CN110100839A - A kind of bacteriostatic agent combination and preparation method thereof and the application in antibacterial tableware washing detergent liquid - Google Patents

A kind of bacteriostatic agent combination and preparation method thereof and the application in antibacterial tableware washing detergent liquid Download PDF

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CN110100839A
CN110100839A CN201910437693.3A CN201910437693A CN110100839A CN 110100839 A CN110100839 A CN 110100839A CN 201910437693 A CN201910437693 A CN 201910437693A CN 110100839 A CN110100839 A CN 110100839A
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quantum dot
graphene quantum
chain alkyl
long
antibacterial
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史东海
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Jiangsu Ao Guang Daily Chemical Group Ltd By Share Ltd
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Jiangsu Ao Guang Daily Chemical Group Ltd By Share Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • A01N65/10Apiaceae or Umbelliferae [Carrot family], e.g. parsley, caraway, dill, lovage, fennel or snakebed
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • A01N65/34Rosaceae [Rose family], e.g. strawberry, hawthorn, plum, cherry, peach, apricot or almond
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/382Vegetable products, e.g. soya meal, wood flour, sawdust
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
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    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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    • C11D1/92Sulfobetaines ; Sulfitobetaines

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Abstract

The invention belongs to daily use chemicals articles for washing technical fields, and in particular to a kind of bacteriostatic agent combination and preparation method thereof and the application in antibacterial tableware washing detergent liquid.The bacteriostatic agent group is combined into long-chain alkyl lycine graphene quantum dot and natural plant extracts, mass ratio 1:8 ~ 1:1 of the long-chain alkyl lycine graphene quantum dot and natural plant extracts;Wherein, the natural plant extracts are one of A meter Qin, cistus incanus and Herba speranskiae tuberculatae extract or a variety of mixtures.This method compounds natural plant antibacterial agent with nano anti-biotic material graphene quantum dot (GQDs), it not only can use the efficient quick-acting of GQDs antimicrobial nano material, it using the feature of environmental protection of natural plants antimicrobial component, complexity, broad spectrum antibacterial and can also be not easy to make the advantages that bacterial resistance occurred, to reach collaboration bacteriostasis, the Compound Resisting microbial inoculum of novel high-efficiency environment friendly is developed.

Description

A kind of bacteriostatic agent combination and preparation method thereof and the application in antibacterial tableware washing detergent liquid
Technical field
The invention belongs to daily use chemicals articles for washing technical fields, and in particular to a kind of bacteriostatic agent combination and preparation method thereof and Application in antibacterial tableware washing detergent liquid.
Background technique
With the development of society, the gradually enhancing of people's ecological, environmental protective consciousness, people are more next to the quality requirement of antibacterial agent It is higher.Chemical synthesis antibacterial agent makes microorganism develop drug resistance etc. not met and work as due to difficult to degrade, high residue in the environment, easily The preceding market demand.Therefore, it under the precondition for ensuring effectively to sterilize, reduces the application of chemical synthesis antibacterial agent and seeks Novel green antibacterial agent has become current research hotspot.
Carbon nanomaterial based on graphene, environmentally friendly, cytotoxicity is low, good biocompatibility, is widely used In medicine and life science.Graphene quantum dot (GQDs) is the newcomer of graphene family, is a kind of with graphene-structured Quanta point material, size is in 10 nm or so.Due to its minimum size, high specific surface area, good water-soluble, adjustable Humorous performance, the research and application of GQDs have been to be concerned by more and more people.Different molecules and functional group pair can be passed through GQDs is functionalized to be modified with surface, to meet the application demands such as bio-imaging, drug conveying, sensing and antibacterial.However, GQDs is since the presoma diversity in synthetic method is high, and the surface charge and functional character of the GODs of distinct methods preparation is not Together, so that but also synthesized GQDs shows different dispersion performance and anti-microbial property.Therefore, developing one kind has The graphene quantum dot nano material of superior dispersibility and anti-microbial property has the very big market demand.
