CN108160991A - Antibacterial composite granule, antibacterial functionalized composite material and preparation method - Google Patents
Antibacterial composite granule, antibacterial functionalized composite material and preparation method Download PDFInfo
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- CN108160991A CN108160991A CN201810026663.9A CN201810026663A CN108160991A CN 108160991 A CN108160991 A CN 108160991A CN 201810026663 A CN201810026663 A CN 201810026663A CN 108160991 A CN108160991 A CN 108160991A
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- silicate
- silver
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- kaolin
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 239000008187 granular material Substances 0.000 title claims abstract description 35
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 69
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000002052 molecular layer Substances 0.000 claims abstract description 12
- 241000446313 Lamella Species 0.000 claims abstract description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 65
- 235000012211 aluminium silicate Nutrition 0.000 claims description 62
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 55
- 239000005995 Aluminium silicate Substances 0.000 claims description 50
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 27
- 229920006152 PA1010 Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000009830 intercalation Methods 0.000 claims description 17
- 230000002687 intercalation Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002421 anti-septic effect Effects 0.000 abstract description 10
- 230000007774 longterm Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 abstract description 7
- 229920001002 functional polymer Polymers 0.000 abstract description 6
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 9
- 229920002521 macromolecule Polymers 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- -1 silicic acid Salt Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A kind of silicate with anti-microbial property/argentum composite powder body and preparation method, the composite granule include the phyllosilicate with two-dimensional nano layer structure, and amorphous state silver is adsorbed with outside the layer of the silicate；In the layer of the silicate, silver ion is closely compound for molecular level with silicate lamella.The present invention also provides a kind of antibacterial functionalized composite materials and preparation method containing the composite granule.Phyllosilicate with two-dimensional nano layer structure can control the size of Argent grain, prevents from growing up and reunite, and form stable compound, overcome the drawbacks of antiseptic nano silver is easily reunited, hardly possible is disperseed；Part silver is inserted into interlayer simultaneously, closely compound with silicate lamella generation molecular level, during the use of material from now on, can gradually discharge, improve the long-term effect of functional polymer anti-microbial property.The raw materials used in the present invention is simple, price is low, and preparation process is simple, at low cost, and the antibiotic rate of antibacterial functionalized composite material reaches as high as 99.2%.
Description
Technical field
The present invention relates to field of functional polymer composites, more particularly, to a kind of silicate with anti-microbial property/
Argentum composite powder body, antibacterial functionalized composite material and preparation method.
Background technology
There are the microorganisms such as a large amount of bacteriums, mould, virus in human habitat, they are in preference temperature and nutrient condition
Under can breed rapidly, substance is caused to go bad, is corrupt, is mouldy and make the mankind by infecting, induce an illness, the serious threat mankind's
Health.High molecular material is in the most contact, such as various fabrics, rubber, electrical package in people's life, generally
In the case of these articles for use do not have anti-microbial property, the favourable places of some even pathogen growths.With the improvement of living standards,
Requirement of the people to living environment is also higher and higher, therefore the exploitation and application of antimicrobial macromolecule material, has become and closes throughout the world
The social sustainable development subject of note.
Antimicrobial macromolecule refers to add antiseptic in macromolecule, and high molecular products is made to have antibiotic property, when certain
Between interior energy kill and suppress growth of microorganism breeding and its activity a kind of new function material.The antiseptic of argentiferous often has
Excellent anti-microbial property plays antibacterial action in being often added into high molecular material.Such as Chinese patent (application number：
2012101288504.2) a kind of preparation method of anti-bacteria nylon composite material is disclosed, is the plastics by nylon and carrying silver ion
Antiseptic mixing and then extrusion obtain antimicrobial composite material.But silver is to exist in the form of an ion in this kind of antiseptic, easily molten
Go out and then influence the long-term effect of antibacterial, while the silver ion dissolved out also pollutes the environment or endanger health.Nano silver equally has
Good anti-microbial property, but nano-silver powder is easily reunited and is aoxidized, it is difficult to be added separately in PA010 plastics because of large specific surface area
To be uniformly dispersed, and the associativity of itself and high molecular material is poor, thus affects the anti-microbial property and timeliness of nano silver.
