Antibacterial polyketone material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of antibacterial high polymer materials, in particular to an antibacterial polyketone material as well as a preparation method and application thereof. The antibacterial polyketone material provided by the invention has good mechanical properties, efficient and long-acting antibacterial properties and ultraviolet degradation resistance. Experiments show that the antibacterial polyketone material provided by the invention has the antibacterial rate of 98.2% on escherichia coli and the antibacterial rate of 99.1% on staphylococcus aureus, and the elongation at break is still maintained at 334% or above after 300 hours of ultraviolet irradiation. The antibacterial polyketone material prepared by the method can be used for antibacterial products such as medical antibacterial tools such as medical trays or food packaging boxes, and food production packaging products such as conveying chain plates in the slaughter industry.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial polymer materials, in particular to an antibacterial polyketone material and a preparation method and application thereof. Background Art

[0002] Polyketone (POK) is a copolymer obtained by alternating copolymerization of carbon monoxide with ethylene, propylene and other olefinic unsaturated hydrocarbons. In addition to being obtained from coal gasification, CO can also be obtained from CO-containing industrial waste gas through purification. It is a green polymer material with excellent comprehensive performance. In terms of performance, polyketone surpasses many traditional engineering plastics, including high mechanical property retention, excellent impact strength, excellent chemical stability, high wear resistance, excellent gas barrier properties, reliable flame retardant properties, extremely low water absorption and hydrolysis stability. These advantages make it an ideal substitute for materials such as PA (polyamide), POM (polyoxymethylene), PBT (polybutylene terephthalate), EVOH (ethylene-vinyl alcohol copolymer), etc., and significantly promote the green transformation of the materials industry.

[0003] Bacterial infection has become one of the biggest health problems facing mankind today, and it has affected all aspects of human production and life, including water purification systems, textiles, food packaging and storage, medicines, sanitary applications, medical devices, etc. With the improvement of people's living standards and the enhancement of health awareness, antibacterial polymer materials are receiving more and more attention. The high wear resistance, chemical corrosion resistance, excellent gas barrier properties and extremely low water absorption of polyketone make polyketone very suitable for use in medical tools or in the catering industry where food or water is in contact. However, its products have no antibacterial properties, and bacteria are easily bred on the surface, causing diseases to the human body, so the research and development of antibacterial polyketone materials has great practical application significance.

[0004] Antimicrobial agents can be divided into three categories according to their composition, namely organic antimicrobial agents, inorganic antimicrobial agents and natural polymer antimicrobial agents. The use environment and scope of each antimicrobial agent are also different, and each has its own advantages and disadvantages. For example, organic antimicrobial agents have strong initial bactericidal power, good broad-spectrum antimicrobial properties, and good dispersibility, but a short effective period; inorganic antimicrobial agents have high antimicrobial properties and safety, good heat resistance, a wide antimicrobial range, and a long effective period, but they are easy to change color, easy to precipitate, unevenly dispersed, and have a high price; natural polymer antimicrobial agents generally do not cause pollution hazards to humans, animals, or the environment, and have good biocompatibility, but the antimicrobial effect is limited and the antimicrobial long-term effect is poor.

[0005] In addition, in the field of medical hygiene, medical tools often need to be disinfected with ultraviolet light. Ordinary polyketone materials are prone to aging during long-term irradiation, which affects their mechanical properties and limits the application of polyketone as a medical antibacterial material. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide an antibacterial polyketone material and a preparation method and application thereof. The antibacterial polyketone material provided by the present invention has good mechanical properties, high-efficiency and long-lasting antibacterial properties and resistance to ultraviolet degradation.

[0007] The present invention provides an antibacterial polyketone material, which is obtained from the following raw materials in terms of mass percentage:

[0008] 80-90 wt% polyketone;

[0009] 4-18 wt% of an antibacterial agent, wherein the antibacterial agent comprises an inorganic antibacterial agent and an organic antibacterial agent, wherein the inorganic antibacterial agent is selected from one or more of nanosilver, nano-TiO2 and nano-ZnO, and the organic antibacterial agent is selected from one or more of chitosan, tea polyphenols, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts and biguanides;

[0010] 3-9 wt% of a coupling agent, wherein the coupling agent is selected from one or more of a silane coupling agent and a titanate coupling agent;

[0011] 0.3~1.2 wt% of UV absorber;

[0012] 0.5~2 wt% of hindered phenol antioxidant;

[0013] 0.2~1.5 wt% of phosphite antioxidant.