Effective antibacterial and sterilization component in plant-source antibacterial agent is extracted out of natural plants body, is had inexpensive, low The advantages that poison, easily decomposition and environmental sound.Since the antibacterial activity of single restraining and sterilizing bacteria ingredient is poor, antimicrobial spectrum is relatively narrow and Long-time service is also easy to produce the defects of drug resistance, therefore compounds to a variety of antibacterial plant ingredients, enhances its antibacterial efficacy, expands it Broad spectrum antibacterial is very important.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of bacteriostatic agent combination and preparation method thereof and in antibacterial tableware washing detergent liquid In application, natural plant antibacterial agent compounds with nano anti-biotic material graphene quantum dot (GQDs), not only may be used by this method With using the efficient quick-acting of GQDs antimicrobial nano material, can also using the feature of environmental protection of natural plants antimicrobial component, complexity, It broad spectrum antibacterial and is not easy to make the advantages that bacterial resistance occurred, to reach collaboration bacteriostasis, develop new and effective The Compound Resisting microbial inoculum of environmental protection.
In order to achieve the above object, the present invention is achieved by the following technical programs:
The first purpose of the invention is to provide a kind of combination of bacteriostatic agent, the bacteriostatic agent group is combined into long-chain alkyl lycine stone Black alkene quantum dot and natural plant extracts, the long-chain alkyl lycine@graphene quantum dot and natural plant extracts Mass ratio 1:8 ~ 1:1;Wherein, the natural plant extracts are one in A meter Qin, cistus incanus and Herba speranskiae tuberculatae extract Kind or a variety of mixtures.
As a preferred solution of the present invention, the long-chain alkyl lycine@graphene quantum dot the preparation method is as follows: with Citric acid is that carbon source pyrolysismethod in ammonium hydroxide prepares amino functional graphene quantum dot;It is reacted again by carboxyl amine, by long-chain Alkyl betaine is supported on amino functional graphene quantum dot surface, and long-chain alkyl lycine@graphene quantum dot is made.
As a preferred solution of the present invention, the partial size of the long-chain alkyl lycine@graphene quantum dot is 5 ~ 15 nm.
A second object of the present invention is to provide a kind of preparation methods of bacteriostatic agent combination, comprising the following steps:
(1) preparation of amino functional graphene quantum dot:
Citric acid is dissolved in secondary distilled water and is added ammonium hydroxide, after mixing, mixture is transferred in polytetrafluoroethylene (PTFE) In the autoclave of lining, 4 ~ 8 h of insulation reaction and it is cooled to room temperature at 100 ~ 200 DEG C;It is filtered to remove insoluble fragment;It will obtain Clarified solution dialysis, freeze-drying obtain solid powder, as amino functional graphene quantum dot;
(2) preparation of long-chain alkyl lycine@graphene quantum dot nano antibacterial agent:
Long-chain alkyl lycine is sub- in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxysuccinimidyl acyl It is activated in 2- (N- morpholine) ethanesulfonic acid buffer of amine, wherein the concentration of 2- (N- morpholine) ethanesulfonic acid buffer is 0.1 mol·L-1, pH value 6.0, after activation, the phosphate buffer solution of addition amino functional graphene quantum dot in mixed liquor Reaction, dialysis, freeze-drying obtain long-chain alkyl lycine@graphene quantum dot, wherein the long-chain alkyl lycine is N- Chain alkyl carboxylic acid type glycine betaine, molecular formula are as follows: CH3(CH2)nN+(CH3)2CH2COO-, n=11 ~ 17 in formula;
(3) preparation of bacteriostatic agent combination:
By long-chain alkyl lycine@graphene quantum dot obtained by step (2) and natural plant extracts according to mass ratio 1:8 ~ 1:1 It prepares, obtains compound;As bacteriostatic agent combines.
Wherein, the natural plant extracts are one of A meter Qin, cistus incanus and Herba speranskiae tuberculatae extract or more Kind mixture.
Specifically, the preparation step of the amino functional graphene quantum dot is as follows:
Citric acid is dissolved in secondary distilled water, is added ammonium hydroxide (28wt% aqueous solution), after mixing, mixture is transferred to In the autoclave of polytetrafluoroethyllining lining, 4 ~ 8 h of insulation reaction at 100 ~ 200 DEG C.After being cooled to room temperature, with 0.22 μm Water system miillpore filter filtering, removes insoluble fragment.By obtained clarified solution through bag filter that molecular cut off is 1 KDa in going Dialyse 48 h in ionized water, then freeze-dried to obtain solid powder, as amino functional graphene quantum dot.
