Polycarbonate composite material resistant to gamma-ray irradiation as well as preparation method and application of polycarbonate composite material

Abstract

The invention discloses a gamma-ray irradiation resistant polycarbonate composite material and a preparation method thereof. The gamma-ray irradiation resistant polycarbonate composite material is prepared from the following raw materials in parts by weight: 85 to 99 parts of polycarbonate resin, 0.1 to 1.0 part of a free radical stabilizer, 0.1 to 1.0 part of an antioxidant, 0.1 to 1.0 part of a chain extender and 0.01 to 5 parts of an auxiliary agent, under the combined action of the free radical stabilizer, the antioxidant and the chain extender, the gamma-ray irradiation resistance effect of the gamma-ray irradiation-resistant polycarbonate composite material is remarkably improved, and after the gamma-ray irradiation-resistant polycarbonate composite material is irradiated by 30 KGY gamma rays, the color only slightly turns yellow and slowly recovers within two weeks; and the original light transmittance performance and conventional mechanical properties of polycarbonate are not changed.

Description

Technical Field

[0001] This invention relates to the field of polycarbonate technology, specifically to a polycarbonate composite material resistant to gamma-ray irradiation, its preparation method, and its application. Background Technology

[0002] Polycarbonate is a high-performance thermoplastic engineering plastic with excellent impact resistance, good creep resistance and dimensional stability, heat resistance, low water absorption, non-toxicity, and good transparency. It is currently used in medical devices, which require gamma-ray sterilization before use. However, ordinary polycarbonate undergoes irreversible and severe yellowing after gamma-ray irradiation sterilization, affecting its normal use. Therefore, this invention is proposed.

[0003] In view of this, the present invention is hereby proposed. Summary of the Invention

[0004] The purpose of this invention is to provide a polycarbonate composite material resistant to gamma-ray irradiation, its preparation method, and its application. The polycarbonate composite material resistant to gamma-ray irradiation of this invention has excellent gamma-ray resistance properties through the selection of various raw materials.

[0005] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0006] The first aspect of this invention provides a polycarbonate composite material resistant to gamma-ray irradiation, the polycarbonate composite material comprising the following raw materials in parts by weight:

[0007] The mixture contains 85-99 parts of polycarbonate resin, 0.1-1.0 parts of free radical stabilizer, 0.1-1.0 parts of antioxidant, 0.1-1.0 parts of chain extender, and 0.01-5 parts of additives.

[0008] Preferably, the polycarbonate resin has a melt flow rate of 7-20 g / 10 min at 300°C and 1.2 kg.

[0009] Preferably, the free radical stabilizer is selected from at least one of 2,5-di-tert-butylhydroquinone, hydroquinone dibenzyl acid, and dibenzyl ketone.

[0010] Preferably, the antioxidant is selected from at least one of antioxidant 1076, antioxidant 168, antioxidant 501 and antioxidant 608.

[0011] Preferably, the chain extender is ADR4385 and / or ADR4368.

[0012] Preferably, the additive is selected from at least one of color powder, lubricant and toughening agent.

[0013] Preferably, the lubricant is selected from at least one of pentaerythritol stearate, polyethylene wax, and silicone lubricant.

[0014] Preferably, the toughening agent is selected from at least one of substituted chloroprene rubber, substituted spiral polypropylene, and cellulose.

[0015] A second aspect of the present invention provides a method for preparing the above-mentioned gamma-ray resistant polycarbonate composite material, the method comprising the following steps:

[0016] (a) Free radical stabilizer, antioxidant, chain extender and additives are mixed and dispersed to obtain a premix;

[0017] (b) The premix and polycarbonate are added to a twin-screw extruder for extrusion molding, and water vapor is introduced during the extrusion process to remove small molecules and impurities in the polycarbonate and additives by devolatilization, thereby obtaining the γ-ray irradiation resistant polycarbonate composite material.

[0018] Preferably, the temperature of the twin-screw extruder is 220~280℃ and the rotation speed is 200~600rpm.

[0019] A third aspect of the present invention provides the application of the gamma-ray irradiation-resistant polycarbonate composite material in the preparation of medical devices.

