A polycarbonate composition, its preparation and use

Abstract

The application discloses a polycarbonate composition and a preparation method and application thereof. The polycarbonate composition comprises the following components in parts by weight: polycarbonate 45-72 parts; siloxane polycarbonate 30-55 parts; triazine ultraviolet light absorber 1-3 parts; phthalocyanine green 0.05-1 part; and crosslinked styrene-acrylonitrile copolymer 0.3-2 parts. The polycarbonate composition of the application introduces siloxane polycarbonate and triazine ultraviolet light absorber in the system, and on the basis of optimizing the light rearrangement reaction of the PC matrix, by adding a certain amount of phthalocyanine green and crosslinked styrene-acrylonitrile copolymer, high transparency is realized, and the UVC irradiation resistance and chemical resistance are significantly improved, the color difference changes little after long-term contact with a disinfectant or repeated UVC irradiation disinfection, excellent color stability and mechanical property stability are exhibited, and the use requirements of medical devices which need to be frequently treated by a disinfectant or ultraviolet irradiation disinfection can be met.

Description

Technical Field

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

[0002] Polycarbonate (PC), as an engineering plastic with excellent comprehensive properties, is widely used in electronics, automobiles, construction, and medical equipment due to its high strength, high transparency, good heat resistance, and processing performance. Especially in the medical device industry, PC is the preferred material for equipment requiring transparent and easily visible operation (such as artificial kidney hemodialysis equipment and artificial organs). However, medical devices often require frequent disinfection by disinfectants (such as quaternary ammonium salts and hydrogen peroxide) or ultraviolet (UVC band, 200-280 nm) irradiation. Traditional polycarbonate materials are prone to yellowing after prolonged contact with disinfectants or repeated UVC irradiation, leading to decreased transparency and significant deterioration of mechanical properties. This defect severely limits the long-term reliable application of traditional polycarbonate materials in scenarios requiring frequent disinfection.

[0003] Current technologies for radiation-stabilized modification of materials mainly involve adding ultraviolet absorbers, light stabilizers, or antioxidants. However, these conventional stabilization methods primarily target the UVB and part of the UVA bands in sunlight, offering limited protection against the higher-energy UVC band. They often fail to effectively suppress yellowing and performance degradation caused by UVC, and do not significantly improve the material's chemical resistance.

[0004] Therefore, developing a polycarbonate material that can simultaneously achieve excellent resistance to UVC radiation and chemical resistance is of great significance for broadening the application of polycarbonate materials in the field of medical devices. Summary of the Invention

[0005] To overcome the shortcomings of the existing technology, the present invention aims to provide a polycarbonate material that simultaneously possesses resistance to UVC radiation and chemical resistance, exhibiting minimal color difference after long-term contact with disinfectants or repeated UVC radiation, thus demonstrating excellent color stability and mechanical property stability.

[0006] This invention is achieved through the following technical solution:

[0007] In a first aspect, the present invention provides a polycarbonate composition, characterized in that it comprises, by weight parts, the following components:

[0008] 45-72 parts polycarbonate;

[0009] 30-55 parts of siloxane polycarbonate;

[0010] 1-3 parts of triazine ultraviolet absorber;

[0011] Phthalocyanine green 0.05-1 part;

[0012] 0.3-2 parts of cross-linked styrene-acrylonitrile copolymer.

[0013] The polycarbonate may be in parts by weight of 45, 50, 55, 60, 65 or 72, or specific parts between the above values.

[0014] Preferably, the number average molecular weight of the polycarbonate is 18,000-32,000.

[0015] The polycarbonate composition contains ≥40% polycarbonate by weight, preferably 50%-60%.

[0016] The weight percentage of the siloxane polycarbonate can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 55 parts, as well as specific values ​​between the above-mentioned values.