The preparation of the long-chain alkyl lycine@graphene quantum dot nano antibacterial agent:
By long-chain alkyl lycine (BS) in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDCHCl) and 2- (N- morpholine) ethanesulfonic acid buffer (0.1 molL of n-hydroxysuccinimide (NHS)-1, pH=6.0) and 0.5 h of middle activation. Wherein, the ratio between amount of substance of each raw material is BS:EDCHCl:NHS=1:4:4.After activation, amino function is added in mixed liquor Can graphite alkene quantum dot phosphate buffer solution, react 12 h, through molecular cut off be 1 KDa bag filter in deionization Dialyse 24 h in water, then freeze-dried to obtain long-chain alkyl lycine@graphene quantum dot nano antibacterial agent, wherein long-chain Alkyl betaine is N- chain alkyl carboxylic acid type glycine betaine, molecular formula are as follows: CH3(CH2)nN+(CH3)2CH2COO-, n=11 in formula ~ 17。
The A meter Qin extract the preparation method comprises the following steps: the seed of A meter Qin (Ammi Visnaga) and aerial part are used After pulverizer crushes, 30-50 mesh powder is collected, powder and 4%NaCl aqueous solution mass ratio 1:6-12 is taken, uses Clevenger type Laser heating flows back 6 hours to there is no until oil droplet drippage to volatile oil determination apparatus under normal pressure, collects upper layer essential oil, nothing is added It is filtered after aqueous sodium persulfate is dry, obtains A meter Qin extract.
The cistus incanus extracts the preparation method comprises the following steps: by the cauline leaf of cistus incanus (Cistus Incanus) After being crushed with pulverizer, 30-50 mesh powder is collected.Take powder and water quality ratio 1:4-6,100 DEG C immersion 5-10 minutes, filtering Filtrate, the active carbon decoloring of filtrate are obtained, the filtrate after decoloration removes solvent and obtains cistus incanus extracts.
The Herba speranskiae tuberculatae extract the preparation method comprises the following steps: lopseed (Phryma leptostachya L.) is used pulverizer After crushing, 30-50 mesh powder is collected.Take powder and 60wt% ethyl alcohol mass ratio 1:8-12,75 DEG C extraction 2-4 hours, filter To filtrate, the active carbon decoloring of filtrate, the filtrate after decoloration removes solvent and obtains Herba speranskiae tuberculatae extract.
Third object of the present invention is to provide a kind of antibacterial tableware washing detergent liquids of bacteriostatic agent combination, and the antibacterial tableware washing detergent liquid is under The group for stating mass fraction is grouped as:
Alkyl polyglycoside 0~30%
Amino acid type surfactant 0~20%
Amphoteric surfactant 0~10%
Thickener 0~3%
Citric acid 0-2%
Chelating agent 0.05~0.1%
Bacteriostatic agent combination 1.5~5.0%
Water Surplus.
As a preferred solution of the present invention, the alkyl polyglycoside is octyl-Plantacare 818, cocoyl glucoside or lauryl Glucoside.
As a preferred solution of the present invention, the amino acid type surfactant is lauroyl glutamate, cocounut oil acyl It is glutamate, Hamposyl L salt, one or more in cocoyl sarcosine salt.
As a preferred solution of the present invention, the thickener be cellulose thickener, guar gum and its derivative species, It is one or more in the double stearates of PEG-120 methyl dioleate, Macrogol 6000.
As a preferred solution of the present invention, the chelating agent is EDTA-2Na.
Fourth object of the present invention is that antibacterial tableware washing detergent liquid of the invention can be applied to meal wash field.Due to chain alkyl sweet tea The collaboration bacteriostasis of dish alkali@graphene quantum dot and natural plant extracts, bacteriostatic activity greatly improve, effectively antibacterial While, dirt can be removed, and play the role of removing odors, realize a step and complete decontamination, antibacterial and taste removal purpose.
The present invention is coated on GQDs nanoparticle surface using long-chain alkyl lycine, constructs long-chain alkyl lycine@stone Black alkene quantum dot nano antibacterial agent, shows the antibacterial activity of enhancing, and minimal inhibitory concentration value is substantially less than free chain alkyl Glycine betaine;Alkyl betaine molecule covalent is bonded to the surface GQDs, makes the surface GQDs that there is apparent local positive charge density With hydrophobic chain number, to greatly improve its anti-microbial property.