Invention content
In view of above-mentioned analysis, the present invention provides a kind of silicate with anti-microbial property/argentum composite powder body, while also carries
For a kind of antibacterial functionalized composite material containing the composite granule and preparation method thereof, antiseptic nano silver is overcome easily to roll into a ball
The drawbacks of poly-, difficult dispersion, while improve the long-term effect of material anti-microbial property.
The purpose of the present invention is mainly achieved through the following technical solutions：
A kind of silicate with anti-microbial property/argentum composite powder body, including the laminar silicic acid with two-dimensional nano layer structure
Salt, the layer of the silicate are adsorbed with amorphous state silver outside；In the layer of the silicate, silver ion is molecular level with silicate lamella
It is close compound.
Phyllosilicate with two-dimensional nano layer structure can control the size of Argent grain, prevents from growing up and reunite, and be formed
Stable compound overcomes the drawbacks of antiseptic nano silver is easily reunited, hardly possible is disperseed；Part silver is inserted into interlayer simultaneously, with silicon
Hydrochlorate lamella generation molecular level is closely compound, during the use of material from now on, can gradually discharge, and improves functional polymer
The long-term effect of anti-microbial property.
Further, the silicate is kaolin.
Kaolin has natural two-dimensional nano layer structure, is a kind of good carrier and template, and kaolin easily obtains
It obtains and cheap, preparation process is simple, at low cost, is a kind of good raw material suitable for producing in enormous quantities.
A kind of preparation method of the silicate with anti-microbial property/argentum composite powder body, using graft process and chemical reduction method
Prepared by the method being combined, include the following steps：
Step 1: by modified Portland and methanol hybrid reaction in proportion, silicate/methanol complex is prepared；
Step 2: by silicate/methanol complex described in step 1 and silver nitrate solution and polyvinylpyrrolidonesolution solution
Hybrid reaction in proportion obtains reaction solution；
Step 3: reducing agent is added in into reaction solution described in step 2, and after the reaction was continued, filtered dry acquisition silicic acid
Salt/argentum composite powder body.
Silicate/argentum composite powder body of the present invention is to be prepared using graft process with the method that chemical reduction method is combined
's.Part silver ion can enter in kaolinic two-dimensional nano layer structure, closely compound with kaolin lamella generation molecular level,
Therefore its stability is strong, good weatherability, and during the use of material from now on, can gradually discharge, and plays the work of sustained release
With increasing the long-term effect of antibacterial.
In order to control to obtain the form and size of silver, polyvinylpyrrolidone (PVP) is selected as dispersant, for height
The native and obtained by the reaction in the future silver-colored simple substance in ridge is disperseed.
Further, the silicate is kaolin；Modified Portland described in step 1 is DMSO modified kaolins.
In order to prepare the composite granule of silver-colored intercalation kaolin soil, selection modified kaolin is needed to prepare kaolin/methanol compound
Object, DMSO is common industrial reagent, and it is very easy to react to form intercalation synthesis system with kaolin, is that efficiency is very high
Precursor, for the later stage prepare methanol and silver kaolin composite advantageous.
Further, the average grain diameter of the DMSO modified kaolins is 10~30 μm, and intercalation rate is not less than 80%.
Kaolinic grain size can influence intercalation rate, can there is good intercalation effect in 10~30 μ ms；Intercalation rate
It is too low, then it can lead to the failure of the intercalation of follow-up methanol and silver.
Further, soluble silver salt described in step 2 is silver nitrate；Reducing agent described in step 3 is NaBH4Solution
With the mixed liquor of sodium citrate solution.
Preferred reducing agent raw material is simple, price is low, and preparation process is simple, at low cost.
A kind of antibacterial functionalized composite material containing the composite granule, including silicate/argentum composite powder body and high score
Sub- material, the flow temperature of the high molecular material is 180-220 DEG C.