[0020] Compared with the prior art, the beneficial effects of the present invention include at least the following:

[0021] The polycarbonate composite material resistant to gamma ray irradiation of this invention has a significantly improved gamma ray irradiation resistance under the combined action of free radical stabilizers, antioxidants and chain extenders. After being irradiated with 30KGY of gamma rays, the color only shows slight yellowing and slowly recovers within two weeks; and it does not change the original light transmittance and conventional mechanical properties of polycarbonate. Detailed Implementation

[0022] The embodiments of the technical solution of the present invention will be described in detail below with reference to the examples. The following embodiments are only used to illustrate the technical solution of the present invention more clearly, and are therefore only examples, and should not be used to limit the scope of protection of the present invention.

[0023] It should be noted that, unless otherwise stated, the technical or scientific terms used in this application should have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0024] This invention provides a polycarbonate composite material resistant to gamma-ray irradiation, the polycarbonate composite material comprising the following raw materials in parts by weight:

[0025] The mixture contains 85-99 parts of polycarbonate resin, 0.1-1.0 parts of free radical stabilizer, 0.1-1.0 parts of antioxidant, 0.1-1.0 parts of chain extender, and 0.01-5 parts of additives.

[0026] The gamma-ray irradiation-resistant polycarbonate composite material of this invention exhibits significantly improved gamma-ray irradiation resistance through the combined action of free radical stabilizers, antioxidants, and chain extenders. After irradiation with 30 kGY of gamma rays, only slight yellowing occurs, which slowly recovers within two weeks; and the original light transmittance and conventional mechanical properties of the polycarbonate are not altered. Antioxidants slow down oxidation reactions during processing and irradiation, while chain extenders primarily inhibit and repair molecular chain breakage during processing and irradiation, maintaining the original mechanical properties of the polycarbonate. Free radical stabilizers delay and prevent material degradation, thereby delaying and restoring the yellowing phenomenon during irradiation.

[0027] In one embodiment, the polycarbonate resin has a melt flow rate of 7 to 20 g / 10 min at 300°C and 1.2 kg.

[0028] In one embodiment, the free radical stabilizer is selected from at least one of 2,5-di-tert-butylhydroquinone, hydroquinone dibenzyl acid, and dibenzyl ketone.

[0029] In one embodiment, the antioxidant is selected from at least one of antioxidant 1076, antioxidant 168, antioxidant 501, and antioxidant 608.

[0030] In one embodiment, the chain extender is ADR4385 and / or ADR4368.

[0031] In one embodiment, the additive is selected from at least one of color powder, lubricant, and toughening agent.

[0032] In one embodiment, the lubricant is selected from at least one of pentaerythritol stearate, polyethylene wax, and silicone lubricants.

[0033] In one embodiment, the toughening agent is selected from at least one of substituted chloroprene rubber, substituted spiral polypropylene, and cellulose.

[0034] Another embodiment of the present invention provides a method for preparing the above-mentioned gamma-ray resistant polycarbonate composite material, the method comprising the following steps:

[0035] (a) Free radical stabilizer, antioxidant, chain extender and additives are mixed and dispersed to obtain a premix;

[0036] (b) The premix and polycarbonate are added to a twin-screw extruder for extrusion molding, and water vapor is introduced during the extrusion process to remove small molecules and impurities in the polycarbonate and additives by devolatilization, thereby obtaining the γ-ray irradiation resistant polycarbonate composite material.

[0037] In one embodiment, the temperature of the twin-screw extruder is 220~280°C and the rotation speed is 200~600 rpm.

[0038] Another embodiment of the present invention provides the application of the gamma-ray irradiation-resistant polycarbonate composite material in the preparation of medical devices.

[0039] The technical solution of the present invention will be further described in detail below through specific embodiments.

[0040] The raw materials used in the following embodiments are as follows:

[0041] Polycarbonate resin: melt flow rate 10g / 10min, PC 910RB, Shengtong Juyuan;

[0042] Free radical stabilizer: Hydroquinone dibenzyl acid: commercially available;

[0043] Chain extender: ADR4368, BASF, Germany;

[0044] Antioxidant: Antioxidant 501, from Taiwan's Chi-Tien;

[0045] Lubricant: Pentaerythritol stearate, commercially available;

[0046] Pigment: Blue pigment, commercially available.