Contain non-terpene ester, terpene and oxygen-containing terpenoid in A meter Qin (Ammi Visnaga), has stronger anti- Bacterial activity, moreover it is possible to enhance vascular dynamics.Contain labdane type diterpene chemical combination in cistus incanus (Cistus Incanus) Object can be used as anti-inflammatory agent treatment local skin inflammation.Effect ingredient wood in lopseed (Phryma leptostachya L.) Rouge element substance has anti-inflammatory, antibacterial, anti-oxidant, antiallergy and antitumor and other effects.
Compared with prior art, the invention has the following advantages:
(1) the method for the present invention raw material is easy to get, simple process: the present invention is using citric acid cheap and easy to get as carbon source, preferably " under On and " one-step synthesis method amino functional graphene quantum dot.It is reacted by simple carboxyl amine, by alkyl betaine and ammonia The graphene quantum dot of base functionalization is coupled, and obtains long-chain alkyl lycine@graphene quantum dot antibacterial agent, and average grain diameter is 5~15 nm.Preparation method is simple and efficient, is at low cost, it can be achieved that industrialized production.
(2) antibacterial agent combination product excellent antibacterial performance obtained by the method for the present invention:
(3) the antibacterial tableware washing detergent liquid of green of the method for the present invention preparation it is antibacterial it is high-efficient, nontoxic, non-stimulated, environmental-friendly, can biology Degradation and with rear noresidue, can be used for the cleaning of tableware.
Specific embodiment
Below by specific embodiment, invention is further described in detail.But those skilled in the art will manage Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment Art or condition person, described technology or conditions carry out to specifications according to the literature in the art.Agents useful for same or instrument Production firm person is not specified, being can be with conventional products that are commercially available.
In specific embodiment 4-10, long-chain alkyl lycine graphene quantum dot is indicated with A, A meter Qin, graywacke rose Common vetch and Herba speranskiae tuberculatae extract group share B expression.Then complex antimicrobials 1 represent A:B=1:8 in following embodiment;Complex antimicrobials 2 Represent A:B=1:4;Complex antimicrobials 3 represent A:B=1:2;Complex antimicrobials 3 represent A:B=1:1.
Embodiment 1
A kind of preparation method of bacteriostatic agent combination, comprising the following steps:
(1) preparation of amino functional graphene quantum dot:
Citric acid is dissolved in secondary distilled water, is added ammonium hydroxide (28wt% aqueous solution), after mixing, mixture is transferred to In the autoclave of polytetrafluoroethyllining lining, 4 ~ 8 h of insulation reaction at 100 ~ 200 DEG C.After being cooled to room temperature, with 0.22 μm Water system miillpore filter filtering, removes insoluble fragment.By obtained clarified solution through bag filter that molecular cut off is 1 KDa in going Dialyse 48 h in ionized water, then freeze-dried to obtain solid powder, as amino functional graphene quantum dot;
(2) preparation of long-chain alkyl lycine@graphene quantum dot nano antibacterial agent:
By long-chain alkyl lycine (BS) in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDCHCl) and 2- (N- morpholine) ethanesulfonic acid buffer (0.1 molL of n-hydroxysuccinimide (NHS)-1, pH=6.0) and 0.5 h of middle activation. Wherein, the ratio between amount of substance of each raw material is BS:EDCHCl:NHS=1:4:4.After activation, amino function is added in mixed liquor Can graphite alkene quantum dot phosphate buffer solution, react 12 h, through molecular cut off be 1 KDa bag filter in deionization Dialyse 24 h in water, then freeze-dried to obtain long-chain alkyl lycine@graphene quantum dot nano antibacterial agent, wherein long-chain Alkyl betaine is N- chain alkyl carboxylic acid type glycine betaine, molecular formula are as follows: CH3(CH2)nN+(CH3)2CH2COO-, n=11 in formula ~ 17。
(3) preparation of bacteriostatic agent combination:
Long-chain alkyl lycine@graphene quantum dot obtained by step (2) and natural plant extracts are matched according to mass ratio 1:8 System, obtains compound;As bacteriostatic agent combines.
Wherein, the natural plant extracts be A meter Qin, the A meter Qin extract the preparation method comprises the following steps: by A meter Qin After the seed and aerial part of (Ammi Visnaga) are crushed with pulverizer, 30-50 mesh powder is collected, powder and 4%NaCl water are taken Solution quality ratio 1:6-12, using Clevenger type volatile oil determination apparatus under normal pressure laser heating flow back 6 hours to there is no Until oil droplet drips, upper layer essential oil is collected, is filtered after anhydrous sodium sulfate drying is added, obtains A meter Qin extract.