It is preferred that the high molecular material that flow temperature is 180-220 DEG C is mixed with silicate/argentum composite powder body, through injection molding
Antibacterial functionalized composite material is made, the too low high molecular material of flow temperature, intensity, impact flexibility are too low, it is impossible to meet
The demand of actual use.During injection molding, high molecular material need to be melted fully, therefore the viscosity flow temperature of high molecular material
Height is spent, the structure of silicate/argentum composite powder body can be destroyed, influence anti-microbial property.
Further, include in parts by weight：80~99 parts of high molecular materials and 1~20 part of silicate/argentum composite powder body.
If silicate/argentum composite powder body content is too low, then the anti-microbial property of composite material is relatively low；Silicate/silver is compound
Powder content is excessively high, can influence the color of high molecular products, and can influence the mechanical property of composite material, such as intensity, impact
Toughness etc..
Further, the high molecular material is polyamide 1010.
Polyamide 1010 (PA1010) have wear-resisting, oil resistant, corrosion-resistant, endurance, good stability of the dimension, it is easy to process and
The advantages that excellent ratio of performance to price, be the engineering plastic for being widely used in the fields such as household electrical appliance, wear part, instrument board
Material, prepares corresponding antimicrobial macromolecule material, can assign high molecular products good anti-microbial property, and product is made to have better city
Field potentiality.
A kind of preparation method of the antibacterial functionalized composite material, using high molecular material as dispersing matrixes, silicate/silver
Composite granule is dispersed phase, and after ball milling mixing, the composite material is obtained through injection molding.
The present invention has the beneficial effect that：
The present invention provides a kind of silicate with anti-microbial property/argentum composite powder body for deficiency of the prior art
And preparation method, while a kind of antibacterial functionalized composite material containing the composite granule and preparation method thereof is also provided.
(1) the raw materials used in the present invention is simple, price is low, and preparation process is simple, at low cost；
(2) there is the phyllosilicate of two-dimensional nano layer structure, can control the size of Argent grain, prevent from growing up and reunite,
Stable compound is formed, overcomes the drawbacks of antiseptic nano silver is easily reunited, hardly possible is disperseed；Preferred kaolin has natural
Two-dimensional nano layer structure, is a kind of good carrier and template, and kaolin is easy to get and cheap, is a kind of good
Raw material；
(3) part silver ion has been entered in kaolinic two-dimensional nano layer structure, and molecular level occurs with kaolin lamella
It is close compound, therefore its stability is strong, good weatherability, and during the use of material from now on, can gradually discharge, and has and holds
Long sustained release performance improves the long-term effect of functional polymer anti-microbial property；
(4) antibiotic rate of antibacterial functionalized composite material provided by the invention reaches as high as 99.2%.
Other features and advantages of the present invention will illustrate in the following description, also, part can become from specification
It obtains it is clear that being understood by implementing the present invention.The purpose of the present invention and other advantages can be by the explanations write
Specifically noted structure is realized and is obtained in book, claims and attached drawing.
Description of the drawings
Attached drawing is only used for showing the purpose of specific embodiment, and is not considered as limitation of the present invention, in entire attached drawing
In, identical reference mark represents identical component.
Fig. 1 is the kaolin of the present invention and the XRD spectrum of kaolin/Ag composite granules, and wherein curve 1 is raw material kaolinite
Soil, curve 2 are intermediate product kaolin/methanol complex, and curve 3 is the kaolin/Ag composite granules being prepared.
Fig. 2 is the kaolin of the present invention and the UV test curves of kaolin/Ag composite granules, and wherein curve 1 is high for raw material
Ridge soil, curve 2 is the kaolin/Ag composite granules being prepared.
Specific embodiment
The preferred embodiment of the present invention is specifically described below in conjunction with the accompanying drawings, wherein, attached drawing forms the application part, and
It is used to illustrate the principle of the present invention together with embodiments of the present invention.
The present invention provides a kind of silicate with anti-microbial property/argentum composite powder body, including with two-dimensional nano layer structure
Phyllosilicate, be adsorbed with amorphous state silver outside the layer of the silicate；In the layer of the silicate, silver ion and silicate plate
Layer is closely compound for molecular level.
