Polycarbonate resin material as well as preparation method and application thereof
By introducing diol monomers containing biaromatic rings and porphyrin monomers with tetracarboxyl groups into the polycarbonate resin, and combining copolymerization technology of micro-nanothermal stabilizers, the problem of polycarbonate resin prone to cracking after chemicals and gamma ray radiation is solved, achieving the retention of high transparency and mechanical properties, and is suitable for the manufacturing of high durability medical devices.
Patent Information
- Application Number
- CN202411979515.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-11
- Estimated Expiration
- 2044-12-31
AI Technical Summary
Existing polycarbonate resins are prone to cracking after being radiated by chemical or gamma rays, and have low retention of mechanical properties, making it difficult to meet the high requirements of medical devices for durability.
By introducing a special structure of diaryl ring-containing diol monomer and a tetracarboxylic porphyrin monomer, combined with bisphenol A and dihydrocarbonyl carbonate copolymerization, a polycopolymerized polycarbonate resin was prepared, and a micro-nanoscale thermal stabilizer was used during the preparation process.
It has achieved high transparency, resistance to organic chemicals and gamma ray radiation of polycarbonate resin, and has high mechanical properties retention rate, which is suitable for the manufacture of medical equipment such as dialysis, injection and diagnosis.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of high-performance resin materials, in particular to a polycarbonate resin material and a preparation method and application thereof. Background Art
[0002] Polycarbonate resin is an engineering plastic with excellent performance. Due to its excellent impact resistance, heat resistance, dimensional stability, creep resistance and transparency, it is widely used in automobiles, electronic appliances, optical equipment, medical equipment and other fields. With the continuous advancement of medical technology and people's growing demand for health, medical-grade polycarbonate has been widely used in medical devices, medical equipment, disposable medical supplies and other fields due to its excellent physical and biocompatibility properties. Especially in high-end medical fields such as surgical instruments, medical containers, artificial joints, and dental implants, polycarbonate is gradually becoming the mainstream choice of the market. At present, major polycarbonate manufacturers around the world have increased their investment and increased production capacity to meet the growing market demand. Therefore, this field has strong market appeal and development potential.
[0003] To ensure the safety of medical products, in addition to passing the biocompatibility requirements of medical devices, medical-grade polycarbonate must also be able to undergo sterilization processes such as high-concentration alcohol, iodine, ethylene oxide gas, gamma rays and electron beam radiation without cracking or becoming brittle, while still maintaining excellent physical property retention.
[0004] In response to the urgent demand for polycarbonate resins in the medical and health fields, we have developed a polycarbonate resin that is resistant to chemical reagents and gamma-ray radiation, and has high transparency and mechanical property retention. This will solve key technical problems in the industry and play a very important supporting role in the vigorous development of my country's medical, public health, and health industries. Summary of the invention
[0005] In view of the above situation, in order to overcome the defects of the prior art, the present invention provides a polycarbonate resin material and a preparation method and application to solve the problem in the background technology that the polycarbonate resin is easy to crack and has a low mechanical property retention rate after being irradiated by chemicals and gamma rays.
[0006] To achieve the above object, the present invention provides the following technical solution: a polycarbonate resin material, the polycarbonate resin material is composed of a segment represented by formula (1) and a structural unit represented by formula (2);
[0007]
[0008]
[0009] In formula (1), R1 to R8 are selected from H, C1 to C 24Hydrocarbon, C3~C 30 Cyclic hydrocarbon groups, C1~C 24 Halogenated hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C1~C 24 Nitroalkyl or C3~C 30 One or more of the nitrocyclic hydrocarbon groups;
[0010] And / or any two adjacent groups of R1 to R8 are directly bonded to form C3 to C 30 Cyclic hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C3~C 30 Nitrocyclic hydrocarbon groups;
[0011] X is a single bond, C1~C 24 Alkylene, C3~C 30 One of cycloalkylidene, oxy, thiol, sulfinic acid, sulfonic acid or carbonyl groups; n is an integer of 10 to 5000;
[0012] In formula (2), Y is C1 to C 24 Alkylene, C3~C 30 * represents the bond between the structural unit represented by formula (2) and the segment represented by formula (1) or the bond between the structural unit represented by another structural unit represented by formula (2).