Embodiment 2
A kind of preparation method of bacteriostatic agent combination, comprising the following steps:
(1) preparation of amino functional graphene quantum dot:
Citric acid is dissolved in secondary distilled water, is added ammonium hydroxide (28wt% aqueous solution), after mixing, mixture is transferred to In the autoclave of polytetrafluoroethyllining lining, 4 ~ 8 h of insulation reaction at 100 ~ 200 DEG C.After being cooled to room temperature, with 0.22 μm Water system miillpore filter filtering, removes insoluble fragment.By obtained clarified solution through bag filter that molecular cut off is 1 KDa in going Dialyse 48 h in ionized water, then freeze-dried to obtain solid powder, as amino functional graphene quantum dot;
(2) preparation of long-chain alkyl lycine@graphene quantum dot nano antibacterial agent:
By long-chain alkyl lycine (BS) in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDCHCl) and 2- (N- morpholine) ethanesulfonic acid buffer (0.1 molL of n-hydroxysuccinimide (NHS)-1, pH=6.0) and 0.5 h of middle activation. Wherein, the ratio between amount of substance of each raw material is BS:EDCHCl:NHS=1:4:4.After activation, amino function is added in mixed liquor Can graphite alkene quantum dot phosphate buffer solution, react 12 h, through molecular cut off be 1 KDa bag filter in deionization Dialyse 24 h in water, then freeze-dried to obtain long-chain alkyl lycine@graphene quantum dot nano antibacterial agent, wherein long-chain Alkyl betaine is N- chain alkyl carboxylic acid type glycine betaine, molecular formula are as follows: CH3(CH2)nN+(CH3)2CH2COO-, n=11 in formula ~ 17。
(3) preparation of bacteriostatic agent combination:
Long-chain alkyl lycine@graphene quantum dot obtained by step (2) and natural plant extracts are matched according to mass ratio 1:2 System, obtains compound;As bacteriostatic agent combines.
Wherein, the natural plant extracts are cistus incanus extracts;The preparation of the cistus incanus extracts Method are as follows: after crushing the cauline leaf of cistus incanus (Cistus Incanus) with pulverizer, collect 30-50 mesh powder.Take powder End and water quality ratio 1:4-6,100 DEG C immersions 5-10 minute, be obtained by filtration filtrate, filtrate use activity carbon decoloring, after decoloration Filtrate removes solvent and obtains cistus incanus extracts.
Embodiment 3
A kind of preparation method of bacteriostatic agent combination, comprising the following steps:
(1) preparation of amino functional graphene quantum dot:
Citric acid is dissolved in secondary distilled water, is added ammonium hydroxide (28wt% aqueous solution), after mixing, mixture is transferred to In the autoclave of polytetrafluoroethyllining lining, 4 ~ 8 h of insulation reaction at 100 ~ 200 DEG C.After being cooled to room temperature, with 0.22 μm Water system miillpore filter filtering, removes insoluble fragment.By obtained clarified solution through bag filter that molecular cut off is 1 KDa in going Dialyse 48 h in ionized water, then freeze-dried to obtain solid powder, as amino functional graphene quantum dot;
(2) preparation of long-chain alkyl lycine@graphene quantum dot nano antibacterial agent:
By long-chain alkyl lycine (BS) in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDCHCl) and 2- (N- morpholine) ethanesulfonic acid buffer (0.1 molL of n-hydroxysuccinimide (NHS)-1, pH=6.0) and 0.5 h of middle activation. Wherein, the ratio between amount of substance of each raw material is BS:EDCHCl:NHS=1:4:4.After activation, amino function is added in mixed liquor Can graphite alkene quantum dot phosphate buffer solution, react 12 h, through molecular cut off be 1 KDa bag filter in deionization Dialyse 24 h in water, then freeze-dried to obtain long-chain alkyl lycine@graphene quantum dot nano antibacterial agent, wherein long-chain Alkyl betaine is N- chain alkyl carboxylic acid type glycine betaine, molecular formula are as follows: CH3(CH2)nN+(CH3)2CH2COO-, n=11 in formula ~ 17。
(3) preparation of bacteriostatic agent combination:
Long-chain alkyl lycine@graphene quantum dot obtained by step (2) and natural plant extracts are matched according to mass ratio 1:4 System, obtains compound;As bacteriostatic agent combines.