Phyllosilicate with two-dimensional nano layer structure can control the size of Argent grain, prevents from growing up and reunite, and be formed
Stable compound overcomes the drawbacks of antiseptic nano silver is easily reunited, hardly possible is disperseed；Part silver is inserted into interlayer simultaneously, with silicon
Hydrochlorate lamella generation molecular level is closely compound, during the use of material from now on, can gradually discharge, and improves functional polymer
The long-term effect of anti-microbial property.
The present invention also provides a kind of antibacterial functionalized composite materials containing the composite granule, multiple including silicate/silver
Powder and high molecular material are closed, the flow temperature of the high molecular material is 180-220 DEG C.
It is preferred that the high molecular material that flow temperature is 180-220 DEG C is mixed with silicate/argentum composite powder body, through injection molding
Antibacterial functionalized composite material is made, the too low high molecular material of flow temperature, intensity, impact flexibility are too low, it is impossible to meet
The demand of actual use.During injection molding, high molecular material need to be melted fully, therefore the viscosity flow temperature of high molecular material
Height is spent, the structure of silicate/argentum composite powder body can be destroyed, influence anti-microbial property.
It is preferred that kaolin and silvery is for kaolin/argentum composite powder body, while preferred polyamide 1010 (i.e. PA1010) conduct
The macromolecule matrix of antibacterial functionalized composite material provides the preparation method of the composite granule and composite material.
Currently preferred kaolin/argentum composite powder body is to be prepared using graft process with the method that chemical reduction method is combined
It obtains, preparation method is：
DMSO modified kaolins and methanol are first pressed mass volume ratio 1 by step 1：10~1：30 mixings 3~10 are small
When, 1-2 hours are stood, after taking out supernatant liquor, obtains kaolin/methanol complex.
DMSO is common industrial reagent, and it is very easy to react to form intercalation synthesis system with kaolin, is effect
The very high precursor of rate, for preparing the kaolin composite advantageous of methanol and silver.By controlling DMSO modified kaolins and first
Ratio, mixing time and the time of repose of alcohol can obtain kaolin/methanol complex of high intercalation rate.
The modified kaolin average grain diameter is 10~30 μm, and the intercalation rate of DMSO modified kaolins is not less than 80%.
Kaolinic grain size can influence intercalation rate, can there is good intercalation effect in 10~30 μ ms；Intercalation rate is too low, then can
Lead to the failure of the intercalation of follow-up methanol and silver.
Kaolin/methanol complex is pressed mass volume ratio 1 by step 2：100 and 1：20 it is separately added into a concentration of 0.5 ×
10-3~2 × 10-3The solvable silver salt solution and mass percent of mol/L is 1%~3% PVP solution, and preferably solvable silver salt is molten
Liquid is silver nitrate solution, is reacted 1~10 hour, obtains reaction solution.
In order to control to obtain the form and size of silver, using PVP as dispersant, for reacting kaolin and future
To silver-colored simple substance disperseed.It will control in reaction time in the range of 1~10 hour, each substance of reaction system can be allowed sufficient
Mixing, in order to the intercalation and reduction reaction of follow-up silver, the reaction time is too short to lead to growing up for Argent grain, form crystalline phase precipitation
Out.
Step 3, according to mass volume ratio 1：40 are added dropwise reducing agent into the reaction solution of step 2, and the reaction was continued 0.5~1.5
Hour, it then filters, kaolin/Ag composite granules is obtained within dry 24 hours through 60 DEG C.It is preferred that reducing agent is 1 for volume ratio：1
NaBH4The mixed liquor of solution and sodium citrate solution, wherein, the NaBH4Solution concentration is 1 × 10-2~2 × 10-2mol/
L, a concentration of 0.01~0.03mol/L of sodium citrate solution.
The too high or too low form size that can influence silver of reductant concentration；Reaction time it is too short then can not intercalation, during reaction
Between it is long, big Argent grain can be formed.In order to control the form and size of silver, when needing concentration and the reaction of preferred reducing agent
Between, kaolin/Ag composite granule of the synthesis with preferably silver-colored form.
