Antibacterial composite pp material and preparation process thereof

Abstract

The invention relates to the technical field of materials, and discloses an antibacterial composite pp material and a preparation process thereof.The antibacterial composite pp material is prepared from polypropylene as a main raw material and a compatilizer, a functional fiber modified additive, a rubber additive and the like as auxiliary materials through mixing and extrusion granulation processes. Wherein the functional fiber modified additive is medical stone fiber of which the surface is modified with a reactive macromolecular antibacterial agent, and the reactive macromolecular antibacterial agent can interact with a maleic anhydride group in a compatilizer structure in a subsequent melt extrusion process, so that the interface bonding performance between the medical stone fiber and polypropylene is greatly improved; further, the reinforcing effect of the medical stone fiber is fully exerted, so that the mechanical strength of the polypropylene material is effectively improved. In addition, triclosan in the structure of the macromolecular antibacterial agent has a broad-spectrum antibacterial effect, so that the polypropylene material can be endowed with excellent broad-spectrum antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and in particular to an antibacterial composite PP material and a preparation process thereof. Background Art

[0002] Polypropylene (PP), an important general-purpose plastic material, has been widely used in home appliance manufacturing, household plastic products, films, pipes, and other fields due to its excellent overall performance, good chemical stability, good molding and processing properties, and relatively low price. In recent years, with the improvement of people's living standards and the strengthening of health awareness, the demand for diversified products has also increased. In particular, the use of antimicrobial modified PP materials can not only improve product hygiene and protect user health, but also extend product lifespan and enhance market competitiveness. However, the inherent defects of PP materials, such as low strength and poor antimicrobial properties, have gradually become significant limitations on their application in products. To overcome these shortcomings, polypropylene materials need to be modified.

[0003] The mechanical properties of polypropylene can be improved by adding functional additives, such as minerals and fibers, to its components. However, conventional inorganic fibers inherently present significant interface issues with the polypropylene matrix, making it difficult to fully utilize these additives, resulting in limited reinforcement effects on polypropylene. Furthermore, the antimicrobial properties of polypropylene can be improved by adding antimicrobial functional additives, such as the inorganic antimicrobial agent silver or the organic antimicrobial agent quaternary ammonium salts. However, inorganic antimicrobials such as silver are heavy metals and can pollute the environment if abandoned, while organic small molecule antimicrobials such as quaternary ammonium salts experience significant migration and volatilization, making it impossible to guarantee the antimicrobial sustainability of polypropylene.

[0004] Based on this, the present invention provides a composite PP material with good mechanical properties and long-lasting antibacterial properties, which can solve the problems existing in the prior art. Summary of the Invention

[0005] (1) Technical problems solved

[0006] In view of the deficiencies of the prior art, the present invention provides an antibacterial composite PP material and a preparation process.

[0007] (2) Technical solution

[0008] A preparation process of an antibacterial composite PP material, wherein the antibacterial composite PP material is made from the following raw materials measured in parts by weight:

[0009]

[0010]

[0011] The preparation process comprises the following steps:

[0012] The first step is to weigh each raw material according to the weight and set aside;

[0013] In the second step, polypropylene, compatibilizer, functional fiber modification additive, rubber additive, antioxidant, inorganic filler and lubricant are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 300-500r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperature of each zone is set to 200±5℃, 210±5℃, 220±5℃, 220±5℃, 210±5℃, 210±5℃, and 210±5℃, and the screw speed is set to 60-80rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

[0014] As a further embodiment of the present invention, the compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.

[0015] As a further embodiment of the present invention, the preparation method of the functionalized fiber modified additive is as follows:

[0016] Step 1: ultrasonically disperse the medical stone fiber in 70-80% ethanol by volume to form a uniform dispersion, then add a silane coupling agent to the dispersion, raise the temperature to 70-80°C, keep stirring for 4-8 hours, cool and discharge, and centrifuge the product to obtain the modified medical stone fiber;

[0017] Step 2: Add the modified medical stone fiber to N,N-dimethylformamide, and after ultrasonic dispersion, continue to add the reactive macromolecular antibacterial agent and phase transfer catalyst. After the addition is completed, stir at room temperature for 20-40 minutes, then increase the temperature to 80-90°C, keep the reaction for 6-9 hours, cool and discharge the material to obtain the functionalized fiber modified additive.

[0018] As a further embodiment of the present invention, in step 1, the silane coupling agent is γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane.