[0014] Preferably, it is obtained from the following raw materials:

[0015] 85-90 wt% polyketone;

[0016] 4-13 wt% antimicrobial agent;

[0017] 4~6 wt% coupling agent;

[0018] 0.8~1.0 wt% of UV absorber;

[0019] 0.8~1.5 wt% of hindered phenol antioxidant;

[0020] 0.2~1.0 wt% of phosphite antioxidant.

[0021] The raw material of the present invention is based on polyketone, and the mass percentage of the polyketone in the raw material is 80-90wt%, preferably 85-90wt%. When the mass percentage of the polyketone drops below 80%, the mechanical properties of the obtained antibacterial material are reduced. The melt mass flow rate (melt index) of the polyketone of the present invention at 240°C and 2.16 kg load is 3-100 g / 10mins, preferably 5-80 g / 10mins; if the melt index of the polyketone is lower than 3 g / 10mins, its processability is reduced; if the melt index of the polyketone is higher than 100 g / 10mins, the mechanical properties may be reduced. In certain embodiments of the present invention, the polyketone is a terpolymer of carbon monoxide, ethylene and propylene, wherein the insertion rate of propylene is 5%-8%, preferably 6%-7.5%. The number average molecular weight of the polyketone measured by gel permeation chromatography is 1000-200000, preferably 30000-100000; the molecular weight distribution of the polyketone is 1-3, preferably 1.5-2.

[0022] The raw material of the present invention includes an antibacterial agent, and the mass percentage of the antibacterial agent in the raw material is 4-18 wt%, preferably 4-13 wt%. The antibacterial agent of the present invention includes an inorganic antibacterial agent and an organic antibacterial agent, and by utilizing the synergistic effect of the two antibacterial agents, a broad-spectrum and efficient bactericidal effect can be achieved. The mass ratio of the inorganic antibacterial agent to the organic antibacterial agent of the present invention is (1-3): (1-3), preferably (1-2): (1-2).

[0023] The inorganic antibacterial agent of the present invention is selected from one or more of nano silver, nano TiO2 and nano ZnO. The particle size of the inorganic antibacterial agent is 10-300 nm. If the particle size of the inorganic antibacterial agent is too large, the compatibility of the system will be reduced, and the partial dissolution of the nano solid particles in the system may be caused, so that the appearance smoothness and antibacterial property of the polyketone are reduced.

[0024] The organic antibacterial agent of the present invention is selected from one or more of chitosan, tea polyphenols, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts and biguanides. Among them, the quaternary ammonium salts include dodecyl dimethyl benzyl ammonium chloride and dodecyl dimethyl benzyl ammonium bromide; the quaternary phosphonium salts include p-vinyl benzyl tributyl phosphonium chloride, triphenyl quaternary phosphonium salt and derivatives of triphenyl quaternary phosphonium salt; the imidazolium salts include IBN-1, PIM-45, etc.; the biguanides include chlorhexidine and polyhexamethylene biguanide hydrochloride, etc. This type of bactericide relies on Coulomb force to adsorb to the surface of negatively charged bacteria, diffuses through the cell wall, combines with the cytoplasmic membrane to rupture it, and the bacteria die due to the release of the contents.

[0025] The raw material of the present invention includes an ultraviolet light absorber, and the mass percentage of the ultraviolet light absorber in the raw material is 0.3-1.2 wt%, preferably 0.8-1.0 wt%, and more preferably 1.0 wt%. The ultraviolet light absorber of the present invention is selected from one or more of 2-hydroxy-4-n-octyloxybenzophenone and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole. The ketone carbonyl group on the polyketone main chain makes it easy to age under the irradiation of ultraviolet light, and the ultraviolet light absorber molecule contains a conjugated π electron system and an o-hydroxyphenyl substituent, and the hydroxyl group and the nitrogen atom form a chelate ring, and this chelate structure, after absorbing ultraviolet light, the molecular structure thermal vibration destroys the hydrogen bond, and the chelate ring opens and converts ultraviolet light into heat energy to release, so as to protect the material structure and its performance.