Preferably polyamide 1010 (i.e. PA1010) antibacterial functionalized composite material containing kaolin/argentum composite powder body,
Be one kind using PA1010 as dispersing matrixes, using kaolin/argentum composite powder body as dispersed phase, through mixing and ball milling, injection molding, prepare
Obtained antibacterial functionalized composite material, is mainly prepared by the raw material of following parts by weight：PA1010 high molecular materials
80~99 parts are 1~20 part with kaolin/argentum composite powder body.
If kaolin/argentum composite powder body content is too low, then the anti-microbial property of composite material is relatively low；Kaolin/silver is compound
Powder content is excessively high, can influence the color of high molecular products, and can influence the mechanical property of composite material, such as intensity, impact
Toughness etc..
Preparation method is kaolin/1~20 part of argentum composite powder body that score weighs by weight, and polyamide 1010 is (i.e.
PA1010 it) 80~99 parts, with the rotating speed ball milling mixing 1 hour of 400~800r/min, is dried after mixing, is then molded
Molding, cavity heating temperature are 210~230 DEG C, and mold temperature is 150 DEG C.
The temperature of control ball milling speed, injection molding cavity and mold is needed in the preparation process of antibacterial functionalized composite material
Degree.In mechanical milling process, rotating speed is too low to cause mixing not uniform enough；Rotating speed is excessively high, can destroy composite granule structure.It is molded into
During type, the temperature of cavity is too low, then nylon cannot be melted fully and viscosity is excessive is unfavorable for being molded；Temperature is excessively high, can lead
Cause macromolecule discoloration.
Antimicrobial macromolecule material provided by the present invention overcomes that antiseptic silver ion easily dissolves out, nano silver is easily reunited oxygen
Change, difficult the drawbacks of disperseing, there is lasting sustained release performance, improve the long-term effect of functional polymer anti-microbial property.
Embodiment 1
DMSO modified kaolins are pressed into mass volume ratio 1 for 1 gram with methanol：10 mixing, suspend stirring 3 hours, and it is small to stand 1
When, after taking out supernatant liquor, add in a concentration of 0.5 × 10-3The silver nitrate solution 100mL of mol/L and mass percent 1%
PVP solution 20mL react 1 hour, and it is 1 that 40mL volume ratios, which are then added dropwise,：1 NaBH4 solution and the mixing of sodium citrate solution
Liquid, the reaction was continued 0.5 hour, then filters, obtains kaolin/Ag composite granules within dry 24 hours through 60 DEG C.Obtain composite powder
The XRD spectrum of body such as Fig. 1.As seen from the figure, compared with kaolin/methanol intercalated compound, in kaolin/Ag intercalated compounds
(001) 2 θ of crystallographic plane diffraction peak move to 10.410 °, d001Value is reduced to 0.849nm, does not observe the characteristic diffraction peak of silver in figure
(38.28 °, 44.52 °, 64.56 °, 77.56 °) show in kaolin/Ag composite granules and there is no the simple substance of crystalline state
Silver.The atomic diameter of single silver atoms is about 0.3nm, and interlamellar spacing is only expanded than protokaolin in intercalated compound
0.136nm, the diffraction maximum in figure judge that Ag may be with monoatomic morphologic arrangement in kaolinic lamella, and adsorbs
Ag outside kaolin particle mainly exists in the form of amorphous.Fig. 2 is the purple of kaolin and kaolin/Ag composite granules
Outer visible light figure, it can be seen that composite granule in 330nm to 500nm sections tool there are one very strong absorption peak, this also table
There is Ag in bright composite granule, generate stronger resonance effects with ultraviolet light and show extinction phenomenon.
