Preparation method and application of surface bonding type antibacterial white carbon black

Abstract

The invention discloses a preparation method and application of surface bonding type antibacterial white carbon black. The preparation method comprises the following two steps: (1) carrying out quaternization reaction on chloropropyl trialkoxysilane and long carbon chain tertiary amine to obtain quaternary ammonium salt silane A; carrying out anion replacement on the quaternary ammonium salt silane A to obtain quaternary ammonium salt silane B containing bromine, iodine or acetate; and (2) carrying out surface treatment on white carbon black by using the quaternary ammonium salt silane A or quaternary ammonium salt silane B to obtain the antibacterial white carbon black with the surface bonded with the long-carbon-chain quaternary ammonium salt. The surface of the antibacterial white carbon black provided by the invention is bonded with a long-carbon-chain antibacterial group, so that the antibacterial effect is stable and lasting, the white carbon black is easily dispersed in a polymer matrix, and a polymer is endowed with long-acting antibacterial performance. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical additives, and particularly relates to a preparation method and application of a surface-bonded antibacterial silica white carbon black. Background Art

[0002] Antibacterial materials can effectively prevent infections and block the transmission of pathogenic microorganisms. For example, in the field of medical and health, the use of antibacterial silicone rubber renal dialysis tubes and catheters can prevent bacterial infections and cross-infections, and improve the service life of the materials and medical safety; in the field of furniture and supplies, materials such as antibacterial polyurethane have the ability to inhibit or kill bacteria on the surface, reducing the risk of disease transmission. Nowadays, polymer-based materials are widely used in many fields such as medical and health, food processing, household supplies, and personal care. However, since the vast majority of polymers themselves do not have antibacterial effects, how to endow polymer materials with antibacterial functions has become a popular research direction. The simplest way to endow polymer materials with antibacterial functions is to blend antibacterial agents, such as quaternary ammonium salts, guanidine salts, silver ions and other antibacterial agents. However, since most antibacterial agents are water-soluble and easily lost when exposed to water, the polymer gradually loses its antibacterial function. To solve the problem of antibacterial agent loss, some people have chemically bonded antibacterial agents to the polymer matrix to obtain a long-lasting and stable antibacterial effect. However, this method has poor universality and problems such as low grafting efficiency or the problem of free antibacterial agents.

[0003] Silica white carbon black is a kind of silica with a particle size of dozens of nanometers. As an additive in the chemical industry, it is widely used in the processing of materials such as rubber, polyolefin, and polyurethane. It has a large specific surface area and contains a large number of polar silanol groups on the surface. When used as a polymer additive, surface hydrophobic treatment is usually required with silane. Combining antibacterial agents with silica white carbon black to prepare an antibacterial silica white carbon black is expected to solve the antibacterial problem of polymer materials.

[0004] Patent CN201810879805.6 discloses a preparation method of a white carbon composite material containing nano silver oxide. The nano silver oxide is crushed into a powder with a particle size of 2-4 μm, and a carbon source is used to modify the silver oxide to form a coating structure, achieving a long-lasting antibacterial effect without affecting the strength of the material. The silver oxide powder used in this method is a commonly used antibacterial agent with good antibacterial effects, but silver ions may cause heavy metal poisoning in organisms and are not suitable for use in the medical and health field, which limits the application scenarios of this silica white carbon black.

[0005] Patent CN201310265998.3 discloses an antibacterial silica white product which uses a mixed acid of bamboo vinegar liquid and sulfuric acid as an acidifying agent, reacts with industrial water glass, and obtains the product through filtration and drying. The silica white prepared by this method is environmentally friendly, low in cost and has good antibacterial effect. However, the bamboo vinegar liquid with antibacterial effect is a by-product obtained from the pyrolysis of bamboo, belonging to a natural organic small molecule antibacterial agent, which is easy to decompose and cannot achieve the effect of long-term antibacterial. Summary of the Invention

[0006] The purpose of the present invention is to provide a surface-bonded antibacterial silica white material, which is added to the matrix material as an additive to endow the material with long-term antibacterial effect.

[0007] The present invention is achieved through the following technical solutions:

[0008] A surface-bonded antibacterial silica white is bonded with a long carbon chain quaternary ammonium salt on the surface of silica white, and its chemical structure is shown as follows:

[0009]

[0010] Among them, X is selected from one or a combination of Cl, Br, I or COO; R1 is selected from -H, -CH3, -C2H5, or -CH(CH3)2; R2 is selected from -C6H 13 、-C 12 H 25 、-C 16 H 33 、-C 18 H 37 or a combination of one or more.

