A polycarbonate composition, a method for preparing the same and use thereof

Abstract

The application discloses a polycarbonate composition and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The polycarbonate composition has good resistance to gamma-ray irradiation, and is prepared from alkyl phenol-terminated polycarbonate with good resistance to gamma-ray irradiation as a base resin and polyphenylsulfone with good resistance to irradiation, and has better resistance to gamma-ray irradiation, and also has good mechanical properties, and is suitable for preparing medical devices.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, specifically to a polycarbonate composition and its preparation method and application. Background Technology

[0002] Polycarbonate (PC) possesses excellent properties such as high transparency, high toughness, high temperature resistance, low temperature resistance, and high dimensional stability, leading to its widespread applications in medical, home appliance, automotive, and telecommunications fields. Polycarbonate can be used to manufacture medical devices. Medical devices frequently require sterilization, and gamma-ray radiation is one of the commonly used sterilization methods. However, polycarbonate is prone to yellowing and embrittlement after irradiation, affecting the product's usability and appearance. Therefore, a technology is needed to improve the yellowing and embrittlement of polycarbonate during gamma-ray irradiation. Summary of the Invention

[0003] Based on the deficiencies of the existing technology, the purpose of this application is to provide a polycarbonate composition, its preparation method and application. The obtained polycarbonate composition not only has good resistance to γ-ray irradiation and is not prone to yellowing and embrittlement after irradiation, but also has good mechanical properties.

[0004] To achieve the above objectives, in a first aspect, this application provides a polycarbonate composition comprising the following components in parts by weight:

[0005] 49-80 parts of alkylphenol-terminated polycarbonate;

[0006] Polyphenylsulfone (PPSU) 20-50 parts;

[0007] Compatibilizer 0.1-3 parts;

[0008] The alkylphenol-terminated polycarbonate contains alkylphenol-terminated groups accounting for 93% to 99.6% of the total number of polycarbonate end groups;

[0009] The compatibilizer is at least one of styrene-acrylonitrile-maleic anhydride terpolymer and epoxy compatibilizer.

[0010] The polycarbonate composition uses a specific alkylphenol-terminated polycarbonate as the matrix resin. Alkylphenol-terminated polycarbonate exhibits good radiation resistance, and the addition of polyphenylene sulfone, which also has good radiation resistance, further enhances the material's radiation resistance. To effectively improve the dispersion between the two resins, the aforementioned specific compatibilizer needs to be added. Under the combined action of specific amounts of the above components, the polycarbonate composition not only exhibits good resistance to gamma-ray radiation and is less prone to yellowing and embrittlement after irradiation, but also possesses good mechanical properties.

[0011] The mass ratio of the alkylphenol-terminated polycarbonate to the polyphenylene sulfone is (1-4):1, such as 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, or any two of the above values. Preferably, the mass ratio of the alkylphenol-terminated polycarbonate to the polyphenylene sulfone is (1.3-2.5):1, so as to improve the resistance to gamma ray irradiation while maintaining the impact resistance of the material.

[0012] Preferably, the method for preparing the alkylphenol-terminated polycarbonate includes the following steps: Bisphenol A and diphenyl carbonate are added to an ester exchange reactor in a certain molar ratio, along with a catalyst. A first-stage ester exchange reaction is carried out at 170–180°C. After distilling off the byproducts, the temperature is raised to 200–230°C, and the reaction continues at a pressure of 10–40 mmHg. The ester exchange reaction is completed when the amount of phenol distilled off reaches 80–90% of the theoretical amount. The oligomer obtained after the ester exchange reaction is transferred to a polycondensation reactor, where a polycondensation reaction is carried out at a higher temperature and vacuum (approximately 260–300°C, <1 mmHg), distilling off phenol and diphenyl carbonate. As the polycondensation reaction proceeds, the melt viscosity and molecular weight of the material increase. When the desired molecular weight is reached, the material is transferred to the next process. The melt ester exchange polycondensation reaction can be carried out in multiple reactors connected in series. The first few reactors mainly carry out transesterification reactions to produce prepolymers. The phenol released from the reaction is distilled off the reactor under vacuum, condensed, and recycled to the diphenyl carbonate synthesis process. The later reactors mainly carry out polycondensation reactions to produce polymers. The reactants are then fed into equipment such as a thin-film evaporator or a twin-screw extruder, where end-capping agents are added to polycarbonate with a number average molecular weight greater than or equal to 15,000. After the end-capping reaction is completed, molten polycarbonate with a certain molecular weight is generated. Residual phenol in the reactants is further removed under high vacuum, and residual end-capping agents are also eliminated during the devolatilization process. Finally, the polycarbonate with the required molecular weight is obtained by granulation.

