CN105968416B - A kind of antibacterial agent for antibiotic plastic - Google Patents

A kind of antibacterial agent for antibiotic plastic Download PDF

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CN105968416B
CN105968416B CN201610354059.XA CN201610354059A CN105968416B CN 105968416 B CN105968416 B CN 105968416B CN 201610354059 A CN201610354059 A CN 201610354059A CN 105968416 B CN105968416 B CN 105968416B
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CN105968416A (en
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吴琦
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Guangzhou Baoshan Science And Technology Application Co Ltd
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    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/26Carbonates; Bicarbonates
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    • C08K3/32Phosphorus-containing compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
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    • C08K2003/324Alkali metal phosphate
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Abstract

The invention belongs to antibacterial agent fields, specifically disclose a kind of antibacterial agent and preparation method thereof for antibiotic plastic.It is characterized in that, it include mainly following raw material, by parts by weight meter: 20~35 parts of white mica powder, 5~15 parts of zeolite powder, 5~15 parts of conch meal, 40~60 parts of 30% hydrogen peroxide, 40~80 parts of trisodium phosphate solution, 0.4~6 part of basic amino acid, 20~35 parts of silver chlorate, 40~55 parts of sodium thiosulfate, 20~30 parts of sodium sulfite, 5~10 parts of acetic acid, Na4P2O7·10H25~15 parts of O, 30~45 parts of thioglycol, 20~35 parts of ethyl alcohol, 10~25 parts of sodium bicarbonate, 15~40 parts of diluent, 5~20 parts of coupling agent.Antibacterial antiplaque agent effect provided by the invention is obvious, good with the compatibility of plastics.

Description

A kind of antibacterial agent for antibiotic plastic
Technical field
The invention belongs to antibacterial agent fields, concretely relate to a kind of for the antibacterial agent of antibiotic plastic and its preparation side Method.
Background technique
With the progress of human society, plastic products occupy increasingly consequence in daily life.At the same time, Various environmental pollutions are also got worse, and plastic products are easy the pollution by bacterium in the long-term use, have been directly resulted in The propagation and sprawling of evil bacterium, endanger people's health.Antibacterial agent can effectively inhibit the taste of bacterium as a kind of additive It is raw.Plastic antimicrobial agent is generally divided into inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and complex antimicrobials.But addition at present Most of antibacterial antiplaque agent effects into plastics are unobvious, bad with the compatibility of plastics.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of antibacterial agent and preparation method thereof for antibiotic plastic, with Improve the problem that existing plastic antimicrobial agent antibacterial effect is unobvious, bad with the compatibility of plastics.
In order to achieve the above objectives, the technical solution used in the present invention are as follows:
A kind of antibacterial agent for antibiotic plastic includes mainly following raw material, by parts by weight meter: white mica powder 20~35 Part, 5~15 parts of zeolite powder, 5~15 parts of conch meal, 40~60 parts of 30% hydrogen peroxide, 40~80 parts of trisodium phosphate solution, alkaline ammonia 0.4~6 part of base acid, 20~35 parts of silver chlorate, 40~55 parts of sodium thiosulfate, 20~30 parts of sodium sulfite, 5~10 parts of acetic acid, Na4P2O7·10H25~15 parts of O, 30~45 parts of thioglycol, 20~35 parts of ethyl alcohol, 10~25 parts of sodium bicarbonate, diluent 15 ~40 parts, 5~20 parts of coupling agent.
Preferably, in the preferred embodiment, the basic amino acid is lysine, arginine, histidine, color It is one or more kinds of in propylhomoserin.
Preferably, in the preferred embodiment, the diluent is ethylene glycol, propylene glycol, wherein ethylene glycol, third The ratio of glycol is 1:1~1.2.
Preferably, in the preferred embodiment, the coupling agent is silane compound.
Preferably, in the preferred embodiment, the silane compound is amino silane, vinyl silanes or first One or both of base acryloxy silane.