[0011] A surface-bonded antibacterial silica white is prepared by the following method:

[0012] (1) Chloropropyltrialkoxysilane and long carbon chain tertiary amine are mixed according to a molar ratio of 1:(0.5 - 1.0), and quaternization reaction is carried out at 80 - 150 °C under vacuum for 5 - 20 h to obtain quaternary ammonium salt silane A.

[0013] (2) 1 - 5 parts by weight of chloropropyltrialkoxysilane quaternary ammonium salt is dissolved in 100 parts by weight of absolute ethanol, 0.2 - 5 parts by weight of inorganic salt is added, stirred for 1 - 5 h, the precipitate is filtered off, and the filtrate is evaporated to dryness to obtain quaternary ammonium salt silane B.

[0014] (3) 10 parts by weight of silica white, 0.5 - 2 parts by weight of quaternary ammonium salt silane A or quaternary ammonium salt silane B are dispersed in 50 - 100 parts by weight of ethanol with a concentration of 75 - 95% (v / v), 0.01 - 0.5 parts of acid is added; stirred at room temperature for 12 - 24 h, and antibacterial silica white is obtained through conventional steps such as static layering, separation and drying.

[0015] The described chloropropyltrialkoxysilane includes chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and chloropropyltriisopropoxysilane;

[0016] The described long-chain tertiary amine includes N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylhexadecylamine, and N,N-dimethyloctadecylamine;

[0017] The described inorganic salt includes potassium bromide, potassium iodide, potassium acetate, sodium bromide, sodium iodide, and sodium acetate;

[0018] The described quaternary ammonium salt silane A is a quaternary ammonium salt silane with chloride ion as the anion; quaternary ammonium salt silane B is a quaternary ammonium salt silane with bromide ion, iodide ion, or acetate ion in the anion;

[0019] The described silica white is fumed or precipitated silica white without surface treatment, and its specific surface area is 100 - 400 m 2 / g;

[0020] The described acid includes acetic acid, hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, and p-toluenesulfonic acid.

[0021] The surface-bonded antibacterial silica white provided by the present invention is a non-leaching antibacterial filler. According to the ASTM E2149 standard for antibacterial testing, the antibacterial rate against Escherichia coli is greater than 99%. As an additive, adding 0.1 - 10 parts by weight of the surface-bonded antibacterial silica white to conventional polymer materials can endow the polymer materials with long-term antibacterial properties.

[0022] The described polymer materials include silicone rubber, fluorosilicone rubber, polypropylene, polyethylene, polystyrene, polyurethane, and nylon.

[0023] The following further explains and illustrates the principle of the technical solution of the present invention:

[0024] Silica white is a commonly used additive in rubber and plastic materials, mainly playing a reinforcing role. Its chemical composition is nano-silicon dioxide, and the surface contains a large number of silanol groups, showing good hydrophilicity. In order to make silica white have better dispersion in the polymer matrix, silane coupling agents are usually used for surface treatment, and specific functional groups are bonded to the silica white surface through silane hydrolysis and hydroxyl condensation reactions. According to this principle, first, a quaternary ammonium salt silane coupling agent containing a long carbon chain is prepared through quaternization reaction, and then the silica white is surface-treated to obtain silica white with surface-bonded quaternary ammonium salt. On the one hand, the hydrophobic long carbon chain improves the dispersion performance of silica white, and on the other hand, the quaternary ammonium salt plays a good bactericidal role.

[0025] Compared with the prior art, the advantages of the present invention mainly include:

[0026] (1) The quaternary ammonium salt functional group with antibacterial activity is firmly bonded to the surface of silica by chemical bonds, resistant to washing with water, and has a long-lasting antibacterial effect.

[0027] (2) Using long-chain tertiary amines as raw materials, the hydrophobic modification effect is obvious. On the one hand, it can increase the antibacterial effect, and on the other hand, it can improve the dispersibility of silica.

[0028] (3) The antibacterial silica does not contain heavy metal ions such as silver and copper, and has good safety.

[0029] (4) As an antibacterial additive, the antibacterial silica has good versatility, low addition amount, and is easy to use.