1 part of the composite granule that score weighs by weight, 99 parts of PA1010 are small with the rotating speed ball milling mixing 1 of 400r/min
When, it is dried after mixing, then injection molding obtains antibacterial functionalized PA1010 composite materials PAKA1.Cavity heating temperature
It is 210 DEG C to spend, and mold temperature is 150 DEG C.Anti-microbial property test the results are shown in Table 1.In order to compare, do at identical conditions
PAK1 (1 part of kaolin, 99 parts of PA1010) and PAK20 (20 parts of kaolin, 80 parts of PA1010) sample.It can see pure kaolinite
The composite material that soil addition is formed does not have anti-microbial property, and PAKA1 antibiotic rates can reach 84.6%.
Embodiment 2
DMSO modified kaolins are pressed into mass volume ratio 1 for 1 gram with methanol：20 mixing, suspend stirring 5 hours, and it is small to stand 2
When, after taking out supernatant liquor, add in a concentration of 1 × 10-3The silver nitrate solution 100mL of the mol/L and PVP of mass percent 2%
Solution 20mL reacts 3 hours, and it is 1 that 40mL volume ratios, which are then added dropwise,：1 NaBH4 solution and the mixed liquor of sodium citrate solution,
The reaction was continued 1 hour, then filters, obtains kaolin/Ag composite granules within dry 24 hours through 60 DEG C.Score weighs by weight
5 parts of composite granule, 95 parts of PA1010 with the rotating speed ball milling mixing 1 hour of 600r/min, are dried after mixing, then note
The type of being moulded into obtains antibacterial functionalized PA1010 composite materials PAKA5.Cavity heating temperature is 220 DEG C, and mold temperature is 150 DEG C.
Anti-microbial property test the results are shown in Table 1.
Embodiment 3
DMSO modified kaolins are pressed into mass volume ratio 1 for 1 gram with methanol：30 mixing, suspend stirring 7 hours, and it is small to stand 2
When, after taking out supernatant liquor, add in a concentration of 1.5 × 10-3The silver nitrate solution 100mL of mol/L and mass percent 3%
PVP solution 20mL react 5 hours, and it is 1 that 40mL volume ratios, which are then added dropwise,：1 NaBH4 solution and the mixing of sodium citrate solution
Liquid, the reaction was continued 1.5 hours, then filters, obtains kaolin/Ag composite granules within dry 24 hours through 60 DEG C.Score by weight
10 parts of the composite granule weighed, 90 parts of PA1010 with the rotating speed ball milling mixing 1 hour of 800r/min, are done after mixing
Dry, then injection molding obtains antibacterial functionalized PA1010 composite materials PAKA10.Cavity heating temperature is 230 DEG C, mold temperature
Spend is 150 DEG C.Anti-microbial property test the results are shown in Table 1.
Embodiment 4
DMSO modified kaolins are pressed into mass volume ratio 1 for 1 gram with methanol：30 mixing, suspend stirring 10 hours, and it is small to stand 2
When, after taking out supernatant liquor, add in a concentration of 2 × 10-3The silver nitrate solution 100mL of the mol/L and PVP of mass percent 3%
Solution 20mL reacts 7 hours, and it is 1 that 40mL volume ratios, which are then added dropwise,：1 NaBH4 solution and the mixed liquor of sodium citrate solution,
The reaction was continued 0.5 hour, then filters, obtains kaolin/Ag composite granules within dry 24 hours through 60 DEG C.Score weighs by weight
15 parts of composite granule, 85 parts of PA1010 with the rotating speed ball milling mixing 1 hour of 400r/min, is dried, so after mixing
Injection molding obtains antibacterial functionalized PA1010 composite materials PAKA15 afterwards.Cavity heating temperature is 210 DEG C, and mold temperature is
150℃.Anti-microbial property test the results are shown in Table 1.