The present invention also provides a kind of preparation methods of antibacterial agent for antibiotic plastic, comprising the following steps:
(1) white mica powder, the zeolite powder, the conch meal are uniformly mixed to obtain hybrid solid powder, it will be described Hybrid solid powder and 30% hydrogen peroxide solution are stirred 10~15min, then stand 50~70min, place it in Dry 6~8h in 100~120 DEG C of baking ovens;
(2) by the hybrid solid powder and the trisodium phosphate solution, basic amino acid stirring 15 after drying ~35min then stands 20~40min, and 5~7min is centrifugated under the speed of 3000~4000r/min, takes lower sediment 3~5h is toasted in 350~400 DEG C of baking ovens, then stands and is cooled to 20~30 DEG C, is prepared into purifying hybrid solid powder, it will The pure solid powder collected is placed in high pressure milling device, is milled and is sieved at 10~15MPa, it is prepared into 120~ 140 mesh ultrafine solids powder;
(3) silver chlorate is dissolved in the mixed solution of the sodium sulphate and the sodium thiosulfate, while uses institute Vinegar acid for adjusting pH is stated 4~5,2~4h is stirred at 20~40 DEG C;
(4) the ultrafine solids powder is added in the mixed solution of step (3) preparation by 1:10~15 in mass ratio, Being warming up to 55~60 DEG C, the acetic acid is added to adjust pH value is 6~8, stirs 1~2h, then be centrifugated to obtain solid product, distills Water wash repeatedly the solid product into washing lotion without Ag+ after, dried at 100~110 DEG C, obtain immobilized silver-colored antibacterial pulvis;
(5) the immobilized silver-colored antibacterial pulvis is added to the Na4P2O7·10H2In O, stirred at 25~65 DEG C molten It solves 2~4 hours, is stirred 10~15min under 600~800r/min revolving speed, continuously adds sodium bicarbonate, the ethyl alcohol, institute Thioglycol is stated, the ultrasound for applying 750~800W at 20~30 DEG C carries out 10~15min of decentralized processing to solution, and 20 4~6h is mixed at~30 DEG C, mixing speed is 100~200r/min;
(6) diluent and coupling agent 3:1~1.5 in mass ratio are first mixed to get mixed solution, then will step Suddenly solution is mixed with above-mentioned mixed solution 1:0.2~0.5 in mass ratio after the dispersion that (5) obtain, then in a high speed mixer Stirring 20~30 minutes after the completion of to be mixed, stands 10~12h, and remove solvent to its rotary evaporation, then be placed in 75~80 DEG C The particle is milled and is sieved again, is prepared into 140~160 by dry 6~8h in baking oven, the particle after collecting drying Mesh powder, then the powder is subjected to 2~4h of activation processing at 180~240 DEG C, then stop heating up and be cooled to 20~ 30 DEG C, obtain the antibacterial agent for antibiotic plastic.
Beneficial effects of the present invention: the present invention is using the high bio-molecules basic amino acid of biological safety as anti- Antibacterial substance silver ion is evenly spread to nanoparticle surface, improves antibacterial agent by bacterium active metallic ion dispersing agent Anti-microbial property.Antibacterial agent provided by the invention is good with Compatibility in Plastics, can effectively inhibit the growth of bacterium, to Escherichia coli, For the inhibition killing rate of the strains such as staphylococcus aureus up to 99% or more, antibacterial effect is obvious.
Specific embodiment
Technical solution of the present invention is further described combined with specific embodiments below.
Embodiment 1:
A kind of antibacterial agent for antibiotic plastic includes mainly following raw material, by parts by weight meter: 20 parts of white mica powder, 5 parts of zeolite powder, 5 parts of conch meal, 40 parts of 30% hydrogen peroxide, 40 parts of trisodium phosphate solution, 0.4 part of basic amino acid, silver chlorate 20 Part, 40 parts of sodium thiosulfate, 20 parts of sodium sulfite, 5 parts of acetic acid, Na4P2O7·10H25 parts of O, 30 parts of thioglycol, ethyl alcohol 20 Part, 10 parts of sodium bicarbonate, 15 parts of diluent, 5 parts of coupling agent.
The present embodiment neutral and alkali amino acid is lysine and arginic mixture.
In the present embodiment diluent be ethylene glycol, propylene glycol, wherein ethylene glycol, propylene glycol ratio be 1:1.
Coupling agent is silane compound in the present embodiment.
Silane compound is amino silane in the present embodiment.