[0030] (5) The raw material cost is low, and the preparation process is simple and feasible. Description of the Drawings

[0031] Figure 1 It is the infrared spectrum of dimethyldodecyl [3-(triethoxysilyl)propyl] ammonium chloride in Example 1.

[0032] Figure 2 It is the infrared spectrum of antibacterial silica SiO2-12CL and silica HL300 in Example 1.

[0033] Figure 3 It is the antibacterial rate results of the antibacterial silica in Examples 1 to 5 detected by the oscillation method according to ASTM E2149 standard.

[0034] Figure 4 It is the antibacterial rate results of the polymer materials in Examples 1 to 5 detected by the film sticking method according to ISO 22196:2011(E) standard.

[0035] Figure 5 It is the antibacterial rate results of the polymer materials in Examples 1 to 5 after washing with water and detected by the film sticking method according to ISO 22196:2011(E) standard.

[0036] Figure 6 It is the antibacterial rate results of the silica in Comparative Example 1 and Comparative Example 2 detected by the oscillation method according to ASTM E2149 standard.

[0037] Figure 7 It is the antibacterial rate results of the silicone rubber in Comparative Example 1 and Comparative Example 2 detected by the film sticking method according to ISO 22196:2011(E) standard.

[0038] Figure 8 It is the antibacterial rate results of the silicone rubber in Comparative Example 1 and Comparative Example 2 after washing with water and detected by the film sticking method according to ISO 22196:2011(E) standard. Detailed Embodiments

[0039] The present invention will be described in detail below in conjunction with specific embodiments.

[0040] Example 1

[0041] 1 part by weight of chloropropyltriethoxysilane (Shanghai Titan Technology, analytical pure) and 1.13 parts by weight of N,N-dimethyldodecylamine (Shanghai Titan Technology, analytical pure) were mixed, and quaternization reaction was carried out at 100 °C under vacuum for 10 h to obtain dimethyldodecyl[3-(triethoxysilyl)propyl]ammonium chloride.

[0042] 10 parts by weight of fumed silica (HL300, Huifu Silicon Materials Co., Ltd.) and 1 part by weight of dimethyldodecyl[3-(triethoxysilyl)propyl]ammonium chloride were dispersed in 100 parts by weight of ethanol with a concentration of 95% (v / v), and 0.1 part of acetic acid was added; stirred at room temperature for 12 h, and antibacterial fumed silica was obtained through conventional steps such as static separation and drying, and labeled as SiO2-12CL.

[0043] Dimethyldodecyl[3-(triethoxysilyl)propyl]ammonium chloride was characterized by infrared spectroscopy using the film coating method; antibacterial fumed silica SiO2-12CL and fumed silica HL300 were characterized by infrared spectroscopy using the tablet pressing method.

[0044] Antibacterial performance of fumed silica SiO2-12CL: According to ASTM E2149 standard, 0.1 g of fumed silica was taken for antibacterial test by the shaking method, and the bacteriostatic rate was recorded.

[0045] 100 parts by weight of silicone rubber (HCR 9600, Elkem Silicones), 8 parts by weight of fumed silica SiO2-12CL, and 0.5 part by weight of polydimethylhydrosiloxane (Shanghai Titan Technology) were mixed in a kneader at 150 °C for 10 min, then 0.1 part of platinum catalyst (0.1%, Shanghai Titan Technology) was added on an open mill, and vulcanized at 170 °C for 10 min with a flat vulcanizer to obtain a silicone rubber sheet. According to ISO 22196:2011(E) standard, a square sheet with a size of 5 cm×5 cm was taken for antibacterial test by the film sticking method.

[0046] The silicone rubber sheet was rinsed 3 times with deionized water for 5 minutes each time, and then antibacterial test was carried out by the film sticking method.

[0047] Example 2

[0048] 1 part by weight of chloropropyltrimethoxysilane (Shanghai Titan Technology, analytical pure) and 0.74 part by weight of N,N-dimethylhexadecylamine (Aladdin Chemistry, analytical pure) were mixed, and quaternization reaction was carried out at 120 °C under vacuum for 8 h to obtain dimethyhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0049] 10 parts by weight of silica (HL300, Huifu Silicon Materials Co., Ltd.), 2 parts by weight of dimethylhexadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were dispersed in 90 parts by weight of ethanol with a concentration of 90% (v / v), and 0.1 part of sulfuric acid was added; stirred at room temperature for 14 h, and antibacterial silica was obtained through conventional steps such as static layering and separation and drying, labeled as SiO2-16CL.