[0013] Furthermore, the molar ratio of formula (1) to formula (2) is 80:20 to 99.95:0.05.
[0014] Furthermore, in the formula (1), n is an integer of 100 to 3000, preferably an integer of 500 to 3000;
[0015] The molar ratio of formula (1) to formula (2) is 85:15 to 99.5:0.5, preferably 90:10 to 99:1.
[0016] Furthermore, X in the formula (1) is one or more of methylene, cyclohexylene or phenylene; Y in the formula (2) is one or more of methylene, ethylene, hexylene, cyclohexylene or phenylene, preferably one or more of cyclohexylene or phenylene.
[0017] Furthermore, the formula (1) is one or more of a bisphenol A carbonate segment, a biphenyl carbonate segment or a benzophenone carbonate segment.
[0018] Preparation method of polycarbonate resin material,
[0019] The diol represented by formula (3), the tetraol represented by formula (4), the dialkyl carbonate represented by formula (5), a catalyst and a heat stabilizer are put into a stirred reactor, replaced with inert gas for multiple times, stirred for a period of time t1 at the initial temperature under the protection of inert gas; then reacted at a certain reaction temperature and pressure for a period of time t2; filled with inert gas protection, unloaded, cooled, and granulated to obtain polycarbonate resin particles;
[0020]
[0021] In formula (3),
[0022] R1 to R8 are selected from H, C1 to C 24 Hydrocarbon, C3~C 30 Cyclic hydrocarbon groups, C1~C 24 Halogenated hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C1~C 24 Nitroalkyl or C3~C 30 One or more of the nitrocyclic hydrocarbon groups;
[0023] And / or any two adjacent groups of R1 to R8 are directly bonded to form C3 to C 30 Cyclic hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C3~C 30 Nitrocyclic hydrocarbon groups;
[0024] X is a single bond, C1~C 24 Alkylene, C3~C 30 One of a cycloalkylidene group, an oxy group, a sulfide group, a sulfinic acid group, a sulfonic acid group or a carbonyl group;
[0025] In formula (4), Y is C1 to C 24 Alkylene, C3~C 30 Cycloalkylene;
[0026] In formula (5), R and R' are selected from C1 to C 24 Hydrocarbon, C3~C 30 One or more of the cyclic hydrocarbon groups, preferably C4 to C 22 Hydrocarbon, C5~C 24 One or more of the cyclic hydrocarbon groups.
[0027] Further, the total molar amount ratio of the formula (3) and the formula (4) to the molar amount ratio of the formula (5) is 1: (0.90-1.30), preferably 1: (0.98-1.20); more preferably 1: (1.01-1.10);
[0028] The amount of the catalyst is 0.0001% to 0.05%, preferably 0.001% to 0.025%, of the total molar amount of the formula (3), formula (4) and formula (5);
[0029] The amount of the heat stabilizer is 0.01% to 1%, preferably 0.05% to 0.75%, of the total weight of the formula (3), formula (4) and formula (5).
[0030] Furthermore,
[0031] The catalyst is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, dibutyltin dilaurate, dihexyltin dilaurate, dioctyltin dilaurate, and didecyltin dilaurate;
[0032] Preferably, it is a combination of sodium bicarbonate and dioctyltin dilaurate; the molar ratio of the sodium bicarbonate to the dioctyltin dilaurate is 1:9 to 9:1;
[0033] The heat stabilizer is selected from one or more of calcium oxide, zinc oxide, calcium carbonate, zinc carbonate, calcium sulfate and zinc sulfate.
