Medical antibacterial PC composite material and preparation method thereof

Abstract

The invention discloses a medical antibacterial PC composite material and a preparation method thereof, and belongs to the technical field of polymer composite material processing.The preparation method of the medical antibacterial PC composite material comprises the following steps that PC resin, ABS resin, bamboo powder, a compatilizer, an antioxidant and a lubricating agent are weighed by weight, fully dried in a blast drying oven and mixed on a high-speed mixer, and a mixture is obtained; and adding the mixture into a double-screw extruder for blending granulation, and drying to obtain the medical antibacterial PC composite material. The compatilizer contains a quaternary ammonium salt group, a bisphenol A chain segment and a polar chain segment. The medical antibacterial PC composite material prepared by the invention has excellent antibacterial property and mechanical property.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer composite material processing, and specifically relates to a medical antibacterial PC composite material and a preparation method thereof. Background Art

[0002] Polycarbonate (PC) resin is a thermoplastic engineering plastic with excellent performance. It has outstanding impact resistance, good creep resistance and dimensional stability, heat resistance and low water absorption. It is widely used in automobiles, electronics and electrical, construction, office equipment, packaging, sports equipment, medical care and other fields, but its flow characteristics are poor and the injection molding process is more difficult.

[0003] In the prior art, PC and ABS are usually compounded to make composite materials. PC / ABS composite materials inherit the characteristics of PC's high heat resistance, high impact and high dimensional stability as well as ABS's high flowability and low internal stress. They are a type of composite materials with excellent comprehensive properties. These properties are crucial for the manufacture of medical device housings because the housings need to protect the internal equipment from the external environment and accidental impacts.

[0004] During the use of medical devices, various bacteria, viruses and other microorganisms are easily attached to their surfaces. If the medical device itself does not have antibacterial properties, these microorganisms may multiply in large numbers and spread to patients through the medical device, causing cross-infection. Medical devices with antibacterial properties can effectively reduce the growth and spread of microorganisms on the surface of the device, thereby reducing the risk of infection. Therefore, it is necessary to prepare a medical antibacterial PC composite material.

[0005] Patent announcement number CN105419293B discloses an antibacterial PC / ABS alloy material and a preparation method thereof. The patent weighs ABS resin, bamboo powder, and compatibilizer by weight, adds them into a mixer extruder for mixing and granulation, and obtains a first mixture; then, the first mixture is stirred and mixed with PC resin, and then added into a twin-screw extruder for blending and granulation, and the target product is obtained. However, the medical antibacterial PC composite material prepared by the patent and the prior art still has the problem of poor antibacterial properties. Summary of the invention

[0006] In order to solve the problem that the medical antibacterial PC composite material prepared by the prior art still has poor antibacterial property, the object of the present invention is to provide a medical antibacterial PC composite material and a preparation method thereof.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] A medical antibacterial PC composite material comprises the following raw materials in parts by weight:

[0009] 50-70 parts of PC resin, 30-50 parts of ABS resin, 7-18 parts of bamboo powder, 0.5-2 parts of compatibilizer, 0.3-0.8 parts of antioxidant and 0.3-0.8 parts of lubricant; the compatibilizer contains quaternary ammonium salt group, bisphenol A chain segment and polar chain segment.

[0010] Furthermore, the molecular weight of the PC resin is 17000-30000 g / mol, and the glass transition temperature is 140-150°C.

[0011] Furthermore, the ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the butadiene content is 10-55wt%.

[0012] Furthermore, the preparation method of the compatibilizer is:

[0013] Bisphenol A glycidyl ether and (6-aminohexyl) trimethylammonium bromide hydrobromide were mixed, stirred evenly, vacuum degassed, and then poured into a standard sample mold. After preheating at 50°C for 30 minutes, the mixture was reacted at 100°C for 3 hours, and finally the temperature was raised to 120°C for post-treatment for 30 minutes, and the mixture was crushed to obtain a compatibilizer.

[0014] The mass ratio of bisphenol A glycidyl ether to (6-aminohexyl)trimethylammonium bromide hydrobromide is 9.6:34.2.

[0015] When bisphenol A glycidyl ether reacts with the primary amine of (6-aminohexyl)trimethylammonium bromide hydrobromide, one active hydrogen of the primary amine reacts with the epoxy group to generate a hydroxyl group and a secondary amine, and the secondary amine continues to react with another epoxy group to generate a hydroxyl group and a tertiary amine, ultimately forming a linear polymer.