[0050] Antibacterial performance of silica SiO2-16CL: According to ASTM E2149 standard, 0.1 g of silica was taken for antibacterial test by the shaking method, and the antibacterial rate was recorded.

[0051] 100 parts by weight of silicone rubber (HCR 9600, Elkem Silicones), 5 parts by weight of silica SiO2-16CL, and 0.5 part by weight of polydimethylhydrogensiloxane (Shanghai Titan Scientific) were mixed in a mixer at 150 °C for 10 min, then 0.1 part of platinum catalyst (0.1%, Shanghai Titan Scientific) was added on an open mill, and vulcanized at 170 °C for 10 min with a flat vulcanizer to obtain a silicone rubber sheet. According to ISO 22196:2011(E) standard, a square sheet with a size of 5 cm×5 cm was taken for antibacterial test by the film sticking method.

[0052] The silicone rubber sheet was rinsed 3 times with deionized water for 5 minutes each time, and then antibacterial test was carried out by the film sticking method.

[0053] Example 3

[0054] 1 part by weight of chloropropyltriethoxysilane (Shanghai Titan Scientific, analytical pure) was mixed with 0.99 part by weight of N,N-dimethyloctadecylamine (Shanghai Titan Scientific, analytical pure), and quaternization reaction was carried out at 140 °C under vacuum for 5 h to obtain dimethyloctadecyl[3-(triethoxysilyl)propyl]ammonium chloride.

[0055] 2 parts by weight of dimethylhexadecyl[3-(triethoxysilyl)propyl]ammonium chloride was dissolved in 100 parts by weight of absolute ethanol, 4 parts by weight of potassium bromide was added, stirred for 3 h, the precipitate was filtered off, and the filtrate was evaporated to dryness to obtain dimethylhexadecyl[3-(triethoxysilyl)propyl]ammonium bromide.

[0056] 10 parts by weight of silica (HL300, Huifu Silicon Materials Co., Ltd.), 1 part by weight of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium bromide were dispersed in 100 parts by weight of ethanol with a concentration of 75% (v / v), and 0.2 part of hydrochloric acid was added; stirred at room temperature for 16 h, and antibacterial silica was obtained through conventional steps such as static layering and separation and drying, labeled as SiO2-18BR.

[0057] Antibacterial properties of silica white SiO2-18BR: According to ASTM E2149 standard, 0.1 g of silica white was taken for antibacterial test by the shaking method, and the antibacterial rate was recorded.

[0058] 100 parts by weight of polypropylene (Y2600T, Shanghai Petrochemical) and 5 parts by weight of silica white SiO2-18BR were mixed in a mixer at 170 °C for 5 min, and then molded by a flat vulcanizer at 170 °C to obtain a 1-mm-thick polypropylene sheet. According to ISO22196:2011(E) standard, a 5 cm × 5 cm square sheet was taken for antibacterial test by the film sticking method.

[0059] The polypropylene sheet was rinsed 3 times with deionized water for 5 minutes each time, and then antibacterial test was carried out by the film sticking method.

[0060] Example 4

[0061] 1 part by weight of chloropropyltriethoxysilane (Shanghai Titan Technology, analytical pure) was mixed with 1.86 parts by weight of N,N-dimethylhexylamine (Shanghai Titan Technology, analytical pure), and quaternization reaction was carried out at 150 °C under vacuum for 15 h to obtain dimethylhexadecyl [3-(triethoxysilyl)propyl] ammonium chloride.

[0062] 1 part by weight of dimethylhexadecyl [3-(triethoxysilyl)propyl] ammonium chloride was dissolved in 100 parts by weight of absolute ethanol, 1 part by weight of potassium iodide was added, and stirred for 5 h. The precipitate was filtered off, and the filtrate was evaporated to dryness to obtain dimethylhexadecyl [3-(triethoxysilyl)propyl] ammonium iodide.

[0063] 10 parts by weight of silica white (VN3, Degussa), 2 parts by weight of dimethylhexadecyl [3-(triethoxysilyl)propyl] ammonium iodide were dispersed in 100 parts by weight of ethanol with a concentration of 95% (v / v), and 0.5 part of oxalic acid was added. Stir at room temperature for 24 h, and antibacterial silica white was obtained through conventional steps such as standing layering, separation and drying, and marked as SiO2-6I.