[0017] Preferably, the silicon content of the siloxane polycarbonate is 6%-10%. The silicon content is determined by nuclear magnetic resonance (NMR): the copolymer's silicon content is determined using NMR. 1 The silicon content was calculated by comparing the integral ratio of the peaks from bisphenol compounds (I) with the integral ratio of the peaks from phenolic hydroxyl-terminated polysiloxanes (II) in the 1H-NMR spectrum.

[0018] Preferably, the triazine ultraviolet absorber is selected from at least one of the hydroxyphenyltriazines. Further, the triazine-based ultraviolet absorber is selected from at least one of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(octyl)phenol, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-5-tert-octylphenyl)-1,3,5-triazine, and 2-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol.

[0019] Preferably, the polycarbonate composition contains 0.1%-0.8% phthalocyanine green by mass.

[0020] Preferably, the degree of crosslinking of the crosslinked styrene-acrylonitrile copolymer is 45%-80%. The degree of crosslinking is measured by the swelling equilibrium method.

[0021] Furthermore, the polycarbonate composition further comprises, by weight, 0.02-0.4 parts of hindered phenolic antioxidant.

[0022] Preferably, the hindered phenolic antioxidant is selected from at least one of monophenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and thiobisphenolic antioxidants.

[0023] The monophenolic antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and hexadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; the bisphenolic antioxidant is selected from at least one of 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), and 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol); the polyphenolic antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris( ... At least one of the following: (-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane; and at least one of the following thiobisphenol antioxidants: 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(2-tert-butyl-5-methylphenol), and 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0024] Secondly, the present invention provides a method for preparing the polycarbonate composition, comprising the following steps: mixing the components according to the proportion to obtain a premix, then feeding the obtained premix into a twin-screw extruder for melt mixing, and extruding and granulating to prepare the polycarbonate composition; wherein the length-to-diameter ratio of the twin-screw extruder is 40:1-48:1; the temperature of the twin-screw extruder is set to 230-300℃, and the screw speed is 300-500 rpm.

[0025] Preferably, the temperatures of the twin-screw extruder are set as follows: 230~280℃ for the first section of the barrel, 240~290℃ for the second section, 240~300℃ for the third section, 240~300℃ for the fourth section, 240~300℃ for the fifth section, 240~300℃ for the sixth section, 240~300℃ for the seventh section, 240~300℃ for the eighth section, 240~300℃ for the ninth section, and 240~300℃ for the tenth section.

[0026] Thirdly, the present invention also provides the use of the polycarbonate composition in the preparation of medical device components.

[0027] Fourthly, the present invention provides a transparent component comprising the polycarbonate composition described herein. The transparent component is a medical device component. Specifically, it can be a transparent component for an artificial kidney hemodialysis device, an artificial organ, etc.

[0028] The present invention has the following beneficial effects:

[0029] The polycarbonate composition of the present invention, based on the optimization of stabilizing the photorearrangement reaction of the PC matrix by introducing siloxane polycarbonate and triazine UV absorbers into the system, achieves high transparency while significantly improving UVC irradiation resistance and chemical resistance by adding a certain amount of phthalocyanine green and crosslinked styrene-acrylonitrile copolymer. It exhibits excellent color stability and mechanical property stability after long-term contact with disinfectants or repeated UVC irradiation, and can meet the usage requirements of medical devices that need to be frequently disinfected by disinfectants or ultraviolet irradiation. Detailed Implementation

[0030] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0031] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0032] The materials used in the embodiments and comparative examples of this invention are described below, but are not limited to these materials.

[0033] Polycarbonate: Number average molecular weight 23,000, PC2100, Wanhua Chemical;

[0034] Siloxane polycarbonate 1: Silicon content is 6%, PC ST4-3022PJ(3), Samyang, South Korea;

[0035] Siloxane polycarbonate 2: Silicon content is 8%; Grade PC8010-10, LG Korea;

[0036] Triazine UV absorber 1: 2-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol, TNUVIN 1600, BASF;

[0037] Triazine UV absorber 2: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, TNUVIN 1577, BASF;

[0038] UV absorber 3: 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, TNUVIN 234, BASF;

[0039] Phthalocyanine Green 1: K8730, BASF;

[0040] Phthalocyanine Green 2: GNX, Clariant;

[0041] Phthalocyanine Blue: BF1535, Steli;

[0042] Azo Green: Pigment Green 7, Beijing Bailingwei Technology;

[0043] Chromium oxide green: PG17, Shanghai Juli Chemical Co., Ltd.

