Antibacterial master batch capable of releasing negative ions and preparation method of antibacterial master batch

Abstract

The invention relates to the field of high polymer materials, in particular to an antibacterial master batch capable of releasing negative ions and a preparation method thereof, and the antibacterial master batch comprises the following components in parts by mass: 30-70 parts of negative ion antibacterial resin, 10-50 parts of toner and a processing aid. The tourmaline is introduced into the polymer master batch in a chemical copolymerization manner, the tourmaline is favorably dispersed, meanwhile, the composite powder and the antibacterial monomer are introduced, so that the master batch with very excellent antibacterial performance is obtained, the release of negative ions in the master batch and the intramolecular and intermolecular interaction of the tourmaline powder, the composite powder and the antibacterial monomer are synergistically promoted, and the antibacterial property of the antibacterial master batch is improved. The negative ions such as hydrogen bonds can regulate and control the space structure and the surface activity of the tourmaline, provide more active reaction centers, and are beneficial to spontaneous polarization effect formation of tourmaline crystals and generation of a large number of negative ions.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to an antibacterial masterbatch releasing negative ions and a preparation method thereof. Background Art

[0002] Masterbatch is a new type of colorant for polymer materials. It is mainly used in plastics. Masterbatch is composed of three basic elements: pigment or dye, carrier and additive. It is an aggregate made by uniformly attaching an extraordinary amount of pigment to the resin. Therefore, its tinting power is higher than the pigment itself. During processing, the pigment has better dispersibility in the product. During the production process of masterbatch, the pigment must be refined to improve the dispersibility and tinting power of the pigment.

[0003] Tourmaline is the general term for tourmaline minerals. It has a complex chemical composition and is a ring-structured silicate mineral of aluminum, sodium, iron, magnesium, and lithium characterized by boron. Tourmaline has unique properties such as piezoelectricity, pyroelectricity, conductivity, far-infrared radiation, and release of negative ions. It can be compounded with other materials by physical or chemical methods to produce a variety of functional materials, which are used in environmental protection, electronics, medicine, chemical industry, light industry, building materials and other fields.

[0004] At present, there are few reports on the introduction of negative ions and antibacterial properties into masterbatches. Summary of the invention

[0005] In order to solve the problems mentioned in the above background technology, the present invention provides an antibacterial masterbatch releasing negative ions and a preparation method thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a first aspect of an antibacterial masterbatch for releasing negative ions, which comprises, by weight: 30-70 parts of negative ion antibacterial resin, 10-50 parts of color powder, and a processing aid; The preparation method of the negative ion antibacterial resin is as follows: Dispersing tourmaline powder and composite powder in water, heating to obtain a reaction system, dispersing methacryloxypropyltriethoxysilane in anhydrous ethanol, dropping into the reaction system, stirring for reaction, filtering, washing with anhydrous ethanol, and drying to obtain negative ion powder containing double bonds, wherein the composite powder is composed of boron nitride powder, calcium carbonate powder, and titanium dioxide powder; Dispersing N-(3-dimethylaminopropyl) methacrylamide, tetradecane bromide and polymerization inhibitor p-hydroxyanisole in acetonitrile, stirring for reaction, freezing for crystallization, washing with ether and drying, to obtain an antibacterial monomer containing a double bond; Under a nitrogen atmosphere, Tween 40 and deionized water are added to a polymerization reaction kettle, stirred and dispersed evenly, anion powder containing double bonds and Span 80 are dispersed in cyclohexane, and then added to the above polymerization reaction kettle, stirred and dispersed evenly, finally styrene, antibacterial monomer containing double bonds, and tert-butyl hydroperoxide are added to the polymerization reaction kettle, emulsified, ferrous chloride is added, polymerization reaction is carried out, ethanol is added to break the emulsion, filtered, washed, and dried to obtain anion antibacterial resin.

[0007] Preferably, the mass ratio of the tourmaline powder to the composite powder is 200:(5-15).

[0008] Preferably, the mass ratio of the boron nitride powder, calcium carbonate powder and titanium dioxide powder is (1-3): (2-8): (1-5).