[0013] The molar ratio of bisphenol A to diphenyl carbonate can be selected as (1.0 to 1.1):1, the molar ratio of bisphenol A to catalyst can be selected as 1:(0.005% to 0.04%), and the weight of the capping agent can be selected as 5% to 50% of the total weight of bisphenol A, diphenyl carbonate and capping agent.

[0014] The catalyst described above can be a basic catalyst, such as LiOH. The end-capping agent described above is any one of cresol, p-tert-butylphenol, cumylphenol, and mixtures thereof, with tert-butylphenol being preferred.

[0015] Preferably, the compatibilizer comprises a styrene-acrylonitrile-maleic anhydride terpolymer and an epoxy compatibilizer, wherein the weight ratio of the styrene-acrylonitrile-maleic anhydride terpolymer to the epoxy compatibilizer is (0.5–5):1. More preferably, the weight ratio of the styrene-acrylonitrile-maleic anhydride terpolymer to the epoxy compatibilizer is (1–3):1. By compounding the styrene-acrylonitrile-maleic anhydride terpolymer and the epoxy compatibilizer, and controlling their weight ratio within the range of (0.5–5):1, especially within the range of (1–3):1, the compatibility between alkylphenol-terminated polycarbonate and polyphenylsulfone can be synergistically improved, resulting in better mechanical properties of the composition, such as higher notched impact strength (Type A).

[0016] Preferably, the epoxy compatibilizer includes at least one of ethylene-acrylate-glycidyl methacrylate and ethylene-butyl acrylate-glycidyl methacrylate copolymer.

[0017] Preferably, the epoxy compatibilizer contains 2% to 6% glycidyl methacrylate by weight.

[0018] Preferably, the maleic anhydride content in the styrene-acrylonitrile-maleic anhydride terpolymer is 6% to 13% by weight.

[0019] Preferably, the weight-average molecular weight of the styrene-acrylonitrile-maleic anhydride terpolymer is 90,000 to 100,000 g / mol.

[0020] Preferably, the melt flow rate of the alkylphenol-terminated polycarbonate at test conditions of 300°C and 1.2 kg is 5-30 g / 10 min. Exemplarily, the melt flow rate of the alkylphenol-terminated polycarbonate at test conditions of 300°C and 1.2 kg is 5 g / 10 min, 7 g / 10 min, 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 20 g / 10 min, 23 g / 10 min, 25 g / 10 min, 27 g / 10 min, 30 g / 10 min, or any two of the above values ​​within a range.

[0021] More preferably, the alkylphenol-terminated polycarbonate has a melt flow rate of 5-15 g / 10 min under test conditions of 300°C and 1.2 kg.

[0022] When the alkylphenol-terminated polycarbonate exhibits better temperature resistance and mechanical properties under test conditions of 300°C and 1.2 kg, with a melt flow rate in the range of 5-30 g / 10 min, especially in the range of 5-15 g / 10 min.

[0023] Preferably, the melt flow rate of the polyphenylene sulfone under test conditions of 365°C and 5.0 kg is 5-25 g / 10 min. For example, the melt flow rate of the polyphenylene sulfone under test conditions of 365°C and 5.0 kg is a range of 5 g / 10 min, 7.5 g / 10 min, 9 g / 10 min, 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 20 g / 10 min, 23 g / 10 min, 25 g / 10 min, or any two of the above values.

[0024] More preferably, the polyphenylene sulfone has a melt flow rate of 15-25 g / 10 min under test conditions of 365°C and 5.0 kg.

[0025] When the melt flow rate of the polyphenylsulfone under test conditions of 365°C and 5.0 kg is in the range of 5-25 g / 10 min, especially in the range of 15-25 g / 10 min, it can achieve better compatibility with polycarbonate.

[0026] The melt flow rates of the alkylphenol-terminated polycarbonate and the polyphenylene sulfone can be selected according to ASTM-D1238-2010.