[0019] As a further embodiment of the present invention, in step 2, the specific preparation method of the reactive macromolecular antibacterial agent comprises the following steps:

[0020] Step S1, adding triclosan to tetrahydrofuran, mechanically stirring until completely dissolved, then placing in an ice bath, followed by adding diallylcarbamoyl chloride and an acid binding agent, removing from the ice bath after addition, stirring at room temperature for 2-4 hours, evaporating to remove the solvent, and collecting the solid product to obtain an antibacterial intermediate monomer;

[0021] Step S2: adding the antibacterial intermediate monomer and dithiocarbamate to toluene, mechanically stirring and mixing to form a reaction solution, and then adding the photoinitiator benzoin dimethyl ether to the reaction solution. After the addition, irradiating the reaction system with a 365nm wavelength ultraviolet lamp at room temperature for 1-2 hours, discharging the material to obtain a reactive macromolecular antibacterial agent.

[0022] As a further embodiment of the present invention, in step S1, the acid binding agent is triethylamine or pyridine.

[0023] As a further embodiment of the present invention, in step S2, the molar ratio of the antibacterial intermediate monomer to dimercaprol is 1:1.

[0024] As a further embodiment of the present invention, in step 2, the phase transfer catalyst is boron trifluoride diethyl ether complex.

[0025] In the above technical solution, an acid-binding agent is first used for catalysis, and a condensation reaction is carried out with triclosan and diallylcarbamoyl chloride as reactants to obtain a triclosan derivative containing two equivalents of unsaturated alkenyl substituents in its structure, i.e., an antibacterial intermediate monomer. Subsequently, a photoinitiator is used to initiate a continuous addition reaction between the unsaturated alkenyl functional groups in the antibacterial intermediate monomer structure and the thiol substituents in the dimercaprol structure, thereby obtaining a block-linked macromolecular polymer, i.e., a reactive macromolecular antibacterial agent.

[0026] Since the reactive macromolecular antibacterial agent contains a hydroxyl substituent that does not participate in the reaction, it can undergo a ring-opening reaction with the medical stone fiber modified with an epoxy silane coupling agent under the action of a phase transfer catalyst, thereby modifying the reactive macromolecular antibacterial agent on the surface of the medical stone fiber to prepare a functional fiber modified additive.

[0027] As a further embodiment of the present invention, the rubber additive is at least one of EPDM rubber, nitrile rubber or styrene-butadiene rubber; the antioxidant is at least one of antioxidant 168, antioxidant 1076 or antioxidant 1010; the inorganic filler is at least one of talc, titanium dioxide, calcium carbonate or fumed silica; and the lubricant is any one of calcium stearate, polyethylene wax or paraffin wax.

[0028] A preparation process of an antibacterial composite PP material is prepared by adopting the above preparation process.

[0029] (3) Beneficial technical effects

[0030] The present invention is by modifying the surface of medical stone fiber with reactive macromolecular antimicrobial agent, obtains functionalized fiber modification additive, and takes it as additive, polypropylene is modified, wherein, there are a large number of hydroxyl functional groups that do not participate in the reaction in the reactive macromolecular antimicrobial agent structure, can produce interaction with the maleic anhydride group in the compatibilizer structure in the subsequent melt extrusion process, thereby being equivalent to producing a layer of "transition" structure between medical stone fiber and polypropylene matrix, can make the connection structure similar to "snap-in" formula produced between medical stone fiber and polypropylene matrix, greatly improve the interface bonding performance between medical stone fiber and polypropylene, and then make the reinforcing effect of medical stone fiber fully play, thereby effectively improve the mechanical strength of polypropylene material. In addition, the triclosan in the macromolecular antimicrobial agent structure has a broad-spectrum antimicrobial effect, can give the polypropylene material excellent broad-spectrum antimicrobial performance, simultaneously because of the existence of interaction, can not migrate and separate out the phenomenon, can guarantee the continuous antimicrobial effect of polypropylene material. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0032] Figure 1 This is the infrared analysis test diagram of the reactive macromolecular antibacterial agent. DETAILED DESCRIPTION

[0033] To facilitate understanding of the present invention, the present invention will be described in more detail below. Preferred embodiments of the present invention are provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0034] Preparation Example 1

[0035] Preparation of functionalized fiber modified additives:

[0036] Step 1: ultrasonically disperse 2.6 g of medical stone fiber in 70% by volume ethanol to form a uniform dispersion, then add 3.5 g of γ-glycidyloxypropyltriethoxysilane to the dispersion. After the addition is complete, heat to 75° C., keep stirring for 6 hours, cool and discharge, and centrifuge the product to obtain modified medical stone fiber;

[0037] Step 2: Add 2.4 g of modified medical stone fiber to N,N-dimethylformamide, and after ultrasonic dispersion, continue to add 5 g of reactive macromolecular antibacterial agent and 0.1 g of boron trifluoride ether complex. After the addition is completed, stir at room temperature for 30 minutes, then increase the temperature to 85°C, keep the reaction for 8 hours, cool and discharge the material to obtain the functionalized fiber modified additive.