Wherein, the natural plant extracts are Herba speranskiae tuberculatae extract;The Herba speranskiae tuberculatae extract the preparation method comprises the following steps: will After lopseed (Phryma leptostachya L.) is crushed with pulverizer, 30-50 mesh powder is collected.Take powder and 60wt% second Alcohol mass ratio 1:8-12,75 DEG C extraction 2-4 hours, be obtained by filtration filtrate, filtrate with active carbon decoloring, remove by the filtrate after decoloration Solvent is gone to obtain Herba speranskiae tuberculatae extract.
Embodiment 4
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauryl glucoside 18%
3 Cocoamidopropyl betaine 5%
4 Lauroyl glutamate potassium 20%
5 The double stearates of Macrogol 6000 2%
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 Complex antimicrobials 2 3%
The above-mentioned antibacterial tableware washing detergent liquid of green the preparation method is as follows:
1,1,2,3,4 raw material is successively weighed and stirring and dissolving is uniform, temperature is maintained at 70-80 DEG C;
2,5 are added, stirring dissolves it sufficiently completely, and stirring starts to cool down after ten minutes;
3,6,7 are added, adjusts pH value between 5.5-6.5
4,8 are added when temperature drops to 45 DEG C or less, discharged after stirring.
Embodiment 5
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauryl glucoside 18%
3 Cocoamidopropyl betaine 5%
4 Lauroyl glutamate potassium 20%
5 The double stearates of Macrogol 6000 2
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 Complex antimicrobials 2 1.5%
Embodiment 6
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauryl glucoside 18%
3 Cocoamidopropyl betaine 5%
4 Lauroyl glutamate potassium 20%
5 The double stearates of Macrogol 6000 2
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 Complex antimicrobials 2 4.5%
Embodiment 7
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Sodium lauroyl glutamate 12%
3 Cocoyl glucoside 20%
4 Cocamidopropyl propyl amide hydroxy sulfo lycine 10%
5 PEG-120 methyl dioleate 1%
6 EDTA-2Na 0.1%
7 Citric acid Appropriate PH5.5-6.5
8 Complex antimicrobials 1 3%
Embodiment 8
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauroyl glutamate potassium 30%
3 Lauroyl both sexes base sodium acetate 15%
4 Hydroxypropyl methyl cellulose 1%
5 EDTA-2Na 0.1%
6 Citric acid Appropriate PH5.5-6.5
7 Complex antimicrobials 3 2%
Embodiment 9
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauryl glucoside 20%
3 Cocamidopropyl propyl amide hydroxy sulfo lycine 15%
4 PEG-120 methyl dioleate 1%
5 EDTA-2Na 0.05%
6 Citric acid Appropriate PH5.5-6.5
7 Complex antimicrobials 4 1.5%
Comparative example 1
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauroyl glutamate potassium 20%
3 Lauryl glucoside 18%
4 Cocoamidopropyl betaine 5%
5 The double stearates of Macrogol 6000 0.6%
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 Shredding 0.06%
Comparative example 2
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauroyl glutamate potassium 20%
3 Lauryl glucoside 18%
4 Cocoamidopropyl betaine 5%
5 The double stearates of Macrogol 6000 0.6%
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 A 0.4%
Comparative example 3
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauroyl glutamate potassium 20%
3 Lauryl glucoside 18%
4 Cocoamidopropyl betaine 5%
5 The double stearates of Macrogol 6000 0.6%
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 B 1.6%
Comparative example 4
A kind of antibacterial tableware washing detergent liquid of bacteriostatic agent combination, the antibacterial tableware washing detergent liquid consist of the following components in percentage by mass:
Serial number Material name Percentage composition
1 Water Surplus
2 Lauroyl glutamate potassium 20%
3 Lauryl glucoside 18%
4 Cocoamidopropyl betaine 5%
5 The double stearates of Macrogol 6000 0.6%
6 EDTA-2Na 0.05%
7 Citric acid Appropriate PH5.5-6.5
8 Nano silver ion antibiotic agent 0.4%
The measurement of dishwashing number:
Artificial dishwashing number test: by made embodiment 4,7,8,9 according to manual dishwashing with detergent national standard GB9985-2000's Artificial dishwashing number test method carries out dishwashing test.The results are shown in Table 1.
The corresponding dishwashing number of each embodiment of table 1
Embodiment 4 7 8 9
Dishwashing number/ 3.5 3.5 3 2.5
From test result as can be seen that each embodiment dishwashing number is all larger than 2.5 plates of national standard.