[0034] Furthermore,
[0035] The stirring rate is 10 to 1000 rpm, preferably 50 to 800 rpm;
[0036] The initial temperature is 120-240°C, preferably 150-200°C;
[0037] The time t1 is 5 to 120 minutes, preferably 15 to 100 minutes;
[0038] The inert gas is nitrogen, argon or helium;
[0039] The reaction temperature is 150-280°C, preferably 180-250°C;
[0040] The pressure is 10 -6 ~10 -3 atm, preferably 10 -5 ~10 -3 atm;
[0041] The time t2 is 30 to 600 minutes, preferably 60 to 450 minutes.
[0042] An application of polycarbonate resin material,
[0043] The polycarbonate resin material is used in the medical, public health or health fields, and is used to manufacture medical equipment for dialysis, injection or diagnosis.
[0044] Compared with the prior art, the present invention has the following beneficial effects:
[0045] The invention introduces a diol monomer containing a double aromatic ring of a special structure into the copolymerization system of bisphenol A monomer and dialkyl carbonate, so as to obtain a multi-component copolymer polycarbonate resin with high transparency and resistance to organic chemicals and gamma rays. The porphyrin monomer with a tetracarboxyl group gives the polycarbonate resin a certain branching structure, improves the processing performance of the resin, and has a more obvious advantage in the manufacture of thin-walled parts; more importantly, it is beneficial to the radiation aging resistance of the resin material, and has a high mechanical property retention rate, thereby achieving a good technical effect. The micro-nanoscale thermal stabilizer not only has a good composite effect with the polycarbonate system, but also improves the stability of the material. The invention has excellent resistance to chemicals and gamma ray radiation and mechanical retention rate, and can be used to manufacture medical equipment such as dialysis, injection, and diagnosis. DETAILED DESCRIPTION
[0047] Embodiment 1:
[0048] A polycarbonate resin material, the polycarbonate resin material is composed of a chain segment represented by formula (1) and a structural unit represented by formula (2); the molar ratio of formula (1) to formula (2) is 80:20 to 99.95:0.05, preferably 85:15 to 99.5:0.5, and more preferably 90:10 to 99:1.
[0049]
[0050] In formula (1), R1 to R8 are selected from H, C1 to C 24 Hydrocarbon, C3~C 30 Cyclic hydrocarbon groups, C1~C 24 Halogenated hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C1~C 24 Nitroalkyl or C3~C 30 One or more of the nitrocyclic hydrocarbon groups;
[0051] And / or any two adjacent groups of R1 to R8 are directly bonded to form C3 to C 30 Cyclic hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C3~C 30 Nitrocyclic hydrocarbon groups;
[0052] X is a single bond, C1~C 24 Alkylene, C3~C 30One of cycloalkylidene, oxy, thiol, sulfinic acid, sulfonic acid or carbonyl, preferably one or more of methylene, cyclohexylidene or phenylene; n is an integer of 10 to 5000; preferably an integer of 100 to 3000, more preferably an integer of 500 to 3000;
[0053] The formula (1) is one or more of bisphenol A carbonate chain segments, biphenyl carbonate chain segments or benzophenone carbonate chain segments.
[0054] In formula (2), Y is C1 to C 24 Alkylene, C3~C 30 The cycloalkylidene group is preferably one or more of methylene, ethylene, hexylene, cyclohexylidene or phenylene, and more preferably one or more of cyclohexylidene or phenylene; * represents the bond between the structural unit represented by formula (2) and the segment represented by formula (1) or the bond with another structural unit represented by formula (2).