[0009] Preferably, the molar ratio of N-(3-dimethylaminopropyl)methacrylamide to tetradecane bromide is 1:(0.95-1.05).

[0010] Preferably, the mass ratio of Tween 40, negative ion powder containing double bonds, Span 80, styrene, antibacterial monomer containing double bonds, tert-butyl hydroperoxide, and ferrous chloride is (50-150): (20-40): (1-10): (50-150): (5-15): (3-7): (5-10).

[0011] Preferably, the processing aid is selected from any one or more of an antioxidant, a dispersant, and a lubricant.

[0012] The second aspect of the present invention provides a method for preparing the above masterbatch, comprising the following steps: The negative ion antibacterial resin, color powder and processing aid are premixed, and the premixed materials are sent to a twin-screw extruder for extrusion granulation to obtain the antibacterial masterbatch releasing negative ions.

[0013] Preferably, the parameters of the twin-screw extruder are: temperature setting: zone 1 80±10℃, zone 2 210±10℃, zone 3 215±10℃, zone 4 215±10℃, zone 5 210±10℃, zone 6 210±10℃, zone 7 210±10℃, zone 8 210±10℃, zone 9 210±10℃, die head 215±10℃; main engine speed: 30±3hz; main engine current: 75±20A; feeding speed: 13±3hz; vacuum: -0.07±0.03MPa.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses methacryloxypropyltriethoxysilane to modify the surface of tourmaline powder and composite powder to obtain negative ion powder containing double bonds, and uses N-(3-dimethylaminopropyl)methacrylamide and tetradecane bromide to carry out quaternization reaction to obtain antibacterial monomer containing double bonds. Since the activity difference between the negative ion powder containing double bonds, the antibacterial monomer containing double bonds and styrene is relatively large, the negative ion powder containing double bonds is placed at the interface of two phases, and an oxidation-reduction initiator is used to initiate emulsion polymerization at the interface to finally obtain negative ion antibacterial resin, and the negative ion antibacterial resin, color powder, antioxidant, dispersant and lubricant are melt-extruded to obtain antibacterial masterbatch releasing negative ions.

[0015] 2. The present invention introduces tourmaline into the polymer masterbatch by chemical copolymerization, which is beneficial to the dispersion of tourmaline. At the same time, the introduction of composite powder and antibacterial monomer not only obtains a masterbatch with excellent antibacterial properties, but also synergistically promotes the release of negative ions in the masterbatch. The intramolecular and intermolecular interactions among tourmaline powder, composite powder and antibacterial monomer, such as hydrogen bonds, can regulate the spatial structure and surface activity of tourmaline, provide more active reaction centers, and are beneficial to the spontaneous formation of polarization effects in tourmaline crystals to generate a large number of negative ions. DETAILED DESCRIPTION

[0016] Unless otherwise specified, the raw materials and reagents used in the present invention are commercially available or can be prepared by known methods.

[0017] Some of the raw materials come from the following sources: Tourmaline powder: Liyang Minerals, Lingshou County, Hebei Province, 600 mesh; Boron nitride powder: Zibo Jingyi Ceramic Technology Co., Ltd., 1-3 microns; Calcium carbonate powder, titanium dioxide powder: Sinopharm Reagent; PS resin: Formosa Chemical Ningbo, 825G; Antioxidant 1076, 168: BASF; Dispersant: Indonesia EBS B50; The lubricant is: Italian calcium stearate; Color powder: BASF; Preparation Example 1 Preparation of negative ion powder containing double bonds: Disperse 200g of tourmaline powder and 10g of composite powder (2g of boron nitride powder, 5g of calcium carbonate powder, and 3g of titanium dioxide powder) in 2L of water, heat to 80°C to obtain a reaction system, disperse 20mL of methacryloxypropyltriethoxysilane in 500mL of anhydrous ethanol, drop into the above reaction system, stir and react for 2h, filter, wash with anhydrous ethanol, and dry to obtain a negative ion powder containing a double bond; Preparation of antibacterial monomers containing double bonds: Disperse (85 g, 1 mol) N-(3-dimethylaminopropyl) methacrylamide, (277 g, 1 mol) tetradecane bromide, and 0.5 g of inhibitor p-hydroxyanisole in 1.5 L acetonitrile, stir at 45 °C for 12 h, freeze crystallize, wash with ether, and dry to obtain an antibacterial monomer containing a double bond; Preparation of negative ion antibacterial resin: Under a nitrogen atmosphere, 5g of Tween 40 and 2L of deionized water were added to the polymerization reactor, and the mixture was stirred and dispersed evenly. 100g of anion powder containing double bonds and 5g of Span 80 were dispersed in 1L of cyclohexane and then added to the above polymerization reactor, and the mixture was stirred and dispersed evenly. Finally, 90g of styrene, 10g of antibacterial monomer containing double bonds, and 5g of tert-butyl hydroperoxide were added to the polymerization reactor, emulsified at 40°C for 0.5min, 7g of ferrous chloride was added, and the polymerization reaction was carried out at 50°C for 8h. Ethanol was added to break the emulsification, and the mixture was filtered, washed, and dried to obtain anion antibacterial resin.