Biocidal property test:
The above is only preferred embodiments of the present invention, is not intended to limit the scope of the present invention, therefore all It is any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, belongs to this In the range of inventive technique scheme.

Claims (10)

1. a kind of combination of bacteriostatic agent, which is characterized in that the bacteriostatic agent group be combined into long-chain alkyl lycine graphene quantum dot and Natural plant extracts, mass ratio 1:8~1 of the long-chain alkyl lycine@graphene quantum dot and natural plant extracts: 1;Wherein, the natural plant extracts are one of A meter Qin, cistus incanus and Herba speranskiae tuberculatae extract or a variety of mixed Close object.
2. a kind of bacteriostatic agent combination according to claim 1, which is characterized in that the long-chain alkyl lycine@graphene Quantum dot the preparation method is as follows: the pyrolysismethod in ammonium hydroxide prepares amino functional graphene quantum dot using citric acid as carbon source; Again by carboxyl-amine reaction, long-chain alkyl lycine is supported on amino functional graphene quantum dot surface, long alkane is made Base glycine betaine@graphene quantum dot.
3. a kind of bacteriostatic agent combination according to claim 2, which is characterized in that the long-chain alkyl lycine@graphene The partial size of quantum dot is 5~15nm.
4. a kind of preparation method of bacteriostatic agent combination as claimed in claim 3, which comprises the following steps:
(1) preparation of amino functional graphene quantum dot:
Citric acid is dissolved in secondary distilled water and is added ammonium hydroxide, after mixing, mixture is transferred in polytetrafluoroethylene (PTFE) In the autoclave of lining, 4~8h of insulation reaction and it is cooled to room temperature at 100~200 DEG C;It is filtered to remove insoluble fragment;Will To clarified solution dialysis, freeze-drying obtain solid powder, as amino functional graphene quantum dot;
(2) preparation of long-chain alkyl lycine@graphene quantum dot nano antibacterial agent:
Long-chain alkyl lycine is sub- in 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxysuccinimidyl acyl It is activated in 2- (N- morpholine) ethanesulfonic acid buffer of amine, wherein the concentration of 2- (N- morpholine) ethanesulfonic acid buffer is 0.1mol·L-1, pH value 6.0, after activation, the phosphate-buffered of addition amino functional graphene quantum dot in mixed liquor Solution reaction, dialysis, freeze-drying obtain long-chain alkyl lycine@graphene quantum dot, wherein the long-chain alkyl lycine For N- chain alkyl carboxylic acid type glycine betaine, molecular formula are as follows: CH3(CH2)nN+(CH3)2CH2COO-, n=11~17 in formula;
(3) preparation of bacteriostatic agent combination:
By long-chain alkyl lycine@graphene quantum dot obtained by step (2) and natural plant extracts according to mass ratio 1:8~1: 1 prepares, and obtains compound;As bacteriostatic agent combines, wherein the natural plant extracts are A meter Qin, cistus incanus With one of Herba speranskiae tuberculatae extract or a variety of mixtures.
5. the antibacterial tableware washing detergent liquid based on a kind of combination of bacteriostatic agent described in claim 1-3 any claim, which is characterized in that The antibacterial tableware washing detergent liquid consists of the following components in percentage by mass:
6. antibacterial tableware washing detergent liquid according to claim 5, which is characterized in that the alkyl polyglycoside is octyl-decyl glucose Glycosides, cocoyl glucoside or lauryl glucoside.
7. antibacterial tableware washing detergent liquid according to claim 5, which is characterized in that the amino acid type surfactant is laurel It is acyl glutamate, cocounut oil acyl glutamate, Hamposyl L salt, one or more in cocoyl sarcosine salt.
8. antibacterial tableware washing detergent liquid according to claim 5, which is characterized in that the thickener is cellulose thickener, melon It is one or more in that glue and its double stearates of derivative species, PEG-120 methyl dioleate, Macrogol 6000.
9. antibacterial tableware washing detergent liquid according to claim 5, which is characterized in that the chelating agent is EDTA-2Na.
10. antibacterial tableware washing detergent liquid described in claim 5 is applied to meal wash field.
CN201910437693.3A 2019-05-24 2019-05-24 A kind of bacteriostatic agent combination and preparation method thereof and the application in antibacterial tableware washing detergent liquid Pending CN110100839A (en)

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