[0055] Embodiment 2:
[0056] A method for preparing a polycarbonate resin material,
[0057] 2280 g of bisphenol A (10 mol), 384.5 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (0.5 mol), 2354 g of diphenyl carbonate (11 mol), 0.67 g of sodium bicarbonate (0.008 mol), and 5.02 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement three times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes. Then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0058] Embodiment 3:
[0059] 2143 g of bisphenol A (9.4 mol), 846 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1.1 mol), 2354 g of diphenyl carbonate (11 mol), 14.45 g of sodium bicarbonate (0.172 mol), and 5.34 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement three times, the reactor was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes. Then, the reactor was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0060] Embodiment 4:
[0061] 1596 g of bisphenol A (7 mol), 2691.5 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (3.5 mol), 2354 g of diphenyl carbonate (11 mol), 14.45 g of sodium bicarbonate (0.172 mol), and 6.64 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement three times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes; then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0062] Embodiment 5:
[0063] 1687 g of bisphenol A (7.4 mol), 428 g of 4,4'-dihydroxybenzophenone (2 mol), 846 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1.1 mol), 2354 g of diphenyl carbonate (11 mol), 14.45 g of sodium bicarbonate (0.172 mol), and 5.32 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement three times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes; then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0064] Embodiment 6:
[0065] 1687 g of bisphenol A (7.4 mol), 428 g of 4,4'-dihydroxybenzophenone (2 mol), 846 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1.1 mol), 1284 g of diphenyl carbonate (6 mol), 870 g of di-tert-butyl carbonate (5 mol), 14.45 g of sodium bicarbonate (0.172 mol), and 5.12 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement for 3 times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes; then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0066] Embodiment 7:
[0067] 1687 g of bisphenol A (7.4 mol), 428 g of 4,4'-dihydroxybenzophenone (2 mol), 846 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1.1 mol), 1914 g of di-tert-butyl carbonate (11 mol), 14.45 g of sodium bicarbonate (0.172 mol), and 4.88 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement three times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes; then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0068] Embodiment 8:
[0069] 1687 g of bisphenol A (7.4 mol), 428 g of 4,4'-dihydroxybenzophenone (2 mol), 846 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1.1 mol), 1284 g of diphenyl carbonate (6 mol), 870 g of di-tert-butyl carbonate (5 mol), 6.05 g of sodium bicarbonate (0.072 mol), 74.4 g of dioctyltin dilaurate (0.1 mol), and 5.12 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement for 3 times, the mixture was stirred at an initial temperature of 175°C and a speed of 500 rpm for 40 minutes; then, the mixture was heated at 195°C and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0070] Embodiment 9:
[0071] 1687 g of bisphenol A (7.4 mol), 428 g of 4,4'-dihydroxybenzophenone (2 mol), 846 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (1.1 mol), 1284 g of diphenyl carbonate (6 mol), 870 g of di-tert-butyl carbonate (5 mol), 128 g of dioctyltin dilaurate (0.172 mol), and 5.12 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement for 3 times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes; then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0072] Comparative Example 1:
[0073] 2394 g of bisphenol A (10.5 mol), 2354 g of diphenyl carbonate (11 mol), 0.67 g of sodium bicarbonate (0.008 mol), and 5.02 g of zinc carbonate were weighed and put into a stirred reactor. After nitrogen replacement three times, the reactor was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes; then the reactor was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0074] Comparative Example 2:
[0075] 2280 g of bisphenol A (10 mol), 384.5 g of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (0.5 mol), 2354 g of diphenyl carbonate (11 mol), and 0.67 g of sodium bicarbonate (0.008 mol) were weighed and put into a stirred reactor. After nitrogen replacement three times, the mixture was stirred at an initial temperature of 175° C. and a speed of 500 rpm for 40 minutes. Then, the mixture was heated at 195° C. and 10 -4 The reaction was carried out for 400 minutes under atm pressure; nitrogen was filled for protection, the material was unloaded, cooled, and granulated to obtain polycarbonate resin particles.
[0076] Comparative Example 3:
[0077] After drying, the comprehensive performance of Makroblend M5005FR polycarbonate resin pellets produced by Covestro was evaluated.
[0078] Performance testing:
[0079] The polycarbonate resin material of the invention comprises bisphenol A, 4,4'-dihydroxybenzophenone, diphenyl carbonate and / or di-tert-butyl carbonate and 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin under the catalysis of sodium bicarbonate and / or dioctyltin dilaurate, and zinc carbonate.