[0018] Preparation Example 2 (lacking composite powder, adding antibacterial monomer) The difference between this preparation example and preparation example 1 is that: Disperse 200g tourmaline powder and 0g composite powder (0g boron nitride powder, 0g calcium carbonate powder, 0g silicon dioxide powder) in 2L water; The rest is exactly the same as Preparation Example 1.

[0019] Preparation Example 3 (lack of antibacterial monomer, adding composite powder) The difference between this preparation example and preparation example 1 is that: Finally, 100 g of styrene, 0 g of an antibacterial monomer containing a double bond, and 5 g of tert-butyl hydroperoxide were added to the polymerization reactor; The rest is exactly the same as Preparation Example 1.

[0020] Preparation Example 4 (lack of antibacterial monomer and composite powder) The difference between this preparation example and preparation example 1 is that: 1. Disperse 200g tourmaline powder and 0g composite powder (0g boron nitride powder, 0g calcium carbonate powder, 0g silicon dioxide powder) in 2L water; 2. Finally, add 100g styrene, 0g antibacterial monomer containing double bonds, and 5g tert-butyl hydroperoxide into the polymerization reactor; The rest is exactly the same as Preparation Example 1.

[0021] Preparation Example 5 The difference between this preparation example and preparation example 1 is that: Disperse 200g tourmaline powder and 5g composite powder (1g boron nitride powder, 2g calcium carbonate powder, 2g silicon dioxide powder) in 2L water; The rest is exactly the same as Preparation Example 1.

[0022] Preparation Example 6 The difference between this preparation example and preparation example 1 is that: Disperse 200g tourmaline powder and 15g composite powder (3g boron nitride powder, 7g calcium carbonate powder, 5g silicon dioxide powder) in 2L water; The rest is exactly the same as Preparation Example 1. Example 1

[0023] An antibacterial masterbatch for releasing negative ions, comprising, by weight: 50 parts of negative ion antibacterial resin (obtained in Preparation Example 1), 30 parts of toner, 0.4 parts of antioxidant 1076, 0.6 parts of antioxidant 168, 2 parts of dispersant, and 3 parts of lubricant; Premixing the materials in the above proportions, feeding the premixed materials into a twin-screw extruder for extrusion granulation, and obtaining an antibacterial masterbatch that releases negative ions; The parameters of the twin-screw extruder are: temperature setting: zone 1 80℃, zone 2 210℃, zone 3 215℃, zone 4 215℃, zone 5 210℃, zone 6 210℃, zone 7 210℃, zone 8 210℃, zone 9 210℃, die head 215℃; main engine speed: 32hz; main engine current: 80-90; feeding speed: 15hz; vacuum: -0.08MPa. Example 2

[0024] The difference between this embodiment and embodiment 1 is that: 30 parts of negative ion antibacterial resin (obtained in preparation example 1); The rest is exactly the same as in Example 1. Example 3

[0025] The difference between this embodiment and embodiment 1 is that: 70 parts of negative ion antibacterial resin (obtained in preparation example 1); The rest is exactly the same as in Example 1. Example 4

[0026] The difference between this embodiment and embodiment 1 is that: 50 parts of negative ion antibacterial resin (obtained in preparation example 5); The rest is exactly the same as in Example 1. Example 5

[0027] The difference between this embodiment and embodiment 1 is that: 50 parts of negative ion antibacterial resin (obtained in Preparation Example 6); The rest is exactly the same as in Example 1.

