at 80℃~105℃ for 6 h under nitrogen protection; the reaction solution was then precipitated by adding it dropwise into methanol, filtered, and dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate. The double bond grafting rate was 96%, and the intrinsic viscosity η = 0.68 dL / g.

[0049] Example 4

[0050] 1. Preparation of polycarbonate backbone containing double bonds

[0051] Raw materials and proportions: propylene oxide to allyl glycidyl ether molar ratio 90:10; catalyst is a composite catalyst of B(C6F5)3 and triethylboron in a molar ratio of 1:8, used in an amount of 0.003% of the total monomer mass; initiator is... The dosage is 0.2% of the total moles of monomers.

[0052] Add the monomer, catalyst and initiator in the specified proportions to the high-pressure reactor; introduce CO2 to a pressure of 2.0 MPa, and heat to 60°C for 12 h; after the reaction is completed, dilute the product with dichloromethane, precipitate it in ethanol, and dry it under vacuum at 120°C and 300 Pa for 4 h to obtain a polycarbonate compound containing double bonds, with a double bond retention rate of >93%, Mn=28,000 g / mol, and Ð=1.25.

[0053] 2. Click functionalization reaction of thiol-alkene

[0054] Initiator: Azobisisobutyronitrile (AIBN), used at 2% of the molar number of double bonds.

[0055] Mercaptopropionic acid (2.2 eq / double bond) and AIBN were added to a polycarbonate compound containing double bonds; the reaction was carried out at 20°C for 6 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate the compound, filtered, and then dried under vacuum at 130°C and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate. The double bond grafting rate was 93%, and the intrinsic viscosity η = 0.65 dL / g.

[0056] Example 5

[0057] 1. Preparation of polycarbonate backbone containing double bonds

[0058] Raw materials and proportions: The monomer containing double bonds is maleic anhydride.

[0059] The molar ratio of propylene oxide (PO), cyclohexane oxide (CHO), and maleic anhydride is 90:5:5. The catalyst is a composite catalyst of B(C6F5)3 and triethylboron in a molar ratio of 1:8, and the amount used is 0.003% of the total mass of the monomers. The initiator is... The dosage is 0.2% of the total moles of monomers.

[0060] Add the monomer, catalyst and initiator in the specified proportions to the high-pressure reactor; introduce CO2 to a pressure of 2.0 MPa, and heat to 60°C for 12 h; after the reaction is completed, dilute the product with dichloromethane, precipitate it in ethanol, and dry it under vacuum at 120°C and 300 Pa for 4 h to obtain a polycarbonate compound containing double bonds, with a double bond retention rate of >90%, Mn=32,000 g / mol, and Ð=1.25.

[0061] 2. Click functionalization reaction of thiol-alkene

[0062] Mercaptopropionic acid (2.2 eq / double bond) was added to the polycarbonate compound containing double bonds; the mixture was heated to 100℃ and reacted for 6 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate the compound, filtered, and then dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate with a double bond grafting rate of 98% and an intrinsic viscosity η = 0.75 dL / g.

[0063] Example 6

[0064] 1. Preparation of polycarbonate backbone containing double bonds

[0065] Raw materials and proportions: The molar ratio of PO, AGE and citrate anhydride is 80:10:10. The catalyst is a composite catalyst of B(C6F5)3 and triethylboron in a molar ratio of 1:7, and the amount used is 0.01% of the total mass of monomers. The initiator is tetrabutylammonium bromide, and the amount used is 0.1% of the total molar mass of monomers.

[0066] Add the monomer, catalyst and initiator in the specified proportions to the high-pressure reactor; introduce CO2 to a pressure of 1.5 MPa, and heat to 45°C for 18 h; after the reaction is completed, dilute the product with dichloromethane, precipitate it in ethanol, and dry it under vacuum at 120°C and 300 Pa for 4 h to obtain a polycarbonate compound containing double bonds, with a double bond retention rate of >92%, Mn=25,000 g / mol, and Ð=1.30.