[0027] Preferably, the alkylphenol-terminated polycarbonate includes alkylphenol-terminated bisphenol A type polycarbonate.

[0028] Preferably, the polycarbonate composition further comprises the following components in parts by weight:

[0029] Weather resistant agent 0.1-2 parts;

[0030] Antioxidant 0.1-1 part;

[0031] Lubricant 0.1-1 part.

[0032] Preferably, the weathering agent includes at least one of benzoxazinone, benzoxazinone, and triazine.

[0033] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the weight ratio of the primary antioxidant to the secondary antioxidant is 1:(0.5-1.0), wherein the primary antioxidant is a hindered phenolic primary antioxidant, and the secondary antioxidant is a phosphite secondary antioxidant. As an example, the hindered phenolic primary antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester; the phosphite secondary antioxidant is tris(2,4-di-tert-butylphenyl) phosphite ester.

[0034] Preferably, the lubricant comprises at least one of oxidized polyethylene wax and pentaerythritol stearate.

[0035] Preferably, the alkylphenol-terminated polycarbonate in the polycarbonate composition has a mass fraction of 46.7% or more, such as a range of 46.7%, 48%, 50%, 55%, 60%, 65%, 50%, 75%, 80%, 85%, 89% or more, or any two of these ranges.

[0036] The polycarbonate composition described in this application may contain commonly used additives such as flame retardants and weather retardants without impairing the effectiveness of this application. The flame retardant may be selected from at least one of brominated flame retardants and phosphorus-based flame retardants, such as brominated polycarbonate; and phosphorus-based flame retardants may be at least one of bisphenol A-bis(diphenyl phosphate) and phenoxy polyphosphazene. The weather retardant is at least one of benzoxazinones, benzoxazinones, and triazines.

[0037] Secondly, this application provides a method for preparing the polycarbonate composition, comprising the following steps: mixing all raw materials, melt extruding, cooling and granulating to obtain the polycarbonate composition.

[0038] Preferably, the melt extrusion is carried out in a twin-screw extruder with a length-to-diameter ratio of 40:1 to 48:1 and a melt extrusion temperature of 220 to 280°C.

[0039] Thirdly, this application provides the use of the polycarbonate composition in medical devices. For example, the polycarbonate composition can be used to manufacture the housing of hemodialyzers, humidifiers, infusion connectors, peritoneal puncture tubes, etc.

[0040] Compared to existing technologies, the advantages of this application are as follows: This application uses alkylphenol-terminated polycarbonate with good gamma-ray irradiation resistance as the matrix resin, and combines it with polyphenylene sulfone with good radiation resistance, thereby improving the radiation resistance of the polycarbonate composition. Simultaneously, specific compatibilizers are added to improve the compatibility between the alkylphenol-terminated polycarbonate and polyphenylene sulfone. The polycarbonate composition obtained by this application, under the combined action of specific amounts of the above components, exhibits good gamma-ray irradiation resistance, is not prone to yellowing or embrittlement after irradiation, and possesses good mechanical properties, making it suitable for manufacturing medical devices, such as the outer shells of hemodialyzers, humidifiers, infusion connectors, and peritoneal puncture tubes. Detailed Implementation

[0041] To better illustrate the purpose, technical solutions, and advantages of this application, the following description, in conjunction with specific embodiments and comparative examples, aims to provide a detailed understanding of the content of this application, rather than limiting it. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this application. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this application are commonly used reagents and instruments. In this application, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0042] The raw material information used in the following embodiments and comparative examples is shown below. In addition, the raw materials used in each parallel experiment are the same.

[0043] Alkylphenol-terminated polycarbonate 1: Alkylphenol-terminated bisphenol A type polycarbonate, with alkylphenol-terminated groups accounting for 99.4% of its total end groups. The melt flow rate at 300℃ and 1.2 kg is 6 g / 10 min. The preparation method is as follows: Bisphenol A and diphenyl carbonate are added to a transesterification reactor at a molar ratio of 1.05:1, along with 0.02% (molar amount) of LiOH from bisphenol A. The first stage of transesterification reaction is carried out at 175℃, and the byproducts are distilled off. The temperature was then raised to 230°C and the reaction continued at a pressure of 20 mmHg. When the amount of phenol distilled off reached 85% of the theoretical amount, the transesterification reaction was completed. The resulting oligomer was transferred to a polycondensation reactor and polycondensation was carried out at 300°C and 0.5 mmHg. When the number average molecular weight reached 20,000, it was transferred to a twin-screw extruder and bisphenol A, diphenyl carbonate, and 10% of the total weight of tert-butylphenol as a capping agent were added for capping reaction to obtain alkylphenol-capped polycarbonate 1.