[0026] The raw materials of the present invention include hindered phenol antioxidants and phosphite antioxidants, wherein the hindered phenol antioxidants play the role of a primary antioxidant, and the phosphite antioxidants play the role of an auxiliary antioxidant. The mass percentage of the hindered phenol antioxidants in the raw materials of the present invention is 0.5-2 wt%, preferably 0.8-1.5 wt%, and more preferably 1 wt%. In certain embodiments of the present invention, the hindered phenol antioxidant is selected from one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 2,6-di-tert-butyl-4-methylphenol, antioxidant 1010 and antioxidant 1076. The mass percentage of the phosphite antioxidants in the raw materials of the present invention is 0.2-1.5 wt%, preferably 0.2-1.0 wt%, and more preferably 0.5 wt%. In certain embodiments of the present invention, the phosphite antioxidant is selected from one or more of antioxidant 168, antioxidant 626, antioxidant 454 and triphenyl phosphite.

[0027] The raw material of the present invention further comprises a coupling agent, and the mass percentage of the coupling agent in the raw material is 3-9 wt%, preferably 4-6 wt%, and more preferably 4 wt%. The coupling agent of the present invention is selected from one or more of silane coupling agents and titanate coupling agents. In certain embodiments of the present invention, the coupling agent is selected from one or more of silane coupling agents KH550 and silane coupling agents KH560.

[0028] In some embodiments of the present invention, the antibacterial polyketone material is obtained from the following raw materials in terms of mass percentage:

[0029] 85-90 wt% polyketone;

[0030] 4-13 wt% of an antibacterial agent, wherein the antibacterial agent is nano ZnO and dodecyl dimethyl benzyl ammonium chloride, or the antibacterial agent is nano TiO2 and dodecyl dimethyl benzyl ammonium chloride, or the antibacterial agent is nano Ag and dodecyl dimethyl benzyl ammonium chloride, or the antibacterial agent is nano ZnO and p-vinylbenzyl tributyl phosphine chloride;

[0031] 4~6 wt% of silane coupling agent KH560;

[0032] 0.8-1.0 wt% of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0033] 0.8-1.5 wt% of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid;

[0034] 0.2~1.0 wt% of antioxidant 168.

[0035] The present invention also provides a method for preparing the antibacterial polyketone material described in any of the above technical solutions, comprising the following steps:

[0036] The polyketone, the ultraviolet absorber, the antibacterial agent, the hindered phenol antioxidant, the phosphite antioxidant and the coupling agent are melt-blended and then injection-molded to obtain the antibacterial polyketone material.

[0037] Specifically, the present invention first mixes polyketone, ultraviolet light absorber, antibacterial agent, hindered phenol antioxidant, phosphite antioxidant and coupling agent, and the mixing is carried out at a rotation speed of 100-400 r / min, and the mixing time is 10-30 minutes. Preferably, the mixing is carried out at a rotation speed of 250-350 r / min, and the mixing time is 20 minutes. In one embodiment of the present invention, the mixing is carried out under a high-speed stirrer. The polyketone, ultraviolet light absorber, antibacterial agent, hindered phenol antioxidant, phosphite antioxidant and coupling agent of the present invention are the same as above, and will not be repeated.

[0038] The present invention mixes polyketone, ultraviolet absorber, antibacterial agent, hindered phenol antioxidant, phosphite antioxidant and coupling agent, melt blends the obtained material, and injection molds the melt blended material to obtain an antibacterial polyketone material. The temperature of the melt blending of the present invention is 190°C~270°C, preferably 200°C~230°C, and more preferably 200°C~223°C. In some embodiments of the present invention, the obtained material is melt blended in a twin-screw extruder, and each heating section of the melt blending section is independently 190°C~270°C, preferably 200°C~230°C, and more preferably 200°C~223°C; the main engine screw speed is 200~400 r / min, preferably 300 r / min; the main feeding screw machine speed is 10~30 r / min, preferably 18~25 r / min; the twin screw aspect ratio range is ≤80, preferably 20~40. The temperature of the melt blending section has a great relationship with the selected polyketone molecular weight. If the selected polyketone number average molecular weight is below 60,000, the melt section temperature can be selected to be below 223°C. Too high a temperature will result in high energy consumption and a slightly yellow product color.

