Polycarbonate composition as well as preparation method and application thereof

Abstract

The invention discloses a polycarbonate composition as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. The polycarbonate composition provided by the invention takes alkylphenol-terminated polycarbonate with good gamma-ray irradiation resistance as matrix resin, and is compounded with polyphenyl sulfone with good irradiation resistance, so that the polycarbonate composition has better gamma-ray irradiation resistance and good mechanical properties, and is suitable for preparing medical instruments.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a polycarbonate composition and a preparation method and application thereof. Background Art

[0002] Polycarbonate (PC) has excellent properties, such as high transparency, high toughness, high temperature resistance, low temperature resistance, high dimensional stability, etc. It is widely used in the fields of medical treatment, home appliances, automobiles, communications, etc. Polycarbonate can be used to prepare medical devices. Medical devices often need to be sterilized, and γ-ray radiation is one of the commonly used sterilization methods. However, after irradiation, polycarbonate is prone to yellowing, brittleness and cracking, which affects the use and appearance of the product. Therefore, it is necessary to find a technology to improve the yellowing and brittleness of polycarbonate during γ-ray irradiation. Summary of the invention

[0003] Based on the defects of the prior art, the purpose of the present application is to provide a polycarbonate composition and a preparation method and application thereof. The obtained polycarbonate composition not only has good resistance to γ-ray radiation, is not prone to yellowing and brittleness after irradiation, but also has good mechanical properties.

[0004] In order to achieve the above objectives, in a first aspect, the present 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 that account for 93% to 99.6% of the total number of polycarbonate end groups;

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

[0010] The polycarbonate composition uses a specific alkylphenol-terminated polycarbonate as a base resin, and the alkylphenol-terminated polycarbonate has good radiation resistance. At the same time, polyphenylsulfone with good radiation resistance is compounded to further improve the radiation resistance of the material; in order to effectively improve the dispersion between the above two resins, the above specific compatibilizer needs to be added. Under the joint action of the above components in specific amounts, the polycarbonate composition not only has good resistance to gamma-ray radiation, is not easy to yellow and embrittle after irradiation, but also has good mechanical properties.

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

[0012] Preferably, the preparation method of the alkylphenol-terminated polycarbonate comprises the following steps: adding bisphenol A and diphenyl carbonate to an ester exchange reactor in a certain molar ratio, adding a catalyst at the same time, carrying out the first stage of ester exchange reaction at 170-180°C, steaming out the by-products, then raising the temperature to 200-230°C, and continuing the reaction at a pressure of 10-40 mmHg, when the amount of phenol steamed out reaches 80-90% of the theoretical amount, the ester exchange reaction is completed. After the ester exchange reaction, the oligomer obtained by the reaction is transferred to a polycondensation reactor, and the polycondensation reaction is carried out at a higher temperature and vacuum degree (about 260-300°C, <1 mmHg), and phenol and diphenyl carbonate are steamed out. As the polycondensation reaction proceeds, the melt viscosity of the material increases and the molecular weight increases. 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 ester exchange reaction to prepare prepolymers. The phenol released by the reaction is evaporated from the reactor under vacuum, condensed and recycled to the diphenyl carbonate synthesis process. The last few reactors mainly carry out polycondensation reaction to prepare polymers. Then the reaction materials enter the thin film evaporator or twin-screw extruder and other equipment, and the end-capping agent is added to the polycarbonate with a number average molecular weight greater than or equal to 15,000. After the end-capping reaction is completed, a molten polycarbonate with a certain molecular weight is generated. The residual phenol in the reaction materials is further removed under high vacuum. The residual end-capping agent will also be removed during the devolatilization process. Finally, the polycarbonate with the required molecular weight is obtained by granulation in a granulator.

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

[0014] The catalyst mentioned above can be a basic catalyst, such as LiOH, etc. The end-capping agent mentioned above is any one of cresol, p-tert-butylphenol, cumylphenol and a mixture thereof, wherein tert-butylphenol is preferred.

[0015] Preferably, the compatibilizer comprises a styrene-acrylonitrile-maleic anhydride terpolymer and an epoxy compatibilizer, and 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 the weight ratio of the two within the range of (0.5-5):1, especially within the range of (1-3):1, the compatibility between the alkylphenol-terminated polycarbonate and the polyphenylsulfone can be synergistically improved, so that the mechanical properties of the composition are better, 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 weight percentage of glycidyl methacrylate in the epoxy compatibilizer is 2% to 6%.

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

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

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

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

[0023] Preferably, the melt flow rate of the polyphenylsulfone under the test conditions of 365° C. and 5.0 kg is 5-25 g / 10 min. Exemplarily, the melt flow rate of the polyphenylsulfone under the test conditions of 365° C. and 5.0 kg is 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 a range formed by any two of the above values.

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

[0025] When the melt flow rate of the polyphenylsulfone under the 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, better compatibility with polycarbonate can be achieved.

[0026] The melt flow rate of the alkylphenol-terminated polycarbonate and the melt flow rate of the polyphenylene sulfone may be measured according to ASTM-D1238-2010.

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

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

[0029] Weathering 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 benzoxazinones, benzoxazinones and triazines.

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

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

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

[0036] The polycarbonate composition described in the present application may contain common additives such as flame retardants and weathering agents without impairing the effects of the present application. The flame retardant may be selected from at least one of bromine flame retardants and phosphorus flame retardants, bromine flame retardants such as brominated polycarbonate; phosphorus flame retardants such as bisphenol A-bis (diphenyl phosphate) and phenoxy polyphosphazene. The weathering agent is at least one of benzoxazinones, benzoxazinones, and triazines.