[0016] Furthermore, the material of the bamboo powder is selected from one of moso bamboo and cycad bamboo, or a mixture of the two.

[0017] Furthermore, the antioxidant is one or a mixture of triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris(2,4-di-tert-butylphenyl) phosphite or dioctadecyl alcohol pentaerythritol diphosphite.

[0018] Furthermore, the lubricant is one or more of zinc stearate, calcium stearate, stearic acid amide, methylene bis stearic acid amide or N,N-ethylene bis stearic acid amide.

[0019] Furthermore, a method for preparing a medical antibacterial PC composite material comprises the following steps:

[0020] PC resin, ABS resin, bamboo powder, compatibilizer, antioxidant and lubricant are weighed in parts by weight, fully dried in a blast oven, mixed on a high-speed mixer, then added into a twin-screw extruder for blending and granulation, and dried to obtain a medical antibacterial PC composite material.

[0021] Furthermore, the rotation speed of the high-speed mixer is 800-1000 r / min, and the time is 20-30 min; the temperature of the twin-screw extruder is 230-270° C., and the screw rotation speed is 300-600 rpm.

[0022] Beneficial effects of the present invention:

[0023] 1. The present invention mixes bisphenol A glycidyl ether with (6-aminohexyl) trimethylammonium bromide hydrobromide to prepare a compatibilizer, which contains a quaternary ammonium salt group, a bisphenol A segment, and a polar segment, and has multiple effects. The quaternary ammonium salt group can form an intermediate of an ion pair with the hydroxyl group of the cellulose of the bamboo powder, thereby improving the dispersibility of the bamboo powder in the composite material, so that the bamboo powder can be more evenly distributed in the composite material, thereby improving the antibacterial property, and the quaternary ammonium salt group itself has antibacterial property, and the introduction of the quaternary ammonium salt group further improves the antibacterial property of the composite material. The bisphenol A chain segments in the compatibilizer and the bisphenol A chain segments in the PC resin have similar chemical structures, thereby improving the compatibility between the two. This close interaction helps to reduce interfacial defects in the composite material, thereby improving its overall mechanical properties; the polar segments are partially compatible with SAN (styrene-acrylonitrile copolymer) in the ABS resin, thereby enhancing the interaction between the compatibilizer and the ABS resin, further improving the overall performance of the composite material. Therefore, the compatibilizer can make the bamboo powder, PC resin, and ABS resin tightly combined, which helps to prevent interfacial separation or peeling when the composite material is subjected to force, thereby improving the mechanical properties of the medical antibacterial PC composite material.

[0024] 2. The present invention is conducive to the preparation of medical antibacterial PC composite materials with the best comprehensive performance by accurately controlling the amount of compatibilizer added. When the amount of compatibilizer added is too little, too little compatibilizer cannot effectively combine bamboo powder, PC resin and ABS resin tightly together. This will cause the composite material to easily undergo interface separation or peeling when subjected to force, thereby reducing its mechanical properties, and too little compatibilizer will lead to an insufficient number of quaternary ammonium salt groups, thereby limiting the antibacterial effect of the composite material; when the amount of compatibilizer added is too much, too much compatibilizer will cause the mechanical properties of the composite material to decrease, because too much compatibilizer will hinder the stress transfer inside the material, thereby reducing the overall strength of the material. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Preparation Example 1

[0027] The preparation method of the compatibilizer of this preparation example is:

[0028] Mix 9.6 g of bisphenol A glycidyl ether and 34.2 g of (6-aminohexyl) trimethylammonium bromide hydrobromide, stir evenly, degas in vacuum, and then pour into a standard sample mold. Preheat at 50°C for 30 minutes, react at 100°C for 3 hours, and finally heat to 120°C for post-treatment for 30 minutes, and crush to obtain a compatibilizer.

[0029] Preparation Example 2

[0030] This preparation example is different from preparation example 1 in that "34.2 g (6-aminohexyl) trimethylammonium bromide hydrobromide" in preparation example 1 is replaced by "6.5 g ethanolamine", and the remaining raw materials, processes and parameters are the same as those in preparation example 1.

[0031] Example 1

[0032] This embodiment provides a medical antibacterial PC composite material, including the following raw materials in parts by weight:

[0033] 70 parts of PC resin, 50 parts of ABS resin, 7 parts of bamboo powder, 0.5 parts of the compatibilizer prepared in Preparation Example 1, 0.8 parts of triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], and 0.8 parts of zinc stearate.

[0034] The molecular weight of PC resin is 17000 g / mol and its glass transition temperature is 140°C.