Embodiment 5
DMSO modified kaolins are pressed into mass volume ratio 1 for 1 gram with methanol：30 mixing, suspend stirring 3 hours, and it is small to stand 2
When, after taking out supernatant liquor, add in a concentration of 1 × 10-3The silver nitrate solution 100mL of the mol/L and PVP of mass percent 1%
Solution 20mL reacts 10 hours, and it is 1 that 40mL volume ratios, which are then added dropwise,：1 NaBH4 solution and the mixed liquor of sodium citrate solution,
The reaction was continued 0.5 hour, then filters, obtains kaolin/Ag composite granules within dry 24 hours through 60 DEG C.Score weighs by weight
20 parts of composite granule, 80 parts of PA1010 with the rotating speed ball milling mixing 1 hour of 400r/min, is dried, so after mixing
Injection molding obtains antibacterial functionalized PA1010 composite materials PAKA20 afterwards.Cavity heating temperature is 220 DEG C, and mold temperature is
150℃.Anti-microbial property test the results are shown in Table 1.
1 anti-microbial property test result of table
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of silicate with anti-microbial property/argentum composite powder body, which is characterized in that including with two-dimensional nano layer structure
Phyllosilicate, the layer of the silicate are adsorbed with amorphous state silver outside；In the layer of the silicate, silver ion and silicate lamella
It is closely compound for molecular level.
2. silicate/argentum composite powder body according to claim 1, which is characterized in that the silicate is kaolin.
3. a kind of preparation method of the silicate with anti-microbial property/argentum composite powder body, which is characterized in that using graft process with changing
It learns the method that reduction method is combined to prepare, include the following steps：
Step 1: by modified Portland and methanol hybrid reaction in proportion, silicate/methanol complex is prepared；
Step 2: by silicate/methanol complex described in step 1 and silver nitrate solution and polyvinylpyrrolidonesolution solution press than
Example hybrid reaction, obtains reaction solution；
Step 3: reducing agent is added in into reaction solution described in step 2, and after the reaction was continued, filtered dry acquisition silicate/silver
Composite granule.
4. preparation method according to claim 3, which is characterized in that the silicate is kaolin；It is modified described in step 1
Silicate is DMSO modified kaolins.
5. preparation method according to claim 3, which is characterized in that the average grain diameter of the DMSO modified kaolins for 10~
30 μm, intercalation rate is not less than 80%.
6. preparation method according to claim 3, which is characterized in that soluble silver salt described in step 2 is silver nitrate；Step
Reducing agent described in rapid three is NaBH4The mixed liquor of solution and sodium citrate solution.
7. a kind of antibacterial functionalized composite material containing composite granule described in claims 1 or 2, compound including silicate/silver
Powder and high molecular material, the flow temperature of the high molecular material is 180-220 DEG C.
8. antibacterial functionalized composite material according to claim 7, which is characterized in that include in parts by weight：80~99 parts
High molecular material and 1~20 part of silicate/argentum composite powder body.
9. antibacterial functionalized composite material according to claim 7, which is characterized in that the high molecular material is polyamide
1010。
10. a kind of preparation method of the antibacterial functionalized composite material containing composite granule described in claims 1 or 2, feature
It is, is dispersed phase using high molecular material as dispersing matrixes, silicate/argentum composite powder body, after ball milling mixing, is obtained through injection molding
Obtain the composite material.
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| CN110526255A (en) * | 2019-09-29 | 2019-12-03 | 福州大学 | A method of dickite/nano-ag composite is prepared using intercalation |
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| CN112521678A (en) * | 2020-12-14 | 2021-03-19 | 台州市路桥瑞康家庭用品厂 | Antibacterial bath ball and preparation process thereof |
| CN112552578A (en) * | 2020-12-14 | 2021-03-26 | 台州市路桥瑞康家庭用品厂 | Antibacterial film product and preparation process thereof |
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| CN112521678A (en) * | 2020-12-14 | 2021-03-19 | 台州市路桥瑞康家庭用品厂 | Antibacterial bath ball and preparation process thereof |
| CN112552578A (en) * | 2020-12-14 | 2021-03-26 | 台州市路桥瑞康家庭用品厂 | Antibacterial film product and preparation process thereof |
| CN113135681A (en) * | 2021-03-16 | 2021-07-20 | 华中科技大学 | Permeable inorganic antibacterial solution and preparation method thereof |
| CN113135681B (en) * | 2021-03-16 | 2022-06-28 | 华中科技大学 | Permeable inorganic antibacterial solution and preparation method thereof |
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