[0038] The specific preparation method of the reactive macromolecular antibacterial agent comprises the following steps:

[0039] Step S1, adding 0.5 g of triclosan to tetrahydrofuran, mechanically stirring until completely dissolved, and then placing in an ice bath, followed by adding 0.28 g of diallylcarbamoyl chloride and 0.1 g of triethylamine. After the addition is complete, removing from the ice bath, stirring at room temperature for 3 hours, evaporating to remove the solvent, and collecting the solid product to obtain an antibacterial intermediate monomer;

[0040] Step S2: add 0.3 g of the antibacterial intermediate monomer and 0.09 g of dithiocarbamate to toluene, stir mechanically and mix evenly to form a reaction solution, then add 0.01 g of the photoinitiator benzoin dimethyl ether to the reaction solution. After the addition, irradiate the reaction system with a 365 nm wavelength ultraviolet lamp at room temperature. After 2 hours, discharge the material to obtain a reactive macromolecular antibacterial agent.

[0041] Figure 1 This is the infrared analysis test diagram of the reactive macromolecular antibacterial agent, where 3321cm -1 The characteristic absorption peak attributed to hydroxyl groups appeared at 2800-3000 cm -1 The characteristic absorption peak of carbon and hydrogen belonging to methylene appeared at 1747 cm -1 The C=O characteristic absorption peak at 1133 cm-1, which belongs to the ester group, appears at -1 A characteristic absorption peak attributed to CS appeared at .

[0042] Example 1

[0043] An antibacterial composite PP material is made of the following raw materials measured in parts by weight:

[0044]

[0045]

[0046] The preparation process comprises the following steps:

[0047] The first step is to weigh each raw material according to the weight and set aside;

[0048] In the second step, polypropylene, compatibilizer maleic anhydride grafted polyethylene, functionalized fiber modified additives, EPDM rubber, antioxidant 168, inorganic filler talc and lubricant calcium stearate are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 300r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200℃, 210℃, 220℃, 220℃, 210℃, and 210℃, respectively, and the screw speed is set to 6rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

[0049] The preparation method of the functionalized fiber modified additive is shown in Preparation Example 1, and the same is true for the following.

[0050] Example 2

[0051] An antibacterial composite PP material is made of the following raw materials measured in parts by weight:

[0052]

[0053]

[0054] The preparation process comprises the following steps:

[0055] The first step is to weigh each raw material according to the weight and set aside;

[0056] In the second step, polypropylene, compatibilizer maleic anhydride grafted polypropylene, functional fiber modification additives, nitrile rubber, antioxidant 1076, inorganic filler titanium dioxide and lubricant polyethylene wax are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 500r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200℃, 210℃, 220℃, 220℃, 210℃, and 210℃ respectively, and the screw speed is set to 80rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

[0057] Example 3

[0058] An antibacterial composite PP material is made of the following raw materials measured in parts by weight:

[0059]

[0060]

[0061] The preparation process comprises the following steps:

[0062] The first step is to weigh each raw material according to the weight and set aside;

[0063] In the second step, polypropylene, compatibilizer maleic anhydride grafted polypropylene, functionalized fiber modified additives, styrene-butadiene rubber, antioxidant 1076, inorganic filler calcium carbonate and lubricant polyethylene wax are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 500r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200℃, 210℃, 220℃, 220℃, 210℃, and 210℃ respectively, and the screw speed is set to 80rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

[0064] Comparative Example 1

[0065] An antibacterial composite PP material is made of the following raw materials measured in parts by weight:

[0066]

[0067]

[0068] The preparation process comprises the following steps:

[0069] The first step is to weigh each raw material according to the weight and set aside;

[0070] In the second step, polypropylene, compatibilizer maleic anhydride grafted polypropylene, medical stone fiber, nitrile rubber, antioxidant 1076, inorganic filler titanium dioxide and lubricant polyethylene wax are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 500r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200℃, 210℃, 220℃, 220℃, 210℃, and 210℃ respectively, and the screw speed is set to 80rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

[0071] Comparative Example 2

[0072] An antibacterial composite PP material is made of the following raw materials measured in parts by weight:

[0073]

[0074]

[0075] The preparation process comprises the following steps:

[0076] The first step is to weigh each raw material according to the weight and set aside;

[0077] In the second step, polypropylene, compatibilizer maleic anhydride grafted polypropylene, reactive macromolecular antibacterial agent, nitrile rubber, antioxidant 1076, inorganic filler titanium dioxide and lubricant polyethylene wax are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 500r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200℃, 210℃, 220℃, 220℃, 210℃, and 210℃ respectively, and the screw speed is set to 80rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

[0078] Comparative Example 3

[0079] A composite PP material is made of the following raw materials measured in parts by weight:

[0080]

[0081]

[0082] The preparation process comprises the following steps:

[0083] The first step is to weigh each raw material according to the weight and set aside;

[0084] In the second step, polypropylene, compatibilizer maleic anhydride grafted polypropylene, nitrile rubber, antioxidant 1076, inorganic filler titanium dioxide and lubricant polyethylene wax are added to the mixing kettle, mechanically stirred and mixed at a stirring rate of 500r / min, and then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200℃, 210℃, 220℃, 220℃, 210℃, and 210℃ respectively, and the screw speed is set to 80rpm. After the masterbatch is naturally cooled, the composite PP material can be obtained.