[0047] Example 1

[0048] This embodiment is a polycarbonate composite material resistant to gamma-ray irradiation, which comprises the following raw materials in parts by weight:

[0049] The mixture contains 99 parts of polycarbonate resin, 0.4 parts of free radical stabilizer, 0.2 parts of antioxidant, 0.2 parts of chain extender, and 0.2 parts of additives. The additives consist of color powder and lubricant in a mass ratio of 1:1.

[0050] The preparation method of the above-mentioned gamma-ray resistant polycarbonate composite material includes the following steps:

[0051] (a) Free radical stabilizer, antioxidant, chain extender and additives are mixed and dispersed to obtain a premix;

[0052] (b) The premix and polycarbonate are added to a twin-screw extruder for extrusion molding, and water vapor is introduced during the extrusion process to remove small molecules and impurities in the polycarbonate and additives by devolatilization, thereby obtaining the γ-ray irradiation resistant polycarbonate composite material.

[0053] In step (b), the length-to-diameter ratio of the twin-screw extruder is 44:1; the barrel temperature is 260°C; and the screw speed is 500 rpm.

[0054] Comparative Example 1

[0055] This comparative example is a polycarbonate composite material resistant to gamma-ray irradiation, which comprises the following raw materials in parts by weight:

[0056] The mixture comprises 99.2 parts of polycarbonate resin, 0.4 parts of free radical stabilizer, 0.2 parts of antioxidant, and 0.2 parts of additives, wherein the additives consist of color powder and lubricant in a mass ratio of 1:1.

[0057] The preparation method of the above-mentioned gamma-ray resistant polycarbonate composite material includes the following steps:

[0058] (a) Free radical stabilizer, antioxidant and additives are mixed and dispersed to obtain a premix;

[0059] (b) The premix and polycarbonate are added to a twin-screw extruder for extrusion molding, and water vapor is introduced during the extrusion process to remove small molecules and impurities in the polycarbonate and additives by devolatilization, thereby obtaining the γ-ray irradiation resistant polycarbonate composite material.

[0060] In step (b), the length-to-diameter ratio of the twin-screw extruder is 44:1; the barrel temperature is 260°C; and the screw speed is 500 rpm.

[0061] Comparative Example 2

[0062] This comparative example is a polycarbonate composite material resistant to gamma-ray irradiation, which comprises the following raw materials in parts by weight:

[0063] The mixture contains 99.2 parts of polycarbonate resin, 0.4 parts of free radical stabilizer, 0.2 parts of chain extender, and 0.2 parts of additives. The additives consist of color powder and lubricant in a mass ratio of 1:1.

[0064] The preparation method of the above-mentioned gamma-ray resistant polycarbonate composite material includes the following steps:

[0065] (a) The free radical stabilizer, chain extender and auxiliaries are mixed and dispersed to obtain a premix;

[0066] (b) The premix and polycarbonate are added to a twin-screw extruder for extrusion molding, and water vapor is introduced during the extrusion process to remove small molecules and impurities in the polycarbonate and additives by devolatilization, thereby obtaining the γ-ray irradiation resistant polycarbonate composite material.

[0067] In step (b), the length-to-diameter ratio of the twin-screw extruder is 44:1; the barrel temperature is 270°C; and the screw speed is 500 rpm.

[0068] Comparative Example 3

[0069] This comparative example is a polycarbonate composite material resistant to gamma-ray irradiation, which comprises the following raw materials in parts by weight:

[0070] The mixture comprises 99.4 parts of polycarbonate resin, 0.2 parts of antioxidant, 0.2 parts of chain extender, and 0.2 parts of additives, wherein the additives consist of color powder and lubricant in a mass ratio of 1:1.

[0071] The preparation method of the above-mentioned gamma-ray resistant polycarbonate composite material includes the following steps:

[0072] (a) Polycarbonate resin, antioxidant, chain extender and additives are mixed and dispersed to obtain a premix;

[0073] (b) The premixed material is added to a twin-screw extruder for extrusion molding, and water vapor is introduced during the extrusion process to remove small molecules and impurities in polycarbonate and additives by devolatilization, thereby obtaining the γ-ray irradiation resistant polycarbonate composite material.