[0044] Alkylphenol-terminated polycarbonate 2: Alkylphenol-terminated bisphenol A type polycarbonate, with alkylphenol-terminated groups accounting for 99.1% of its total end groups, and a melt flow rate of 10 g / 10 min at 300 °C and 1.2 kg. Its preparation method differs from that of alkylphenol-terminated polycarbonate 1 in that the polycondensation reaction temperature is 280 °C, and the product obtained from the polycondensation reaction is transferred to a twin-screw extruder when the number average molecular weight reaches 18,000.

[0045] Alkylphenol-terminated polycarbonate 3: Alkylphenol-terminated bisphenol A type polycarbonate, with alkylphenol-terminated groups accounting for 98.5% of its total end groups, and a melt flow rate of 15 g / 10 min at 300°C and 1.2 kg. Its preparation method differs from that of alkylphenol-terminated polycarbonate 1 in that the polycondensation reaction temperature is 260°C, and the product obtained from the polycondensation reaction is transferred to a twin-screw extruder when the number average molecular weight reaches 15,000.

[0046] Polycarbonate 4: Bisphenol A type polycarbonate, with a melt flow rate of 15 g / 10 min at 300℃ and 1.2 kg. Its preparation method differs from that of alkylphenol-terminated polycarbonate 1 in that it does not use the terminator tert-butylphenol.

[0047] Polycarbonate 5: Bisphenol A type polycarbonate, non-alkylphenol end capped, melt flow rate of 10 g / 10 min at 300℃ and 1.2 kg, Chi Mei, PC110;

[0048] PPSU 1: Melt flow rate at 365℃ and 5.0 kg is 7.5 g / 10 min, DURASON PSU 1700;

[0049] PPSU 2: Melt flow rate of 10 g / 10 min at 365℃ and 5.0 kg, RTP, 1400R-5500;

[0050] PPSU 3: Melt flow rate of 15 g / 10 min at 365℃ and 5.0 kg, Synesqo, R-5100NT ECHORP;

[0051] Styrene-acrylonitrile-maleic anhydride terpolymer, maleic anhydride content 10±2wt.%, SAM-010, Jia Yi Rong;

[0052] Maleic anhydride-grafted styrene-acrylonitrile copolymer: prepared according to patent CN118271818A, with a maleic anhydride content of 1.5 wt.%;

[0053] Epoxy compatibilizer 1: Styrene-acrylonitrile-glycidyl methacrylate terpolymer (SAG-002, Jia Yi Rong);

[0054] Epoxy compatibilizer 2: Styrene-butyl acrylonitrile-glycidyl methacrylate terpolymer (DuPont, ELVALOY RESINS PTW);

[0055] Weather resistant agent: UV-1600, 2,4-bis(4-biphenyl)-6-(2,4-dihydroxy)phenyl-1,3,5-triazine, commercially available;

[0056] Antioxidant: a mixture of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester and phosphite co-antioxidant tris(2,4-di-tert-butylphenyl) phosphite, with a weight ratio of 1:0.8, commercially available;

[0057] Lubricant: Pentaerythritol stearate, commercially available;

[0058] The following examples and comparative examples all provide a polycarbonate composition, including the following steps: mixing and dispersing all raw materials, adding them to a twin-screw extruder, melt extruding, cooling and granulating to obtain a polycarbonate composition, wherein the length-to-diameter ratio of the twin-screw extruder is 40:1, and the melt extrusion temperature is 220-280℃.

[0059] The formulations of these example and comparative polycarbonate compositions are shown in Tables 1 and 2. The following performance tests were performed on these polycarbonate compositions:

[0060] Color difference test: Prepare sample strips with a size of 55mm*85mm, irradiate with γ-rays, and test the b value of the material color plate under the conditions of D65 and 10° according to GB / T3979-2008, where the γ-ray irradiation energy is 50KGy.