[0035] ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the butadiene content is 10-55wt%.

[0036] The preparation method of the medical antibacterial PC composite material is as follows:

[0037] PC resin, ABS resin, bamboo powder, compatibilizer, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], and zinc stearate were weighed by weight and fully dried in a blast oven, mixed on a high-speed mixer, and then added to a twin-screw extruder for blending and granulation, and dried to obtain a medical antibacterial PC composite material. The speed of the high-speed mixer is 800r / min, the time is 20min; the temperature of the twin-screw extruder is 230℃, and the screw speed is 300rpm.

[0038] Example 2

[0039] This embodiment provides a medical antibacterial PC composite material, including the following raw materials in parts by weight:

[0040] 60 parts of PC resin, 40 parts of ABS resin, 13 parts of bamboo powder, 1.25 parts of the compatibilizer prepared in Preparation Example 1, 0.25 parts of tris(2,4-di-tert-butylphenyl)phosphite or dioctadecyl alcohol pentaerythritol diphosphite, 0.25 parts of tetrakis[β-(3,5-di-tert-butyl 4-hydroxyphenyl) propionate] pentaerythritol ester, and 0.5 parts of stearic acid amide.

[0041] The molecular weight of PC resin is 23000 g / mol and its glass transition temperature is 145°C.

[0042] ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the butadiene content is 55wt%.

[0043] The preparation method of the medical antibacterial PC composite material is as follows:

[0044] PC resin, ABS resin, bamboo powder, compatibilizer, tris(2,4-di-tert-butylphenyl)phosphite or dioctadecyl alcohol pentaerythritol diphosphite, tetrakis[β-(3,5-di-tert-butyl 4-hydroxyphenyl) propionate] pentaerythritol ester, stearic acid amide were weighed by weight, fully dried in a blast oven, mixed on a high-speed mixer, and then added to a twin-screw extruder for blending and granulation, and dried to obtain a medical antibacterial PC composite material. The speed of the high-speed mixer is 900r / min, the time is 25min; the temperature of the twin-screw extruder is 250℃, and the screw speed is 450rpm.

[0045] Example 3

[0046] This embodiment provides a medical antibacterial PC composite material, including the following raw materials in parts by weight:

[0047] 50 parts of PC resin, 30 parts of ABS resin, 18 parts of bamboo powder, 2 parts of the compatibilizer prepared in Preparation Example 1, 0.3 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl 4-hydroxyphenyl) propionate, and 0.3 parts of N,N-ethylene bisstearamide.

[0048] The molecular weight of PC resin is 30,000 g / mol and its glass transition temperature is 150°C.

[0049] ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the butadiene content is 35wt%.

[0050] The preparation method of the medical antibacterial PC composite material is as follows:

[0051] PC resin, ABS resin, bamboo powder, compatibilizer, pentaerythritol tetra[β-(3,5-di-tert-butyl 4-hydroxyphenyl) propionate], and N,N-ethylene bisstearic acid amide were weighed by weight and fully dried in a blast oven, mixed on a high-speed mixer, and then added to a twin-screw extruder for blending and granulation, and dried to obtain a medical antibacterial PC composite material. The speed of the high-speed mixer is 1000r / min, the time is 30min; the temperature of the twin-screw extruder is 270℃, and the screw speed is 600rpm.

[0052] Comparative Example 1

[0053] A medical antibacterial PC composite material, compared with Example 1, the difference is that the compatibilizer in Example 1 is replaced by the product prepared in Preparation Example 2, and the other raw materials, processes and parameters are the same as Example 1.

[0054] Comparative Example 2

[0055] A medical antibacterial PC composite material, compared with Example 1, the difference is that the compatibilizer in Example 1 is replaced by SAN-g-GMA copolymer, and the other raw materials, processes and parameters are the same as Example 1.

[0056] Comparative Example 3

[0057] A medical antibacterial PC composite material, compared with Example 1, is different in that the compatibilizer in Example 1 is replaced by SAN-g-MAH copolymer, and the other raw materials, processes and parameters are the same as Example 1.

[0058] Comparative Example 4

[0059] A medical antibacterial PC composite material, compared with Example 1, the difference is that "0.5 parts of compatibilizer" in Example 1 is replaced by "0.4 parts of compatibilizer", and the other raw materials, processes and parameters are the same as Example 1.

[0060] Comparative Example 5

[0061] A medical antibacterial PC composite material, compared with Example 3, the difference is that "2 parts of compatibilizer" in Example 3 is replaced by "2.1 parts of compatibilizer", and the other raw materials, processes and parameters are the same as Example 3.