[0080] Among them, bisphenol A is a product of Sinopec Mitsui Chemicals; 4,4'-dihydroxybenzophenone is a product of Sigma-Aldrich (Shanghai) Trading Co., Ltd.; diphenyl carbonate is a product of Wuhan Kmik Biotechnology Co., Ltd.; di-tert-butyl carbonate is a product of Shanghai Haohong Biotechnology Co., Ltd.; 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin is a product of Shanghai Bid Pharmaceutical Technology Co., Ltd.; sodium bicarbonate is a product of Weifang Ruidesheng Chemical Co., Ltd.; dioctyltin dilaurate is a product of Shandong Moore Chemical Co., Ltd.; zinc carbonate is a product of Jiangxi Hillman New Materials Co., Ltd.
[0081] Comprehensive performance test:
[0082] The polycarbonate resin materials in the above 8 embodiments and 3 comparative examples were injection molded on an injection molding machine, and the specimens were placed in a constant temperature and humidity chamber with a humidity of 50% and 23° C. for 48 hours for testing.
[0083] Transparency: Tested with a transmittance tester, the sample diameter is 100 mm and the thickness is 2 mm;
[0084] Notched impact strength: tested according to ISO 179 standard;
[0085] Elastic modulus: tested according to ISO 527 standard, tensile speed 5mm / min;
[0086] Chemical resistance test: Soak the injection molded specimens in 95% alcohol for 24 hours, then test the transparency, notched impact strength and elastic modulus;
[0087] Gamma ray resistance test: The injection molded specimens were irradiated with 50 kGy gamma rays for 24 hours, and then the transparency, notched impact strength and elastic modulus were tested.
[0088] The test results are shown in Table 1
[0089] Table 1
[0090]
[0091]
[0092] By comparing the data of Examples 2 to 4 in Table 1, it can be seen that when only a certain ratio of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin is copolymerized with bisphenol A and diphenyl carbonate, the transparency, impact strength and elastic modulus of the resin material are highly retained after disinfectant and gamma ray treatment, which is better than the resin materials in Comparative Examples 1 and 2; when Examples 3 and 5 use an appropriate amount of 4,4'-dihydroxybenzophenone to replace part of bisphenol A, Examples 4, 6 and 7 use a combination of diphenyl carbonate and / or di-tert-butyl carbonate, and Examples 6, 8 and 9 use a combination of sodium bicarbonate and / or dioctyltin dilaurate, polycarbonate resin materials with excellent comprehensive performance can be obtained, which show obvious advantages over commercially available products.
[0093] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A polycarbonate resin material, characterized in that: The polycarbonate resin material is composed of a chain segment represented by formula (1) and a structural unit represented by formula (2); In formula (1), R1 to R8 are selected from H, C1 to C 24 Hydrocarbon, C3~C 30 Cyclic hydrocarbon groups, C1~C 24 Halogenated hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C1~C 24 Nitroalkyl or C3~C 30 One or more of the nitrocyclic hydrocarbon groups; And / or any two adjacent groups of R1 to R8 are directly bonded to form C3 to C 30 Cyclic hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C3~C 30 Nitrocyclic hydrocarbon groups; X is a single bond, C1~C 24 Alkylene, C3~C 30 One of cycloalkylidene, oxy, thiol, sulfinic acid, sulfonic acid or carbonyl groups; n is an integer of 10 to 5000; In formula (2), Y is C1 to C 24 Alkylene, C3~C 30 * represents the bond between the structural unit represented by formula (2) and the segment represented by formula (1) or the bond between the structural unit represented by another structural unit represented by formula (2).
2. The polycarbonate resin material according to claim 1, characterized in that: The molar ratio of the formula (1) to the formula (2) is 80:20 to 99.95:0.
05.
3. The polycarbonate resin material according to claim 2, characterized in that: In the formula (1), n is an integer of 100 to 3000, preferably an integer of 500 to 3000; The molar ratio of formula (1) to formula (2) is 85:15 to 99.5:0.5, preferably 90:10 to 99:
1.
4. The polycarbonate resin material according to claim 1, characterized in that: X in the formula (1) is one or more of methylene, cyclohexylene or phenylene; Y in the formula (2) is one or more of methylene, ethylene, hexylene, cyclohexylene or phenylene, preferably one or more of cyclohexylene or phenylene.