[0061] Impact strength test: The sample was made into a type A notch specimen with dimensions of 3.2mm*12.7mm*64mm and irradiated with gamma rays at an energy of 50KGy. The cantilever beam impact strength of the specimen before and after irradiation at 23℃ was measured according to ASTM D256-2010.

[0062] Table 1

[0063]

[0064]

[0065] Table 2

[0066]

[0067] Table 3

[0068]

[0069]

[0070] As can be seen from the above data, the compositions of each embodiment possess both good resistance to gamma ray irradiation and good mechanical properties. For example, after irradiation with gamma rays of 50 KGy energy, the color difference Δb is less than 5, the notched impact strength (Type A) of the cantilever beam at 23°C before irradiation is above 540 J / m, and the retention rate of the notched impact strength (Type A) of the cantilever beam at 23°C after irradiation with gamma ray energy of 50 KGy is above 55%.

[0071] A comparison of Examples 1-4 with Comparative Examples 1-2 shows that when the mass ratio of alkylphenol-terminated polycarbonate to polyphenylsulfone is (1-4):1, especially (1.3-2.5):1, the balance between gamma ray irradiation resistance and mechanical properties is better.

[0072] As can be seen from the comparison of Examples 1, 9-14 and Comparative Example 5, the combined use of maleimide and epoxy compatibilizer, especially when the mass ratio of the two is (1-3):1, has a better effect on improving the compatibility of alkylphenol-terminated polycarbonate with PPSU, which is beneficial to improving the mechanical properties of the composition.

[0073] As can be seen from the comparison of Examples 1, 5-6 and Comparative Examples 3-4, alkylphenol end-capping of polycarbonate is beneficial to improving its resistance to gamma-ray irradiation.

[0074] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A polycarbonate composition, characterized in that, Components including the following weight fractions: 49-80 parts of alkylphenol-terminated polycarbonate; 20-50 parts of polyphenylsulfone; Compatibilizer 0.1-3 parts; The alkylphenol-terminated polycarbonate contains alkylphenol-terminated groups accounting for 93% to 99.6% of the total number of polycarbonate end groups; The compatibilizer is at least one of styrene-acrylonitrile-maleic anhydride terpolymer and epoxy compatibilizer.

2. The polycarbonate composition according to claim 1, characterized in that, The mass ratio of the alkylphenol-terminated polycarbonate to the polyphenylsulfone is (1.3~2.5):

1.

3. The polycarbonate composition according to claim 1, characterized in that, The compatibilizer includes a styrene-acrylonitrile-maleic anhydride terpolymer and an epoxy compatibilizer, wherein the weight ratio of the styrene-acrylonitrile-maleic anhydride terpolymer to the epoxy compatibilizer is (0.5~5):

1.

4. The polycarbonate composition according to claim 3, characterized in that, The weight ratio of the styrene-acrylonitrile-maleic anhydride terpolymer to the epoxy compatibilizer is (1~3):

1.

5. The polycarbonate composition according to claim 1, characterized in that, The epoxy compatibilizer includes at least one of ethylene-acrylate-glycidyl methacrylate and ethylene-butyl acrylate-glycidyl methacrylate copolymer.

6. The polycarbonate composition according to claim 1, characterized in that, The alkylphenol-terminated polycarbonate exhibits a melt flow rate of 5-30 g / 10 min under test conditions of 300°C and 1.2 kg.

7. The polycarbonate composition according to claim 1, characterized in that, The polyphenylene sulfone has a melt flow rate of 5-25 g / 10 min under the test conditions of 365°C and 5.0 kg.

8. The polycarbonate composition according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The alkylphenol-terminated polycarbonate includes alkylphenol-terminated bisphenol A type polycarbonate; (2) It also contains the following components in parts by weight: Weather resistant agent 0.1-2 parts; Antioxidant 0.1-1 part; Lubricant 0.1-1 part.

9. The method for preparing the polycarbonate composition according to any one of claims 1 to 8, characterized in that, The process includes the following steps: mixing and dispersing all raw materials, melt extrusion, cooling and granulation to obtain a polycarbonate composition.

10. The use of the polycarbonate composition according to any one of claims 1 to 8 in the preparation of medical devices.

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