[0044] Crosslinked styrene-acrylonitrile copolymer 1: AM-08, Hannano; crosslinking degree is 50%;

[0045] Crosslinked styrene-acrylonitrile copolymer 2: INPBMAT-1000, SABIC-based; crosslinking degree 60%;

[0046] Non-crosslinked styrene-acrylonitrile copolymer: SAN 350 N, Kumho Sunrise;

[0047] Hindered phenolic antioxidant: β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester, commercially available.

[0048] Preparation method of polycarbonate compositions in examples and comparative examples: According to the proportions in Table 1 or Table 2, the raw materials are mixed evenly in a high-speed mixer to obtain a premix. The obtained premix is ​​then fed into a twin-screw extruder for melt mixing and extrusion granulation to prepare a polycarbonate composition. The twin-screw extruder has an aspect ratio of 48:1. The twin-screw extruder temperatures are set as follows: first section barrel temperature 240℃, second section barrel temperature 250℃, third section barrel temperature 250℃, fourth section barrel temperature 250℃, fifth section barrel temperature 270℃, sixth section barrel temperature 270℃, seventh section barrel temperature 270℃, eighth section barrel temperature 270℃, ninth section barrel temperature 280℃, and tenth section barrel temperature 280℃. The screw speed is 500 rpm.

[0049] Relevant performance testing methods:

[0050] 1. Transparency: The light transmittance of a 1.5mm thick color sample was tested using an optical transmittance meter.

[0051] 2. UVC irradiation resistance test:

[0052] Irradiation conditions: In accordance with ASTM F 997-2003, the UVC lamp wavelength is 252 nm, the irradiation time is 48 h, and the irradiation intensity is 50 W;

[0053] (1) Color stability test: For the 2mm thick color sample, the L*, a*, and b* values ​​of the color sample were tested by the Datacolor1050 spectrophotometer (D65 light source). After UVC irradiation, the L*, a*, and b* values ​​of the color sample were tested again. For transparent materials, white paper was placed at the bottom of the color sample to eliminate the influence. The ΔE value was calculated by the color difference calculation formula. Three points were tested at different positions on the color sample, and the corresponding test values ​​were recorded. The final result was obtained by calculating the average value. The color difference value ΔE is shown in Table 1 or Table 2. The smaller the color difference value ΔE, the higher the color stability of the material.

[0054] (2) Mechanical property stability test:

[0055] The notched impact strength of the specimens before and after irradiation was tested according to ASTM D256-2010 standard, using a ASTM A-type notched impact specimen with a thickness of 3.2 mm; the notched impact strength retention rate after irradiation was calculated.

[0056] 3. Chemical resistance test: The sample prepared according to ISO-527 standard is clamped to maintain a curvature of 0.5%, and then wrapped with a reagent (disacyldimethylammonium chloride and hydrogen peroxide in a mass ratio of 1:1) for 200 hours. The surface condition of the sample is then observed.

[0057] Table 1: Distribution ratios (by weight) and performance test results for each group in Examples 1-5

[0058] Example 1 Example 2 Example 3 Example 4 Example 5 polycarbonate 60 45 70 60 60 Siloxane polycarbonate 1 40 35 40 40 Siloxane polycarbonate 2 52 Triazine UV absorbers 1 2 1 2 2 Triazine UV absorbers 2 3 Phthalocyanine Green 1 0.4 1 0.4 0.4 Phthalocyanine Green 2 0.1 Crosslinked styrene-acrylonitrile copolymer 1 1 0.3 2 1 Crosslinked styrene-acrylonitrile copolymer 2 1 Hindered phenolic antioxidants 1 0.2 0.4 0.1 / 0.2 transmittance % 83 85 82 81 81 Color difference value ΔE after irradiation 4.5 6.2 7.6 5.9 5.2 Notched impact strength J / m 857 817 805 798 815 Notched impact strength retention rate after irradiation / % 89 82 79 80 85 Chemical resistance test results No cracks No cracks No cracks No cracks No cracks