[0039] The present invention also provides an antibacterial product, which is composed of the antibacterial polyketone material described in any of the above technical solutions. The present invention controls the content of each component in the antibacterial polyketone material and the production process, so that the antibacterial polyketone material prepared by the present invention exhibits good thermodynamic properties, high-efficiency and long-lasting antibacterial properties and anti-ultraviolet degradation properties, and has excellent inhibitory effects on a variety of bacteria such as Escherichia coli and Staphylococcus aureus. Therefore, the antibacterial polyketone material prepared by the method can be used for antibacterial products such as medical antibacterial tools such as medical trays or food packaging boxes, slaughter industry transmission chain plates and other food production packaging products.

[0040] The present invention provides an antibacterial polyketone material and a preparation method and application thereof. The antibacterial polyketone material provided by the present invention has good mechanical properties, high-efficiency and long-lasting antibacterial properties and anti-ultraviolet degradation properties. Experiments show that the antibacterial polyketone material provided by the present invention has an antibacterial rate of up to 98.2% against Escherichia coli and an antibacterial rate of up to 99.1% against Staphylococcus aureus. After 300 hours of ultraviolet light irradiation, the elongation at break is still maintained at more than 334%. The antibacterial polyketone material prepared by the method can be used for antibacterial products such as medical antibacterial tools such as medical trays or food production packaging products such as food packaging boxes and conveyor chain plates in the slaughtering industry. DETAILED DESCRIPTION

[0041] The present invention discloses an antibacterial polyketone material and a preparation method and application thereof. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve the same. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0042] The polyketone raw materials used in the following examples of the present invention are homemade products of our company (can be prepared according to patent CN110684189B), and the remaining raw materials are commercially available products, specifically including:

[0043] A: Polyketone powder product, propylene insertion rate is 7%, when the ambient temperature is 240℃ and the load is 2.16 kg, the melt index is 55~65 g / 10min;

[0044] B: Inorganic antibacterial agent: nano ZnO;

[0045] C: Organic antibacterial agent: dodecyl dimethyl benzyl ammonium chloride

[0046] D: UV absorber: 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0047] E: Primary antioxidant: β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid;

[0048] F: Auxiliary antioxidant: antioxidant 168;

[0049] G: Coupling agent: silane coupling agent KH560;

[0050] The present invention will be further described below in conjunction with embodiments:

[0051] Examples 1 to 6 and Comparative Examples 1 to 6

[0052] See Table 1, which is a raw material composition table of Examples 1 to 6 and Comparative Examples 1 to 6, calculated in terms of mass percentage.

[0053] Table 1

[0054]

[0055] The specific preparation method is as follows:

[0056] (1) Add the raw materials in the proportions listed in Table 1 into a high-speed mixer and mix them evenly (the order of adding materials is ABEFDCG), the speed is 300 r / min, and stir for 15 minutes;

[0057] (2) adding the stirred raw materials into a screw extruder and a twin-screw extruder, wherein each heating section of the melt blending section is independently selected to be 230° C., the main screw speed is 300 r / min, and the main feeding screw speed is 20 r / min;

[0058] (3) Injection molding.

[0059] Example 7

[0060] The inorganic antibacterial agent was replaced with nano-TiO2, and the rest was the same as in Example 4.

[0061] Example 8

[0062] The inorganic antibacterial agent was replaced with nano-Ag, and the rest was the same as in Example 4.

[0063] Example 9

[0064] The organic antibacterial agent was replaced with p-vinylbenzyltributylphosphonium chloride (the preparation of which can be found in Modern Plastic Processing Applications, 2012 (3), 27-30). The rest was the same as in Example 4.

[0065] Example 10

[0066] The organic antibacterial agent was replaced with 1-butyl-3-methylimidazolium bromide, and the rest was the same as in Example 4.