[0067] 2. Click functionalization reaction of thiol-alkene

[0068] Mercaptopropionic acid (2.0 eq / double bond) was added to the polycarbonate compound containing double bonds; the mixture was heated to 80℃ and reacted for 12 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate the precipitate, filtered, and then dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate with a grafting rate of 95% and an intrinsic viscosity η = 0.60 dL / g.

[0069] Example 7

[0070] 1. Preparation of polycarbonate backbone containing double bonds

[0071] The molar ratio of propylene oxide (PO) to norbornyl adiene anhydride is 90:10. The catalyst is a composite catalyst of B(C6F5)3 and triethylboron in a molar ratio of 1:9, and the amount used is 0.001% of the total monomer mass. The initiator is... The dosage is 0.5% of the total moles of monomers.

[0072] Add the monomer, catalyst and initiator in the specified proportions to the high-pressure reactor; introduce CO2 to a pressure of 3.5 MPa, and heat to 70°C for 2 hours; after the reaction is complete, dilute the product with dichloromethane, precipitate it in ethanol, and dry it under vacuum at 120°C and 300 Pa for 4 hours to obtain a polycarbonate compound containing double bonds with a double bond retention rate of >94%, Mn=35,000 g / mol, and Ð=1.25.

[0073] 2. Click functionalization reaction of thiol-alkene

[0074] Mercaptopropionic acid (2.4 eq / double bond) was added to the polycarbonate compound containing double bonds; the mixture was heated to 105℃ and reacted for 3 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate the precipitate, filtered, and then dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate with a grafting rate of 98% and an intrinsic viscosity η = 0.80 dL / g.

[0075] The functionalized polycarbonates obtained in Examples 1-7 were tested for performance. The test results are shown in Table 1.

[0076] Table 1 Performance test results of functionalized polycarbonate

[0077] Testing items Detection methods Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Tg (°C) <![CDATA[DSC (10℃ / min, N2 atmosphere)]]> 40.2 39.8 40.0 38.5 48.3 42.1 45.7 Tensile strength (MPa) (ISO 527, 50 mm / min) 42.5 41.0 40.8 38.2 50.1 35.3 47.6 Water contact angle (°) Contact angle meter (static water droplet method) 68.3 69.5 70.1 72.8 65.2 75.4 67.8 Degradation rate (weight loss in 14 days) PBS buffer (37°C, pH 7.4) 8.2% 7.8% 7.5% 6.9% 5.1% 4.3% 5.8%

[0078] Example 8

[0079] 1. The preparation of the polycarbonate backbone containing double bonds is the same as in Example 1.

[0080] 2. Thiol-olefin click functionalization reaction: 2-Mercaptothiophene (2.2 eq / double bond) was added to the polycarbonate material containing double bonds; the temperature was raised to 95℃ and reacted for 6 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate, filtered, and then dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate with a grafting rate of 95% and intrinsic viscosity η=0.78dL / g.

[0081] The functionalized polycarbonate obtained in Example 8 was subjected to performance testing, and the test results are shown in Table 2.

[0082] Table 2 Performance test results of functionalized polycarbonate

[0083] Testing items Detection methods result Volume resistivity High resistance meter method (GB / T 1410) <![CDATA[1.2×10 9 Ohm]]> electrical conductivity Four-point probe method (ASTM D4496) <![CDATA[5.3×10⁻ 6 S / cm]]> Dielectric strength Breakdown voltage test (GB / T 1408.1) 28 kV / mm 5% thermal weight loss at temperature <![CDATA[TGA(N2, 10°C / min, ISO 11358)]]> 312℃

[0084] Example 9

[0085] 1. The preparation of the polycarbonate backbone containing double bonds is the same as in Example 1.