[0059] Table 2: Distribution ratios (by weight) and performance test results for each group in Comparative Examples 1-10

[0060] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 polycarbonate 60 60 60 60 60 60 60 60 100 60 Siloxane polycarbonate 1 40 40 40 40 40 40 40 40 / 40 Triazine UV absorbers 1 2 2 2 2 2 2 2 2 2 UV absorber 3 2 Phthalocyanine Green 1 / 3 0.4 0.4 0.4 0.4 0.4 Phthalocyanine Blue 0.4 Azo Green 0.4 Chromium oxide green 0.4 Crosslinked styrene-acrylonitrile copolymer 1 1 1 1 1 1 / 5 1 1 Non-crosslinked SAN 1 Hindered phenolic antioxidants 1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 transmittance % 81 79 75 81 48 87 38 85 85 84 Color difference value ΔE after irradiation 10.9 11.8 6.8 12.5 6.5 6.5 5.9 8.5 7.1 7.5 Notched impact strength J / m 805 795 758 785 685 851 375 795 755 718 Notched impact strength retention rate after irradiation / % 75 72 68 59 75 69 80 75 42 41 Chemical resistance test results No cracks No cracks No cracks No cracks Cracks Cracks Cracks Cracks Cracks Cracks

[0061] As can be seen from the above results, the polycarbonate composition of the present invention, by introducing siloxane polycarbonate and triazine ultraviolet absorber into the system, and adding a certain amount of phthalocyanine green and crosslinked styrene-acrylonitrile copolymer, achieves high transparency while significantly improving UVC irradiation resistance and chemical resistance. After long-term contact with disinfectants or repeated UVC irradiation, the color difference changes little, exhibiting excellent color stability and mechanical property stability, which can meet the usage requirements of medical devices that need to be frequently disinfected by disinfectants or ultraviolet irradiation.

[0062] The above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A polycarbonate composition, characterized in that, By weight, it includes the following components: 45-72 parts polycarbonate; 30-55 parts of siloxane polycarbonate; 1-3 parts of triazine ultraviolet absorber; Phthalocyanine green 0.05-1 part; 0.3-2 parts of cross-linked styrene-acrylonitrile copolymer.

2. The polycarbonate composition according to claim 1, characterized in that, The polycarbonate has a number average molecular weight of 18,000-32,000.

3. The polycarbonate composition according to claim 1, characterized in that, The silicon content of the siloxane polycarbonate is 6%-10%.

4. The polycarbonate composition according to claim 1, characterized in that, The triazine ultraviolet absorber is selected from at least one of the hydroxyphenyltriazine class.

5. The polycarbonate composition according to claim 1, characterized in that, The polycarbonate composition contains 0.1%-0.8% phthalocyanine green by mass.

6. The polycarbonate composition according to claim 1, characterized in that, The degree of crosslinking of the crosslinked styrene-acrylonitrile copolymer is 45%-80%.

7. The polycarbonate composition according to claim 1, characterized in that, The product also includes 0.02-0.4 parts by weight of hindered phenolic antioxidants; the hindered phenolic antioxidants are selected from at least one of monophenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and thiobisphenolic antioxidants.

8. A method for preparing a polycarbonate composition according to any one of claims 1-7, characterized in that, Includes the following steps: The components are stirred and mixed according to the formula to obtain a premix. The premix is ​​then fed into a twin-screw extruder for melt mixing and extrusion granulation to prepare a polycarbonate composition.

9. A transparent component, characterized in that, Includes the polycarbonate composition according to any one of claims 1-7.