[0067] Performance Test:

[0068] The tensile performance test of the specimen was conducted in accordance with GB / T 1040.1 and GB / T 1040.2; the antibacterial performance test was conducted in accordance with QB / T2591-2003; the bending performance test was conducted in accordance with GB / T 9341 (test speed 2 mm / min), and the notched impact performance test was conducted in accordance with GB / T 1843. The test results are shown in Table 2:

[0069] Table 2

[0070]

[0071] Accelerated aging is performed by exposing the specimens to a UV-340A fluorescent light source in a UV aging device. The material UV exposure test is conducted in accordance with GB / T 16422.3. The test results are shown in Table 3:

[0072] Table 3

[0073]

[0074] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. An antibacterial polyketone material, characterized in that: Calculated by mass percentage, it is obtained from the following raw materials: 80-90 wt% polyketone; 4-18 wt% of an antibacterial agent, wherein the antibacterial agent comprises an inorganic antibacterial agent and an organic antibacterial agent, wherein the inorganic antibacterial agent is selected from one or more of nanosilver, nano-TiO2 and nano-ZnO, and the organic antibacterial agent is selected from one or more of chitosan, tea polyphenols, quaternary ammonium salts, quaternary phosphonium salts, imidazolium salts and biguanides; 3-9 wt% of a coupling agent, wherein the coupling agent is selected from one or more of a silane coupling agent and a titanate coupling agent; 0.3~1.2 wt% of UV absorber; 0.5~2 wt% of hindered phenol antioxidant; 0.2~1.5 wt% of phosphite antioxidant.

2. The antibacterial polyketone material according to claim 1, characterized in that: Obtained from the following raw materials: 85-90 wt% polyketone; 4-13 wt% antimicrobial agent; 4~6 wt% coupling agent; 0.8~1.0 wt% of UV absorber; 0.8~1.5 wt% of hindered phenol antioxidant; 0.2~1.0 wt% of phosphite antioxidant.

3. The antibacterial polyketone material according to claim 1, characterized in that: The mass ratio of the inorganic antibacterial agent to the organic antibacterial agent is (1-3): (1-3).

4. The antibacterial polyketone material according to claim 1, characterized in that: The particle size of the inorganic antibacterial agent is 10-300 nm.

5. The antibacterial polyketone material according to claim 1, characterized in that: The coupling agent is selected from one or more of silane coupling agent KH550 and silane coupling agent KH560; The ultraviolet absorber is selected from one or more of 2-hydroxy-4-n-octyloxybenzophenone and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; The hindered phenol antioxidant is selected from one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 2,6-di-tert-butyl-4-methylphenol, antioxidant 1010 and antioxidant 1076; The phosphite antioxidant is selected from one or more of antioxidant 168, antioxidant 626, antioxidant 454 and triphenyl phosphite.

6. The antibacterial polyketone material according to claim 1, characterized in that: The melt index of the polyketone is 3 to 100 g / 10 mins.

7. The antibacterial polyketone material according to any one of claims 1 to 6, characterized in that: Obtained from the following raw materials: 85-90 wt% polyketone; 4-13 wt% of an antibacterial agent, wherein the antibacterial agent is nano ZnO and dodecyl dimethyl benzyl ammonium chloride, or the antibacterial agent is nano TiO2 and dodecyl dimethyl benzyl ammonium chloride, or the antibacterial agent is nano Ag and dodecyl dimethyl benzyl ammonium chloride, or the antibacterial agent is nano ZnO and p-vinylbenzyl tributyl phosphine chloride; 4~6 wt% of silane coupling agent KH560; 0.8-1.0 wt% of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; 0.8-1.5 wt% of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid; 0.2~1.0 wt% of antioxidant 168.

8. The method for preparing the antibacterial polyketone material according to any one of claims 1 to 7, characterized in that: The following steps are involved: The polyketone, the ultraviolet absorber, the antibacterial agent, the hindered phenol antioxidant, the phosphite antioxidant and the coupling agent are melt-blended and then injection-molded to obtain the antibacterial polyketone material.

9. The method for preparing the antibacterial polyketone material according to claim 8, characterized in that: The temperature of the melt blending is 190°C to 270°C.

10. Antibacterial product, characterized in that The invention is composed of the antibacterial polyketone material described in any one of claims 1 to 7.

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