[0028] Comparative Example 1 The difference between this comparative example and Example 1 is that: 50 parts of negative ion antibacterial resin (obtained in Preparation Example 2); The rest is exactly the same as in Example 1.

[0029] Comparative Example 2 The difference between this comparative example and Example 1 is that: 50 parts of negative ion antibacterial resin (obtained in Preparation Example 3); The rest is exactly the same as in Example 1.

[0030] Comparative Example 3 The difference between this comparative example and Example 1 is that: 50 parts of negative ion antibacterial resin (obtained in Preparation Example 4); The rest is exactly the same as in Example 1.

[0031] Comparative Example 4 An antibacterial masterbatch for releasing negative ions, calculated by weight, includes: 25 parts of tourmaline powder, 25 parts of PS, 30 parts of color powder, 0.4 parts of antioxidant 1076, 0.6 parts of antioxidant 168, 2 parts of dispersant, and 3 parts of lubricant; Premixing the materials in the above proportions, feeding the premixed materials into a twin-screw extruder for extrusion granulation, and obtaining an antibacterial masterbatch that releases negative ions; The parameters of the twin-screw extruder are: temperature setting: zone 1 80℃, zone 2 210℃, zone 3 215℃, zone 4 215℃, zone 5 210℃, zone 6 210℃, zone 7 210℃, zone 8 210℃, zone 9 210℃, die head 215℃; main engine speed: 32hz; main engine current: 80-90; feeding speed: 15hz; vacuum: -0.08MPa.

[0032] Results and Testing Negative ion detection method: solid negative ion release instrument COM-3010PRO was used for detection, and the test was conducted at room temperature and pressure. The masterbatch and raw material tourmaline powder obtained in Examples 1-5 and Comparative Examples 1-4 were placed on the detection table, with the instrument 10 cm away from the sample, to test the negative ion release.

[0033] The antibacterial test method is as follows: First, the master batches obtained in Examples 1-5 and Comparative Examples 1-4 are cut into samples with a particle size of 1 mm, and then 1 mL of a 100 mL phosphate buffer solution is added. 8 CFU / mL of Escherichia coli suspension was added with 1g sample as the experimental group and the blank group without sample. The suspension was shaken at room temperature for 5h, and 2ml was inoculated into beef extract peptone basal medium respectively. The suspension was cultured at 37℃ for 24h. The experiment was repeated 5 times, and the viable bacteria were counted and the average value was taken to calculate the inhibition rate. The inhibition rate = (the number of colonies in the blank group - the number of colonies in the experimental group) / the number of colonies in the blank group × 100%. The results are shown in Table 1.

[0034] Table 1

[0035] According to Table 1, compared with the raw material tourmaline powder, the negative ion release of the masterbatch prepared in Examples 1-5 and Comparative Examples 1-4 of the present application (calculated according to the actual proportion of tourmaline powder, for example, in Example 1, 50 parts of negative ion antibacterial resin contains 25 parts of tourmaline powder, so the proportion of tourmaline powder in the masterbatch is 25 divided by (50+30+0.4+0.6+2+3), which is equal to 0.29) is significantly improved, and the best effect is Example 1, whose negative ion release reaches 15682 ions / cm 3 .