The present embodiment additionally provides a kind of preparation method of antibacterial agent for antibiotic plastic, comprising the following steps:
(1) white mica powder, zeolite powder, conch meal are uniformly mixed to obtain hybrid solid powder, by hybrid solid powder and 30% Hydrogen peroxide solution is stirred 10min, then stands 50min, places it in dry 6h in 100 DEG C of baking ovens;
(2) it by the hybrid solid powder and trisodium phosphate solution, basic amino acid stirring 15min after drying, then stands 20min is centrifugated 5min under the speed of 3000r/min, takes lower layer to be deposited in 350 DEG C of baking ovens and toasts 3h, then stands 20 DEG C are cooled to, purifying hybrid solid powder is prepared into, the pure solid powder of collection is placed in high pressure milling device, It mills and is sieved under 10MPa, be prepared into 120 mesh ultrafine solids powder;
(3) silver chlorate is dissolved in the mixed solution of sodium sulphate and sodium thiosulfate, while with vinegar acid for adjusting pH 4, 2h is stirred at 20 DEG C;
(4) ultrafine solids powder is added in the mixed solution of step (3) preparation by 1:10 in mass ratio, is warming up to 55 DEG C, acetic acid is added to adjust pH value is 6, stirs 1h, then is centrifugated to obtain solid product, distilled water washs solid product to washing repeatedly In liquid without Ag+ after, dried at 100 DEG C, obtain immobilized silver-colored antibacterial pulvis;
(5) immobilized silver-colored antibacterial pulvis is added to Na4P2O7·10H2In O, stirring and dissolving 2 hours, 600r/ at 25 DEG C It is stirred 10min under min revolving speed, continuously adds sodium bicarbonate, ethyl alcohol, thioglycol, applies the ultrasound of 750W at 20 DEG C Decentralized processing 10min is carried out to solution, and 4h is mixed at 20 DEG C, mixing speed 100r/min;
(6) diluent and coupling agent 3:1 in mass ratio are first mixed to get mixed solution, then point that step (5) is obtained Solution is mixed with above-mentioned mixed solution 1:0.2 in mass ratio after dissipating, and is then stirred 20 minutes in a high speed mixer, to be mixed complete Cheng Hou stands 10h, and removes solvent to its rotary evaporation, then is placed in 75 DEG C of baking ovens dry 6h, the particle after collecting drying, Particle is milled and is sieved again, is prepared into 140 mesh powders, then powder is subjected to activation processing 2h at 180 DEG C, with Stop heating up and being cooled to 20 DEG C afterwards, obtains the antibacterial agent for antibiotic plastic.
Embodiment 2:
A kind of antibacterial agent for antibiotic plastic includes mainly following raw material, by parts by weight meter: 35 parts of white mica powder, 15 parts of zeolite powder, 15 parts of conch meal, 60 parts of 30% hydrogen peroxide, 80 parts of trisodium phosphate solution, 6 parts of basic amino acid, silver chlorate 35 Part, 55 parts of sodium thiosulfate, 30 parts of sodium sulfite, 10 parts of acetic acid, Na4P2O7·10H215 parts of O, 45 parts of thioglycol, ethyl alcohol 35 parts, 25 parts of sodium bicarbonate, 40 parts of diluent, 20 parts of coupling agent.
The present embodiment neutral and alkali amino acid is the mixture of arginine and histidine.
In the present embodiment diluent be ethylene glycol, propylene glycol, wherein ethylene glycol, propylene glycol ratio be 1:1.2.
Coupling agent is silane compound in the present embodiment.
Silane compound is vinyl silanes in the present embodiment.
The present embodiment additionally provides a kind of preparation method of antibacterial agent for antibiotic plastic, comprising the following steps:
(1) white mica powder, zeolite powder, conch meal are uniformly mixed to obtain hybrid solid powder, by hybrid solid powder and 30% Hydrogen peroxide solution is stirred 15min, then stands 70min, places it in dry 8h in 120 DEG C of baking ovens;
(2) it by the hybrid solid powder and trisodium phosphate solution, basic amino acid stirring 35min after drying, then stands 40min is centrifugated 7min under the speed of 4000r/min, takes lower layer to be deposited in 400 DEG C of baking ovens and toasts 5h, then stands 30 DEG C are cooled to, purifying hybrid solid powder is prepared into, the pure solid powder of collection is placed in high pressure milling device, It mills and is sieved under 15MPa, be prepared into 140 mesh ultrafine solids powder;
(3) silver chlorate is dissolved in the mixed solution of sodium sulphate and sodium thiosulfate, while with vinegar acid for adjusting pH 5, 4h is stirred at 40 DEG C;
(4) ultrafine solids powder is added in the mixed solution of step (3) preparation by 1:15 in mass ratio, is warming up to 60 DEG C, acetic acid is added to adjust pH value is 8, stirs 2h, then is centrifugated to obtain solid product, distilled water washs solid product to washing repeatedly In liquid without Ag+ after, dried at 110 DEG C, obtain immobilized silver-colored antibacterial pulvis;
(5) immobilized silver-colored antibacterial pulvis is added to Na4P2O7·10H2In O, stirring and dissolving 4 hours at 65 DEG C, It is stirred 15min under 800r/min revolving speed, continuously adds sodium bicarbonate, ethyl alcohol, thioglycol, applies 800W's at 30 DEG C Ultrasound carries out decentralized processing 15min to solution, and 6h is mixed at 30 DEG C, mixing speed 200r/min;
(6) diluent and coupling agent 3:1.5 in mass ratio are first mixed to get mixed solution, then step (5) is obtained Solution is mixed with above-mentioned mixed solution 1:0.5 in mass ratio after dispersion, is then stirred 30 minutes in a high speed mixer, wait stir After the completion of mixing, 12h is stood, and solvent is removed to its rotary evaporation, then is placed in 80 DEG C of baking ovens dry 8h, after collecting drying Grain, particle is milled and is sieved again, be prepared into 160 mesh powders, then powder is activated at 240 DEG C 4h then stops heating up and being cooled to 30 DEG C, obtains the antibacterial agent for antibiotic plastic.