[0074] In step (b), the length-to-diameter ratio of the twin-screw extruder is 44:1; the barrel temperature is 270°C; and the screw speed is 500 rpm.

[0075] The γ-ray irradiation resistant polycarbonate composite materials prepared in Example 1 and Comparative Examples 1-3 were obtained respectively;

[0076] The following performance tests were conducted on the γ-ray irradiation-resistant polycarbonate composite materials obtained in Comparative Example 1 and Comparative Examples 1-3: The samples were injection molded into 3mm color plates, irradiated with 30KGY of γ-rays, and the impact resistance and yellowing index were tested after 15 days. The test results are shown in Table 1.

[0077] Table 1

[0078] Weight / Components Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength before irradiation 67.31 67.35 67.42 67.29 Impact strength after irradiation 66.49 63.84 65.53 65.31 Yellowness index before irradiation -12.4 -11.9 -9.8 -12.1 Yellowness index after irradiation -4.5 -3.9 3.2 -1.3

[0079] As shown in Table 1:

[0080] Comparative Example 1, lacking a chain extender, experienced molecular chain breakage in the polycarbonate after irradiation, resulting in a slight decrease in mechanical properties. Comparative Example 2, lacking an antioxidant, exhibited severe yellowing during processing, which worsened after irradiation. Comparative Example 3, lacking a free radical stabilizer, resulted in severe yellowing before and after irradiation. The gamma-ray irradiation-resistant polycarbonate composite material prepared in the embodiments of this application has superior gamma-ray irradiation resistance.

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be covered within the scope of the claims and specification of the present invention.

Claims

1. A gamma radiation resistant polycarbonate composite material, characterized by, The gamma ray irradiation resistant polycarbonate composite material comprises the following raw materials by weight: polycarbonate resin 85-99 parts, free radical stabilizer 0.1-1.0 parts, antioxidant 0.1-1.0 parts, chain extender 0.1-1.0 parts, and auxiliary agent 0.01-5 parts.

2. The gamma radiation resistant polycarbonate composite of claim 1, wherein, The polycarbonate resin has a melt flow rate of 7-20 g / 10 min at 300℃, 1.2 kg.

3. The gamma radiation resistant polycarbonate composite of claim 1, wherein, The free radical stabilizer is selected from at least one of 2,5-di-tert-butyl hydroquinone, hydroquinone dibenzyl acid, and dibenzyl ketone.

4. The gamma radiation resistant polycarbonate composite of claim 1, wherein, The antioxidant is selected from at least one of antioxidant 1076, antioxidant 168, antioxidant 501, and antioxidant 608.

5. The gamma radiation resistant polycarbonate composite of claim 1, wherein, The chain extender is ADR4385 and / or ADR4368.

6. The gamma radiation resistant polycarbonate composite of claim 1, wherein, The auxiliary agent is selected from at least one of toner, lubricant, and toughening agent.

7. The gamma radiation resistant polycarbonate composite of claim 6, wherein, The lubricant is selected from at least one of pentaerythritol stearate, polyethylene wax, and silicone lubricant. The toughening agent is selected from at least one of substituted neoprene, substituted helical polypropylene, and cellulose.

8. A method of producing the γ-ray irradiation resistant polycarbonate composite material according to any one of claims 1 to 7, characterized by, The preparation method comprises the following steps: (a) mixing and dispersing the free radical stabilizer, antioxidant, chain extender, and auxiliary agent to obtain a premix; (b) respectively feeding the premix and PC particles into a twin-screw extruder through different loss-on-ignition scales for extrusion molding, and passing water vapor in the extrusion process to remove small molecules and impurities in the polycarbonate and auxiliary agent by devolatilization, thereby obtaining the gamma ray irradiation resistant polycarbonate composite material.

9. The production method according to claim 8, characterized by, The temperature of the twin-screw extruder is 220-280℃, and the rotation speed is 200-600 rpm.

10. Use of the gamma ray irradiation resistant polycarbonate composite material according to any one of claims 1-7 in the preparation of medical devices.