[0062] The medical antibacterial PC composite materials prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were subjected to antibacterial performance tests and mechanical performance tests. The antibacterial performance tests were conducted in accordance with the GB / T20944.2-2007 method. The antibacterial performance and mechanical performance test results are shown in Table 1:

[0063] Table 1

[0064]

[0065]

[0066] It can be seen from Table 1 that the antibacterial properties and mechanical properties of the medical antibacterial PC composite materials prepared in Examples 1 to 3 are better than those in Comparative Examples 1 to 5. Comparative Example 1 does not contain quaternary ammonium salt groups, which have antibacterial properties and can be combined with bamboo powder, so the antibacterial properties and mechanical properties of Comparative Example 1 are reduced; the MAH group or GMA group at one end of the compatibilizer of Comparative Example 2 and Comparative Example 3 can react with polar functional groups such as hydroxyl groups on the surface of bamboo powder, and the SAN group at the other end can be compatible with ABS resin, but the compatibilizers of Comparative Example 2 and Comparative Example 3 cannot be compatible with PC resin and do not contain quaternary ammonium salt groups, and their antibacterial properties and mechanical properties are lower than those of Example 1; Comparative Example 4 adds too little compatibilizer, and too little compatibilizer cannot effectively combine bamboo powder, PC resin and ABS resin tightly together, which will cause the composite material to easily undergo interface separation or peeling when subjected to force, thereby reducing its mechanical properties, and too little compatibilizer leads to insufficient number of quaternary ammonium salt groups, thereby limiting the antibacterial effect of the composite material; Comparative Example 5 adds too much compatibilizer, and too much compatibilizer will cause the mechanical properties of the composite material to decrease, because too much compatibilizer will hinder the stress transfer inside the material, thereby reducing the overall strength of the material.

[0067] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0068] 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 medical antibacterial PC composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 50-70 parts of PC resin, 30-50 parts of ABS resin, 7-18 parts of bamboo powder, 0.5-2 parts of compatibilizer, 0.3-0.8 parts of antioxidant and 0.3-0.8 parts of lubricant; the compatibilizer contains quaternary ammonium salt group, bisphenol A chain segment and polar chain segment.

2. The medical antibacterial PC composite material according to claim 1, characterized in that: The molecular weight of PC resin is 17000-30000 g / mol, and the glass transition temperature is 140-150°C.

3. The medical antibacterial PC composite material according to claim 1, characterized in that: ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the butadiene content is 10-55wt%.

4. The medical antibacterial PC composite material according to claim 1, characterized in that: The preparation method of the compatibilizer is: Bisphenol A glycidyl ether and (6-aminohexyl) trimethylammonium bromide hydrobromide were mixed, stirred evenly, vacuum degassed, and then poured into a mold. After preheating at 50° C. for 30 minutes, the mixture was reacted at 100° C. for 3 hours, and finally the mixture was heated to 120° C. for post-treatment for 30 minutes, and crushed to obtain a compatibilizer.

5. The medical antibacterial PC composite material according to claim 4, characterized in that: The mass ratio of bisphenol A glycidyl ether to (6-aminohexyl)trimethylammonium bromide hydrobromide is 9.6:34.

2.

6. The medical antibacterial PC composite material according to claim 1, characterized in that: The material of bamboo powder is selected from one of moso bamboo and cycad bamboo or a mixture of the two.

7. The medical antibacterial PC composite material according to claim 1, characterized in that: The antioxidant is one of triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris(2,4-di-tert-butylphenyl) phosphite or dioctadecyl alcohol pentaerythritol diphosphite or a mixture of several thereof.

8. The medical antibacterial PC composite material according to claim 1, characterized in that: The lubricant is one or more of zinc stearate, calcium stearate, stearic acid amide, methylene bis stearic acid amide or N,N-ethylene bis stearic acid amide.

9. A method for preparing a medical antibacterial PC composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: PC resin, ABS resin, bamboo powder, compatibilizer, antioxidant and lubricant are weighed in parts by weight, fully dried in a blast oven, mixed on a high-speed mixer, then added into a twin-screw extruder for blending and granulation, and dried to obtain a medical antibacterial PC composite material.

10. The method for preparing a medical antibacterial PC composite material according to claim 9, characterized in that: The speed of the high-speed mixer is 800-1000r / min, and the time is 20-30min; the temperature of the twin-screw extruder is 230-270°C, and the screw speed is 300-600rpm.

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