[0064] Antibacterial properties of silica white SiO2-6I: According to ASTM E2149 standard, 0.1 g of silica white was taken for antibacterial test by the shaking method, and the antibacterial rate was recorded.

[0065] 100 parts by weight of silicone rubber (HCR 9600, Elkem Silicones), 10 parts by weight of fumed silica SiO2-6I, and 0.5 parts by weight of polydimethylhydrogensiloxane (Shanghai Titan Scientific) were mixed in a Banbury mixer at 150 °C for 10 min. Then, 0.1 part of a platinum catalyst (0.1%, Shanghai Titan Scientific) was added on a two-roll mill, and the mixture was vulcanized at 170 °C for 10 min using a flat-bed vulcanizer to obtain a silicone rubber sheet. According to the ISO 22196:2011(E) standard, a 5 cm × 5 cm square sheet was taken for antibacterial testing by the film method.

[0066] The silicone rubber sheet was rinsed 3 times with deionized water for 5 minutes each time, and then antibacterial testing was carried out by the film method.

[0067] Example 5

[0068] 1 part by weight of chloropropyltrimethoxysilane (Shanghai Titan Scientific, analytical grade) was mixed with 0.93 parts by weight of N,N-dimethyldodecylamine (Shanghai Titan Scientific, analytical grade), and quaternization reaction was carried out at 100 °C under vacuum for 10 h to obtain dimethyldodecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0069] 1 part by weight of dimethyldodecyl[3-(trimethoxysilyl)propyl]ammonium chloride was dissolved in 100 parts by weight of absolute ethanol, 1 part by weight of potassium acetate was added, and the mixture was stirred for 3 h. The precipitate was filtered off, and the filtrate was evaporated to dryness to obtain dimethyldodecyl[3-(trimethoxysilyl)propyl]ammonium acetate.

[0070] 10 parts by weight of fumed silica (VN3, Degussa), 1.5 parts by weight of dimethyldodecyl[3-(trimethoxysilyl)propyl]ammonium acetate were dispersed in 100 parts by weight of ethanol with a concentration of 95% (v / v), and 0.2 part of methylbenzenesulfonic acid was added. The mixture was stirred at room temperature for 24 h, and antibacterial fumed silica was obtained through conventional steps such as static layering, separation, and drying, and was labeled as SiO2-12COO.

[0071] Antibacterial performance of fumed silica SiO2-12COO: According to the ASTM E2149 standard, 0.1 g of fumed silica was taken for antibacterial testing by the shaking method, and the antibacterial rate was recorded.

[0072] 100 parts by weight of silicone rubber (HCR 9600, Elkem Silicones), 8 parts by weight of fumed silica SiO2 - 12COO, and 0.5 parts by weight of polydimethylhydrogensiloxane (Shanghai Titan Scientific) were mixed in a Banbury mixer at 150 °C for 10 min. Then, 0.1 part of a platinum catalyst (0.1%, Shanghai Titan Scientific) was added on a two-roll mill, and the mixture was vulcanized at 170 °C for 10 min using a flat vulcanizer to obtain a silicone rubber sheet. According to the ISO 22196:2011(E) standard, a 5 cm × 5 cm square sheet was taken for the antibacterial test by the film adhesion method.

[0073] The silicone rubber sheet was rinsed 3 times with deionized water for 5 minutes each time, and then the antibacterial test was carried out by the film adhesion method.

[0074] Comparative Example 1

[0075] 10 parts by weight of fumed silica (HL300, Huifu Silicon Materials Co., Ltd.) and 1 part by weight of chloropropyltriethoxysilane (Shanghai Titan Scientific, analytical grade) were dispersed in 100 parts by weight of ethanol with a concentration of 95% (v / v), and 0.1 part of acetic acid was added. The mixture was stirred at room temperature for 12 h, and antibacterial fumed silica was obtained through conventional steps such as standing for stratification, separation, and drying, and was labeled as SiO2 - CL.

[0076] Antibacterial performance of fumed silica SiO2 - CL: According to the ASTM E2149 standard, 0.1 g of fumed silica was taken for the antibacterial test by the shaking method, and the antibacterial rate was recorded.