Embodiment 3:
A kind of antibacterial agent for antibiotic plastic includes mainly following raw material, by parts by weight meter: 27 parts of white mica powder, 10 parts of zeolite powder, 10 parts of conch meal, 50 parts of 30% hydrogen peroxide, 60 parts of trisodium phosphate solution, 3.2 parts of basic amino acid, silver chlorate 27 Part, 48 parts of sodium thiosulfate, 25 parts of sodium sulfite, 7 parts of acetic acid, Na4P2O7·10H210 parts of O, 37 parts of thioglycol, ethyl alcohol 27 Part, 17 parts of sodium bicarbonate, 27 parts of diluent, 12 parts of coupling agent.
The present embodiment neutral and alkali amino acid is the mixture of arginine, histidine and tryptophan.
In the present embodiment diluent be ethylene glycol, propylene glycol, wherein ethylene glycol, propylene glycol ratio be 1:1~1.1.
Coupling agent is silane compound in the present embodiment.
Silane compound is the mixing of amino silane, vinyl silanes or methacryloxypropyl silane in the present embodiment Object.
The present embodiment additionally provides a kind of preparation method of antibacterial agent for antibiotic plastic, comprising the following steps:
(1) white mica powder, zeolite powder, conch meal are uniformly mixed to obtain hybrid solid powder, by hybrid solid powder and 30% Hydrogen peroxide solution is stirred 12min, then stands 60min, places it in dry 7h in 110 DEG C of baking ovens;
(2) it by the hybrid solid powder and trisodium phosphate solution, basic amino acid stirring 25min after drying, then stands 30min is centrifugated 6min under the speed of 3500r/min, takes lower layer to be deposited in 375 DEG C of baking ovens and toasts 4h, then stands 25 DEG C are cooled to, purifying hybrid solid powder is prepared into, the pure solid powder of collection is placed in high pressure milling device, It mills and is sieved under 12MPa, be prepared into 130 mesh ultrafine solids powder;
(3) silver chlorate is dissolved in the mixed solution of sodium sulphate and sodium thiosulfate, while being existed with vinegar acid for adjusting pH 4.5,3h is stirred at 30 DEG C;
(4) ultrafine solids powder is added in the mixed solution of step (3) preparation by 1:12 in mass ratio, is warming up to 57 DEG C, acetic acid is added to adjust pH value is 7, stir 1.5h, then be centrifugated to obtain solid product, distilled water washs solid product extremely repeatedly In washing lotion without Ag+ after, dried at 105 DEG C, obtain immobilized silver-colored antibacterial pulvis;
(5) immobilized silver-colored antibacterial pulvis is added to Na4P2O7·10H2In O, stirring and dissolving 3 hours, 700r/ at 45 DEG C It is stirred 12min under min revolving speed, continuously adds sodium bicarbonate, ethyl alcohol, thioglycol, applies the ultrasound of 770W at 25 DEG C Decentralized processing 12min is carried out to solution, and 5h is mixed at 25 DEG C, mixing speed 150r/min;
(6) diluent and coupling agent 3:1.2 in mass ratio are first mixed to get mixed solution, then step (5) is obtained Solution is mixed with above-mentioned mixed solution 1:0.3 in mass ratio after dispersion, is then stirred 25 minutes in a high speed mixer, to be mixed After the completion, 11h is stood, and solvent is removed to its rotary evaporation, then is placed in 77 DEG C of baking ovens dry 7h, after collecting drying Grain, particle is milled and is sieved again, be prepared into 150 mesh powders, then powder is activated at 210 DEG C 3h then stops heating up and being cooled to 25 DEG C, obtains the antibacterial agent for antibiotic plastic.
Antibacterial agent quality made from embodiment 1-3 is detected, by carrying out 96 hours ultraviolet lights to product, Discoloration-resistant, the anti-microbial property of antibacterial agent are detected.By comparison, it was found that product made from embodiment 3 and plastic compatible Property it is more preferable, discoloration-resistant is stronger, inhibit bacterium ability it is stronger, anti-microbial property is more preferable.