[0036] Comparing Example 1 with Comparative Example 1, it can be seen that the negative ion release of Comparative Example 1 is from 15682 ions / cm 3 Down to 11534 ions / cm 3 ; Comparing Example 1 with Comparative Example 2, it can be seen that due to the lack of antibacterial monomer, the negative ion release of Comparative Example 2 increased from 15682 ions / cm 3 Down to 13231 ions / cm 3 ; Comparing Example 1 with Comparative Example 3, it can be seen that the negative ion release of Comparative Example 3 is from 15682 ions / cm 3 Down to 11104 ions / cm 3 ; Comparing Example 1 and Comparative Example 4, it can be seen that under the condition of the same amount of tourmaline powder added, the masterbatch prepared by the present invention has an anion release amount from 11080 ions / cm 3 Increased to 15682 ions / cm 3 ; In other words, the addition of composite powder and antibacterial monomer can increase the release of negative ions, and when the two are used at the same time, the release of negative ions is significantly improved. The two have a synergistic enhancement effect, and the masterbatch also has very excellent antibacterial properties.

[0037] 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 masterbatch that releases negative ions, characterized in that: Calculated by weight, it includes: 30-70 parts of negative ion antibacterial resin, 10-50 parts of color powder, and processing aids; The preparation method of the negative ion antibacterial resin is as follows: Dispersing tourmaline powder and composite powder in water, heating to obtain a reaction system, dispersing methacryloxypropyltriethoxysilane in anhydrous ethanol, dropping into the reaction system, stirring for reaction, filtering, washing with anhydrous ethanol, and drying to obtain negative ion powder containing double bonds, wherein the composite powder is composed of boron nitride powder, calcium carbonate powder, and titanium dioxide powder; Dispersing N-(3-dimethylaminopropyl) methacrylamide, tetradecane bromide and polymerization inhibitor p-hydroxyanisole in acetonitrile, stirring for reaction, freezing for crystallization, washing with ether and drying, to obtain an antibacterial monomer containing a double bond; Under a nitrogen atmosphere, Tween 40 and deionized water are added to a polymerization reaction kettle, stirred and dispersed evenly, anion powder containing double bonds and Span 80 are dispersed in cyclohexane, and then added to the above polymerization reaction kettle, stirred and dispersed evenly, finally styrene, antibacterial monomer containing double bonds, and tert-butyl hydroperoxide are added to the polymerization reaction kettle, emulsified, ferrous chloride is added, polymerization reaction is carried out, ethanol is added to break the emulsion, filtered, washed, and dried to obtain anion antibacterial resin.

2. The antibacterial masterbatch for releasing negative ions according to claim 1, characterized in that: The mass ratio of the tourmaline powder to the composite powder is 200:(5-15).

3. The antibacterial masterbatch for releasing negative ions according to claim 1, characterized in that: The mass ratio of the boron nitride powder, calcium carbonate powder and titanium dioxide powder is (1-3): (2-8): (1-5).

4. The antibacterial masterbatch for releasing negative ions according to claim 1, characterized in that: The molar ratio of N-(3-dimethylaminopropyl)methacrylamide to tetradecane bromide is 1:(0.95-1.05).

5. The antibacterial masterbatch for releasing negative ions according to claim 1, characterized in that: The mass ratio of Tween 40, negative ion powder containing double bonds, Span 80, styrene, antibacterial monomer containing double bonds, tert-butyl hydroperoxide, and ferrous chloride is (50-150): (20-40): (1-10): (50-150): (5-15): (3-7): (5-10).

6. The antibacterial masterbatch for releasing negative ions according to claim 1, characterized in that: The processing aid is selected from any one or more of antioxidants, dispersants and lubricants.

7. The method for preparing the masterbatch according to any one of claims 1 to 6, characterized in that: The steps include: The negative ion antibacterial resin, color powder and processing aid are premixed, and the premixed materials are sent to a twin-screw extruder for extrusion granulation to obtain the antibacterial masterbatch releasing negative ions.

8. The method for preparing the masterbatch according to claim 7, characterized in that: The parameters of the twin-screw extruder are: temperature setting: zone 1 80±10℃, zone 2 210±10℃, zone 3 215±10℃, zone 4 215±10℃, zone 5 210±10℃, zone 6 210±10℃, zone 7 210±10℃, zone 8 210±10℃, zone 9 210±10℃, die head 215±10℃; main engine speed: 30±3hz; main engine current: 75±20A; feeding speed: 13±3hz; vacuum: -0.07±0.03MPa.

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