[0085] Test Case

[0086] The composite PP materials in the examples and comparative examples were made into test samples that met the specifications, and various performance tests were performed. The results are recorded in the following table:

[0087]

[0088]

[0089] The antibacterial rate test selected Staphylococcus aureus as the test sample.

[0090] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that are not substantially different from the literal description of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A preparation process of an antibacterial composite PP material, characterized in that: The antibacterial composite PP material is made of the following raw materials measured in parts by weight: Polypropylene 75-85 parts; Compatibilizer 10-20 parts; 3-6 parts of functional fiber modified additives; Rubber additives 5-10 parts; 0.5-1.5 parts of antioxidant; 4-8 parts of inorganic filler; 1-3 parts of lubricant; The preparation process comprises the following steps: The first step is to weigh each raw material according to its weight and set it aside for later use; In the second step, polypropylene, compatibilizer, functional fiber modification additive, rubber additive, antioxidant, inorganic filler and lubricant are added to the mixing kettle, and mechanically stirred and mixed at a stirring rate of 300-500r / min. Then the formed mixture is fed into a twin-screw extruder for melt extrusion. The temperatures of each zone are set to 200±5℃, 210±5℃, 220±5℃, 220±5℃, 210±5℃, 210±5℃, and 210±5℃ respectively. The screw speed is set to 60-80rpm. After the masterbatch is naturally cooled, the antibacterial composite PP material can be obtained.

2. The preparation process of an antibacterial composite PP material according to claim 1, characterized in that: The compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.

3. The preparation process of an antibacterial composite PP material according to claim 1, characterized in that: The preparation method of the functionalized fiber modified additive is as follows: Step 1: using a silane coupling agent to modify the surface of the medical stone fiber to obtain modified medical stone fiber; Step 2: Use a reactive macromolecular antibacterial agent to carry out a grafting reaction on the modified medical stone fiber under the catalytic action of a phase transfer catalyst to obtain a functionalized fiber modified additive.

4. The preparation process of an antibacterial composite PP material according to claim 3, characterized in that: In step 1, the silane coupling agent is γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane.

5. The preparation process of an antibacterial composite PP material according to claim 3, characterized in that: In step 2, the specific preparation method of the reactive macromolecular antibacterial agent comprises the following steps: Step S1, adding triclosan to tetrahydrofuran, mechanically stirring until completely dissolved, and then placing in an ice bath, followed by adding diallylcarbamoyl chloride and an acid binding agent, after the addition is complete, removing from the ice bath, stirring at room temperature for 2-4 hours, evaporating to remove the solvent, collecting the solid product, and obtaining an antibacterial intermediate monomer; Step S2, adding the antibacterial intermediate monomer and dimercaprol to toluene, mechanically stirring and mixing to form a reaction solution, and then adding a photoinitiator benzoin dimethyl ether to the reaction solution. After the addition, irradiating the reaction system with a 365nm wavelength ultraviolet lamp at room temperature, and discharging the material after 1-2h to obtain a reactive macromolecular antibacterial agent.

6. The preparation process of an antibacterial composite PP material according to claim 5, characterized in that: In step S1, the acid binding agent is triethylamine or pyridine.

7. The preparation process of an antibacterial composite PP material according to claim 5, characterized in that: In step S2, the molar ratio of the antibacterial intermediate monomer to dimercaprol is 1:

1.

8. The preparation process of an antibacterial composite PP material according to claim 3, characterized in that: In step 2, the phase transfer catalyst is boron trifluoride ether complex.

9. The preparation process of an antibacterial composite PP material according to claim 1, characterized in that: The rubber additive is at least one of EPDM rubber, nitrile rubber or styrene-butadiene rubber; the antioxidant is at least one of antioxidant 168, antioxidant 1076 or antioxidant 1010; the inorganic filler is at least one of talc, titanium dioxide, calcium carbonate or fumed silica; the lubricant is any one of calcium stearate, polyethylene wax or paraffin.

10. A preparation process of an antibacterial composite PP material, characterized in that: The method is prepared by the preparation process according to any one of claims 1 to 9.

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