5. The polycarbonate resin material according to claim 1, characterized in that: The formula (1) is one or more of bisphenol A carbonate chain segments, biphenyl carbonate chain segments or benzophenone carbonate chain segments.
6. The method for preparing a polycarbonate resin material according to any one of claims 1 to 5, characterized in that: The diol represented by formula (3), the tetraol represented by formula (4), the dialkyl carbonate represented by formula (5), a catalyst and a heat stabilizer are put into a stirred reactor, replaced with inert gas for multiple times, stirred for a period of time t1 at the initial temperature under the protection of inert gas; then reacted at a certain reaction temperature and pressure for a period of time t2; filled with inert gas protection, unloaded, cooled, and granulated to obtain polycarbonate resin particles; In formula (3), R1 to R8 are selected from H, C1 to C 24 Hydrocarbon, C3~C 30 Cyclic hydrocarbon groups, C1~C 24 Halogenated hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C1~C 24 Nitroalkyl or C3~C 30 One or more of the nitrocyclic hydrocarbon groups; And / or any two adjacent groups of R1 to R8 are directly bonded to form C3 to C 30 Cyclic hydrocarbon groups, C3~C 30 Halogenated cyclic hydrocarbon group, C3~C 30 Nitrocyclic hydrocarbon groups; X is a single bond, C1~C 24 Alkylene, C3~C 30 One of a cycloalkylidene group, an oxy group, a sulfide group, a sulfinic acid group, a sulfonic acid group or a carbonyl group; In formula (4), Y is C1 to C 24 Alkylene, C3~C 30 Cycloalkylene; In formula (5), R and R' are selected from C1 to C 24 Hydrocarbon, C3~C 30 One or more of the cyclic hydrocarbon groups, preferably C4 to C 22 Hydrocarbon, C5~C 24 One or more of the cyclic hydrocarbon groups.
7. The method for preparing a polycarbonate resin material according to claim 6, characterized in that: The molar ratio of the total molar amount of formula (3) and formula (4) to the molar amount of formula (5) is 1: (0.90-1.30), preferably 1: (0.98-1.20); more preferably 1: (1.01-1.10); The amount of the catalyst is 0.0001% to 0.05%, preferably 0.001% to 0.025%, of the total molar amount of the formula (3), formula (4) and formula (5); The amount of the heat stabilizer is 0.01% to 1%, preferably 0.05% to 0.75%, of the total weight of the formula (3), formula (4) and formula (5).
8. The method for preparing a polycarbonate resin material according to claim 6, characterized in that: The catalyst is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, dibutyltin dilaurate, dihexyltin dilaurate, dioctyltin dilaurate, and didecyltin dilaurate; Preferably, it is a combination of sodium bicarbonate and dioctyltin dilaurate; the molar ratio of the sodium bicarbonate to the dioctyltin dilaurate is 1:9 to 9:1; The heat stabilizer is selected from one or more of calcium oxide, zinc oxide, calcium carbonate, zinc carbonate, calcium sulfate and zinc sulfate.
9. The method for preparing a polycarbonate resin material according to claim 6, characterized in that: The stirring rate is 10 to 1000 rpm, preferably 50 to 800 rpm; The initial temperature is 120-240°C, preferably 150-200°C; The time t1 is 5 to 120 minutes, preferably 15 to 100 minutes; The inert gas is nitrogen, argon or helium; The reaction temperature is 150-280°C, preferably 180-250°C; The pressure is 10 -6 ~10 -3 atm, preferably 10 -5 ~10 -3 atm; The time t2 is 30 to 600 minutes, preferably 60 to 450 minutes.
10. An application of the polycarbonate resin material according to any one of claims 1 to 5, wherein the polycarbonate resin material is prepared by the preparation method according to any one of claims 6 to 9, characterized in that: The polycarbonate resin material is used in the medical, public health or health fields, and is used to manufacture medical equipment for dialysis, injection or diagnosis.
Citation Information
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