[0037] In a second aspect, the present 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, the aspect ratio of the twin-screw extruder is 40:1 to 48:1, and the melt extrusion temperature is 220 to 280°C.

[0039] In a third aspect, the present application provides an application of the polycarbonate composition in medical devices. For example, the polycarbonate composition can be used to prepare the outer shell of a hemodialyzer, a respiratory humidifier, an infusion connector, a peritoneal puncture tube, etc.

[0040] Compared with the prior art, the beneficial effect of the present application is that the present application uses an alkylphenol-terminated polycarbonate with good γ-ray radiation resistance as a base resin, and compounded with polyphenylsulfone with good radiation resistance, thereby improving the radiation resistance of the polycarbonate composition, and at the same time, adding a specific compatibilizer to improve the compatibility between the alkylphenol-terminated polycarbonate and the polyphenylsulfone. Under the joint action of the above-mentioned components in specific amounts, the polycarbonate composition obtained by the present application has good γ-ray radiation resistance, is not easy to yellow and embrittle after irradiation, and has good mechanical properties, and is suitable for preparing medical devices, such as preparing the outer shells of hemodialyzers, respiratory humidifiers, infusion connectors, and peritoneal puncture tubes. DETAILED DESCRIPTION

[0041] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present application in detail, rather than to limit the present application. All other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present application. The experimental reagents and instruments involved in the implementation of this application are all commonly used ordinary reagents and instruments unless otherwise specified. In the present application, the technical features described in an open manner include closed technical schemes composed of the listed features, and also include open technical schemes containing the listed features.

[0042] The raw material information used in the following examples and comparative examples is as follows. In addition, the component raw materials used in each parallel experiment are all of the same type.

[0043] Alkylphenol-terminated polycarbonate 1: Alkylphenol-terminated bisphenol A type polycarbonate, alkylphenol-terminated groups account for 99.4% of the total number of its end groups, and the melt flow rate at 300° C. and 1.2 kg is 6 g / 10 min. The preparation method is as follows: bisphenol A and diphenyl carbonate are added to an ester exchange reactor in a molar ratio of 1.05:1, and LiOH with a molar amount of 0.02% of bisphenol A is added at the same time, and the first stage of ester exchange reaction is carried out at 175° C., and the by-products are evaporated. The temperature was then raised to 230° C. and the reaction was continued at a pressure of 20 mmHg. When the amount of phenol distilled out reached 85% of the theoretical amount, the transesterification reaction was completed. The resulting oligomer was transferred to a polycondensation reactor for polycondensation 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 the end-capping agent, tert-butylphenol, were added for end-capping reaction to obtain alkylphenol-end-capped polycarbonate 1.

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

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

[0046] Polycarbonate 4: bisphenol A type polycarbonate, melt flow rate at 300°C and 1.2 kg is 15 g / 10 min, and its preparation method is different from that of alkylphenol-terminated polycarbonate 1 in that the end-capping agent tert-butylphenol is not used;

[0047] Polycarbonate 5: Bisphenol A polycarbonate, non-alkylphenol end-capped, melt flow rate at 300°C and 1.2kg is 10g / 10min, Chimei, PC110;

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

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

[0050] PPSU 3: Melt flow rate at 365°C and 5.0 kg is 15 g / 10 min, Syensqo, R-5100NT ECHORP;

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

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

[0053] Epoxy compatibilizer 1: styrene-acrylonitrile-glycidyl methacrylate terpolymer (SAG-002, Jiayirong);

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

[0055] Weathering agent: UV-1600, 2,4-di(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 and tris(2,4-di-tert-butylphenyl) phosphite as a secondary antioxidant, the weight ratio of the two being 1:0.8, and commercially available;

[0057] Lubricant: pentaerythritol stearate, commercially available;

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

[0059] The formulations of the polycarbonate compositions of these embodiments and comparative examples 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 gamma 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 gamma ray irradiation energy is 50KGy.

[0061] Impact strength test: The sample was made into a 3.2mm*12.7mm*64mm A-notched specimen, irradiated with γ-rays, and the γ-ray irradiation energy was 50KGy. The cantilever beam impact strength of the specimen before and after irradiation at 23°C was measured according to ASTM D256-2010.

[0062] Table 1

[0063]

[0064]

[0065] Table 2

[0066]

[0067] Table 3

[0068]

[0069]

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

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

[0072] From the comparison of Examples 1, 9 to 14 and Comparative Example 5, it can be seen that the compounding of maleimide and epoxy compatibilizer, especially when the mass ratio of the two is (1 to 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] Comparison of Examples 1, 5 to 6 with Comparative Examples 3 to 4 shows that alkylphenol end-capping of polycarbonate is beneficial to improving the γ-ray irradiation resistance.

[0074] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application rather than to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, ordinary technicians in this field should understand that the technical solution of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present application.

Claims

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

2. The polycarbonate composition according to claim 1, wherein 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, wherein The compatibilizer comprises a styrene-acrylonitrile-maleic anhydride terpolymer and an epoxy compatibilizer, and 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, wherein 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, wherein The melt flow rate of the alkylphenol-terminated polycarbonate under the test conditions of 300° C. and 1.2 kg is 5-30 g / 10 min.

7. The polycarbonate composition according to claim 1, wherein The polyphenylsulfone 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, wherein At least one of the following conditions is met: (1) The alkylphenol-terminated polycarbonate comprises alkylphenol-terminated bisphenol A polycarbonate; (2) It also contains the following components in parts by weight: Weathering agent 0.1-2 parts; Antioxidant 0.1-1 part; Lubricant 0.1-1 part.

9. The method for preparing a polycarbonate composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing and dispersing all raw materials, melting and extruding, cooling and granulating to obtain a polycarbonate composition.

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

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