[0086] 2. Thiol-olefin click functionalization reaction: 2-aminoethanethiol (2.2 eq / double bond) was added to the polycarbonate material containing double bonds; the temperature was raised to 95℃ and reacted for 6 h under nitrogen protection; the reaction solution was dropped into methanol to precipitate, filtered, and then dried under vacuum at 130℃ and 200 Pa for 3 h to obtain carboxyl-functionalized polycarbonate with a grafting rate of 93% and intrinsic viscosity η=0.72 dL / g.

[0087] The functionalized polycarbonate obtained in Example 9 was subjected to performance testing, and the test results are shown in Table 3.

[0088] Table 3 Performance test results of functionalized polycarbonate

[0089] Testing items Detection methods result Antibacterial rate (E. coli) Shaking culture method (GB / T 21510) 99.2% Hydrolysis rate (pH10) Alkali loss method (37℃, 24h) 15.7% swelling rate Mass fractionation (PBS, 37℃, 24h) 8.5%

[0090] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A functionalized polycarbonate material, characterized in that, The polycarbonate main chain has one or more functional side chains attached to it. The polycarbonate main chain is composed of random or block polycarbonate segments, polyether segments and any polyester segments. The functional side chains contain at least one functional group selected from carboxyl, hydroxyl, amino or heterocyclic groups.

2. The functionalized polycarbonate material according to claim 1, characterized in that, The structural formula is: ； Wherein, R is hydrogen-based, methyl, ethyl, propyl, butoxymethyl, or long-chain alkoxymethyl; R1 is phenyl or naphthyl; R2 and R3 are alkyl groups; R4 is a functional group containing at least one of carboxyl, hydroxyl, amino, or heterocyclic groups; and 10≤a≤300, 0≤b≤50, 0≤c≤10, and 1≤m+n≤75.

3. The functionalized polycarbonate material according to claim 1, characterized in that, The molar ratio of copolymer segments with functional side chains in all copolymer segments of the polycarbonate backbone is 1% to 25%.

4. The functionalized polycarbonate material according to claim 1, characterized in that, The comonomer of the polycarbonate backbone includes an epoxy compound, carbon dioxide, and any cyclic anhydride, wherein at least one double-bonded epoxy compound or double-bonded cyclic anhydride is included.

5. The functionalized polycarbonate material according to claim 4, characterized in that, The double-bonded epoxy compounds include one or both of allyl glycidyl ether and 1,2-epoxy-4-vinylcyclohexane.

6. The functionalized polycarbonate material according to claim 4, characterized in that, The double-bonded cyclic anhydride is at least one of maleic anhydride, citraconic anhydride, norbornene anhydride, halomaleic anhydride, dimethylmaleic anhydride, dodecenylsuccinic anhydride, itaconic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

7. A method for preparing the functionalized polycarbonate material according to any one of claims 1 to 6, characterized in that, Includes the following steps: 1) Add ring-opening catalyst, initiator and comonomer to high-pressure reactor, and react for 2h to 18h under carbon dioxide pressure of 1.5MPa~3.5MPa, reaction temperature of 45℃~70℃ and stirring conditions; 2) The reaction product was diluted with a solvent and then precipitated in ethanol to obtain a polycarbonate compound containing double bonds; 3) Add 2 to 2.4 times the molar number of double bonds to the polycarbonate compound containing double bonds; initiate the reaction and react for 3 to 12 hours; the product is dried to obtain the functionalized polycarbonate material.

8. The method for preparing a functionalized polycarbonate material according to claim 6, characterized in that, The ring-opening catalyst mentioned in step 1) is a metal catalyst or an organoborane catalyst; the initiator is a saturated or unsaturated onium salt of an organic acid.

9. The method for preparing a functionalized polycarbonate material according to claim 6, characterized in that, The thiol functional monomers mentioned in step 3) include one or more of the following: mercaptopropionic acid, mercaptoethanol, 2-aminoethanethiol, 2-mercaptothiophene, and furfuryl mercaptool.

10. The method for preparing a functionalized polycarbonate material according to claim 6, characterized in that, The initiation reaction described in step 3) is initiated under heating conditions of 160℃~180℃.

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