[0077] 100 parts by weight of silicone rubber (HCR 9600, Elkem Silicones), 8 parts by weight of fumed silica SiO2 - CL, and 0.5 parts by weight of polydimethylhydrogensiloxane (Shanghai Titan Scientific) were mixed in a Banbury mixer at 150 °C for 10 min. Then, 0.1 part of a platinum catalyst (0.1%, Shanghai Titan Scientific) was added on a two-roll mill, and the mixture was vulcanized at 170 °C for 10 min using a flat vulcanizer to obtain a silicone rubber sheet. According to the ISO 22196:2011(E) standard, a 5 cm × 5 cm square sheet was taken for the antibacterial test by the film adhesion method.

[0078] The silicone rubber sheet was rinsed 3 times with deionized water for 5 minutes each time, and then the antibacterial test was carried out by the film adhesion method.

[0079] Comparative Example 2

[0080] 10 parts by weight of fumed silica (HL300, Huifu Silicon Materials Co., Ltd.) was dispersed in 100 parts by weight of ethanol with a concentration of 95% (v / v), and 0.1 part of acetic acid was added. The mixture was stirred at room temperature for 12 h, and antibacterial fumed silica was obtained through conventional steps such as standing for stratification, separation, and drying, and was labeled as SiO2 - Si.

[0081] Antibacterial properties of silica white SiO2 - Si: According to ASTM E2149 standard, 0.1 g of silica white was taken for antibacterial test by the shaking method, and the antibacterial rate was recorded.

[0082] 100 parts by weight of silicone rubber (HCR 9600, Elkem Silicones), 8 parts by weight of silica white SiO2 - Si, and 0.5 part by weight of polydimethylhydrogensiloxane (Shanghai Titan Scientific) were mixed in a kneader at 150 °C for 10 min, and then 0.1 part of platinum catalyst (0.1%, Shanghai Titan Scientific) was added on an open mill. The mixture was vulcanized at 170 °C for 10 min using a flat vulcanizer to obtain a silicone rubber sheet. According to ISO 22196:2011(E) standard, a square sheet with a size of 5 cm × 5 cm was taken for antibacterial test by the film - sticking method.

[0083] The silicone rubber sheet was rinsed 3 times with deionized water, 5 minutes each time, and then antibacterial test was carried out by the film - sticking method.

[0084] Infrared test was carried out on the synthesized dimethyldodecyl[3 - (triethoxysilyl)propyl]ammonium chloride. The infrared spectrum is as Figure 1 shown.

[0085] It can be seen from Figure 1 that the wave number at 2924 cm -1 is the antisymmetric stretching vibration peak of -CH2, the wave number at 1492 cm -1 is the asymmetric angular deformation vibration absorption peak of -CH3 connected to N + , the wave number at 3400 cm -1 is the stretching vibration absorption peak of -OH, and the characteristic absorption peak at 1100 cm -1 is the stretching vibration peak of Si - O - C. The wave number at 810 cm -1 is the stretching vibration peak of Si - C bond. The above results indicate that dimethyldodecyl[3 - (triethoxysilyl)propyl]ammonium chloride is successfully synthesized.

[0086] Figure 2 For the infrared spectra of silica white HL300 and antibacterial silica white SiO2 - 12CL in Example 1, it can be seen that obvious infrared absorption peaks appear at 2700 - 2800 cm -1 for the antibacterial silica white, and the vibration absorption peak of silanol groups at 3450 cm -1 weakens. This indicates that quaternary ammonium salt antibacterial groups are introduced on the surface of silica white.

[0087] The antibacterial test results of silica white by the shaking method and the antibacterial test results of material sheets by the film - sticking method in the above examples and comparative examples are shown in the following table:

[0088] Examples / Comparative Examples Bacteriostatic rate of silica white Bacteriostatic rate of material thin slice Bacteriostatic rate of material thin slice after water washing Example 1 99％ 99.9％ 99.9％ Example 2 99.9％ 99％ 99.9％ Example 3 99.9％ 99.9％ 99％ Example 4 99.9％ 99.9％ 99.9％ Example 5 99.9％ 99.9％ 99.9％ Comparative Example 1 10％ 5％ 5％ Comparative Example 2 10％ 3％ 3％

[0089] The results show that silica itself does not have antibacterial effect, while surface-bonded antibacterial silica has excellent antibacterial effect. Adding a small amount of bonded antibacterial silica to polymer materials can significantly inhibit the growth of bacteria and has the function of being wash-resistant, providing long-term antibacterial properties for the materials.