Claims (4)

1. a kind of antibacterial agent for antibiotic plastic, which is characterized in that include mainly following raw material, by parts by weight meter: white clouds 20~35 parts of female powder, 5~15 parts of zeolite powder, 5~15 parts of conch meal, 40~60 parts of 30% hydrogen peroxide, trisodium phosphate solution 40~80 Part, 0.4~6 part of basic amino acid, 20~35 parts of silver chlorate, 40~55 parts of sodium thiosulfate, 20~30 parts of sodium sulfite, acetic acid 5~10 parts, Na4P2O7·10H25~15 parts of O, 30~45 parts of thioglycol, 20~35 parts of ethyl alcohol, 10~25 parts of sodium bicarbonate, 15~40 parts of diluent, 5~20 parts of coupling agent;
The basic amino acid is lysine, arginine, histidine, one or more kinds of in tryptophan;
The diluent be ethylene glycol, propylene glycol, wherein ethylene glycol, propylene glycol ratio be 1:1~1.2.
2. a kind of antibacterial agent for antibiotic plastic according to claim 1, it is characterised in that: the coupling agent is silicon Hydride compounds.
3. a kind of antibacterial agent for antibiotic plastic according to claim 2, it is characterised in that: the silane compound For one or both of amino silane, vinyl silanes or methacryloxypropyl silane.
4. a kind of preparation method of the antibacterial agent as described in any one of claims 1-3 for antibiotic plastic, which is characterized in that The following steps are included:
(1) white mica powder, the zeolite powder, the conch meal are uniformly mixed to obtain hybrid solid powder, by the mixing Solid powder and 30% hydrogen peroxide solution are stirred 10~15min, then stand 50~70min, place it in 100~ Dry 6~8h in 120 DEG C of baking ovens;
(2) by after drying the hybrid solid powder and the trisodium phosphate solution, the basic amino acid stirring 15~ 35min then stands 20~40min, and 5~7min is centrifugated under the speed of 3000~4000r/min, lower layer is taken to be deposited in 3~5h is toasted in 350~400 DEG C of baking ovens, then stands and is cooled to 20~30 DEG C, is prepared into purifying hybrid solid powder, will be received The pure solid powder of collection is placed in high pressure milling device, is milled and is sieved at 10~15MPa, is prepared into 120~140 Mesh ultrafine solids powder;
(3) silver chlorate is dissolved in the mixed solution of the sodium sulfite and the sodium thiosulfate, while described in use Vinegar acid for adjusting pH stirs 2~4h 4~5 at 20~40 DEG C;
(4) the ultrafine solids powder is added in the mixed solution of step (3) preparation by 1:10~15 in mass ratio, heating Adjusting pH value to 55~60 DEG C, the addition acetic acid is 6~8, stirs 1~2h, then be centrifugated to obtain solid product, distilled water is anti- After backwashing wash the solid product into washing lotion without Ag+ after, in 100~110 DEG C of baking ovens, obtain immobilized silver-colored antibacterial pulvis;
(5) the immobilized silver-colored antibacterial pulvis is added to the Na4P2O7·10H2In O, the stirring and dissolving 2~4 at 25~65 DEG C Hour, it is stirred 10~15min under 600~800r/min revolving speed, continuously adds sodium bicarbonate, the ethyl alcohol, the sulfenyl Ethyl alcohol, the ultrasound for applying 750~800W at 20~30 DEG C carry out 10~15min of decentralized processing to solution, and at 20~30 DEG C 4~6h of lower mixing, mixing speed are 100~200r/min;
(6) diluent and coupling agent 3:1~1.5 in mass ratio are first mixed to get mixed solution, then by step (5) Solution is mixed with above-mentioned mixed solution 1:0.2~0.5 in mass ratio after obtained dispersion, then stirs 20 in a high speed mixer ~30 minutes, after the completion of to be mixed, 10~12h is stood, and solvent is removed to its rotary evaporation, then be placed in 75~80 DEG C of baking ovens Dry 6~8h, the particle after collecting drying, the particle is milled and is sieved again, be prepared into the powder of 140~160 mesh End, then the powder is subjected to 2~4h of activation processing at 180~240 DEG C, then stop heating up and being cooled to 20~30 DEG C, Obtain the antibacterial agent for antibiotic plastic.
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CN113462028B (en) * 2021-07-02 2023-05-02 科迈特新材料有限公司 Nanometer antibacterial agent for plastics and preparation method thereof

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