[0090] The antibacterial effect detection of silica in Examples 1-5 is as Figure 3 shown, where the leftmost petri dish is the control group and the other petri dishes are the example groups.

[0091] The antibacterial effect detection of polymer materials in Examples 1-5 (Example 3 is polypropylene and the rest are silicone rubbers) is as Figure 4 shown, where the leftmost petri dish is the control group and the other petri dishes are the example groups.

[0092] The antibacterial effect detection of polymer materials after washing in Examples 1-5 (Example 3 is polypropylene and the rest are silicone rubbers) is as Figure 5 shown, where the leftmost petri dish is the control group and the other petri dishes are the example groups.

[0093] The antibacterial effect detection of silica in Comparative Examples 1-2 is as Figure 6 shown, where the leftmost petri dish is the control group and the other petri dishes are the comparative example groups.

[0094] The antibacterial effect detection of silicone rubber in Comparative Examples 1-2 is as Figure 7 shown, where the leftmost petri dish is the control group and the other petri dishes are the comparative example groups.

[0095] The antibacterial effect detection of silicone rubber after washing in Comparative Examples 1-2 is as Figure 8 shown, where the leftmost petri dish is the control group and the other petri dishes are the comparative example groups.

[0096] The above description of the embodiments is for the convenience of those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A preparation method and application of surface-bonded antibacterial white carbon black, characterized in that: Surface-bonded antibacterial silica is a silica with a long carbon chain quaternary ammonium salt bonded to its surface. Its chemical structure is as follows: Wherein, X is selected from one or a combination of Cl, Br, I or COO; R1 is selected from -H, -CH3, -C2H5, or -CH(CH3)2; R2 is selected from -C6H 13 , -C 12 H 25 , -C 16 H 33 , -C 18 H 37 One or a combination of . The antibacterial white carbon black is prepared by the following method: (1) Chloropropyltrialkoxysilane and long carbon chain tertiary amine are mixed in a molar ratio of 1:(0.5-1.0), and a quaternization reaction is carried out at 80-150° C. under vacuum for 5-20 hours to obtain quaternary ammonium salt silane A. (2) 1 to 5 parts by weight of chloropropyltrialkoxysilane quaternary ammonium salt is dissolved in 100 parts by weight of anhydrous ethanol, 0.2 to 5 parts by weight of inorganic salt is added, and the mixture is stirred for 1 to 5 hours. The precipitate is filtered off, and the filtrate is evaporated to dryness to obtain quaternary ammonium salt silane B. (3) 10 parts by weight of white carbon black and 0.5-2 parts by weight of quaternary ammonium silane A or quaternary ammonium silane B are dispersed in 50-100 parts by weight of ethanol with a concentration of 75-95% (v / v), and 0.01-0.5 parts of acid are added; the mixture is stirred at room temperature for 12-24 hours, and antibacterial white carbon black is obtained by conventional steps such as standing for stratification, separation and drying. The chloropropyltrialkoxysilane includes chloropropyltrimethoxysilane, chloropropyltriethoxysilane and chloropropyltriisopropoxysilane. The long carbon chain tertiary amines include N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylhexadecylamine and N,N-dimethyloctadecylamine. The inorganic salts include potassium bromide, potassium iodide, potassium acetate, sodium bromide, sodium iodide and sodium acetate. The quaternary ammonium salt silane A is a quaternary ammonium salt silane whose anion is chloride ion; the quaternary ammonium salt silane B is a quaternary ammonium salt silane whose anion contains bromide ion, iodide ion or acetate ion. The white carbon black is a gas phase or precipitation white carbon black without surface treatment, and the specific surface area is 100 to 400 m 2 / g. The acid includes acetic acid, hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, and p-toluenesulfonic acid.

2. The antibacterial white carbon black and its application according to claim 1, characterized in that: The antibacterial white carbon black is a non-dissolving antibacterial filler. According to the antibacterial test of ASTM E2149 standard, the antibacterial rate of Escherichia coli is greater than 99%.

3. The antibacterial white carbon black and its application according to claim 1, characterized in that: Adding 0.1 to 10 parts by weight of antibacterial white carbon black to a polymer can give the polymer material long-lasting antibacterial properties. The polymer material includes silicone rubber, fluorosilicone rubber, polypropylene, polyethylene, polystyrene, polyurethane and nylon.

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