CN106084406B - A kind of antimicrobial composite material and the mat of composite material preparation - Google Patents
A kind of antimicrobial composite material and the mat of composite material preparation Download PDFInfo
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- CN106084406B CN106084406B CN201610543476.9A CN201610543476A CN106084406B CN 106084406 B CN106084406 B CN 106084406B CN 201610543476 A CN201610543476 A CN 201610543476A CN 106084406 B CN106084406 B CN 106084406B
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- composite material
- mat
- zine oxide
- nano zine
- oxide particle
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
- A47G2009/001—Anti-allergen; Anti-mite
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The present invention provides the mat of a kind of antimicrobial composite material and composite material preparation, the composite material includes polymeric substrate and polymer overmold nano zine oxide particle, and polymer overmold nano zine oxide particle is covering material using the copolymer of divinylbenzene and 1- vinyl imidazole or 1- vinyl -3- alkyl imidazo ion liquid.
Description
Technical field
The present invention relates to a kind of antimicrobial composite material and the mats prepared by the composite material.
Background technique
Existing common straw mat is generally woven using the processing of natural seat grass, and this straw mat is not washable, is easy aging, is soft
It is soft bad, and acarid easy to breed, bacterium, human health is had an impact.
Summary of the invention
The main purpose of the present invention is to provide a kind of antimicrobial composite material for being used to prepare mat, which has
Good anti-microbial property, therefore also there is good anti-microbial property with its mat prepared.
It is another object of the present invention to provide a kind of antimicrobial composite material for being used to prepare mat, composite material tools
There is good flame retardant property, therefore also there is good flame retardant property with its mat prepared.
It is another object of the present invention to provide a kind of mats, have good anti-microbial property.
To achieve the above objectives, the present invention provides a kind of antimicrobial composite material, is used to prepare mat comprising polymer matrix
Material and polymer overmold nano zine oxide particle, the polymeric substrate are selected from one or more of following polymer: poly-
Ethylene, polypropylene, polyester, polyacrylonitrile, polyamide.
Preferably, the polymer overmold nano zine oxide particle using divinylbenzene and 1- vinyl imidazole and/or
The copolymer of 1- vinyl -3- alkyl imidazo ion liquid is covering material, wherein 1- vinyl -3- alkyl imidazo ion liquid
Alkyl can be methyl, ethyl, propyl or butyl, the anion of 1- vinyl -3- alkyl imidazole ionic liquid is halogen
Anion.
Preferably, the composite material further includes fire retardant, and the fire retardant is the fire retardant of phosphoric acid ester, the polymerization
The mass fraction ratio of object substrate, the polymer overmold nano zine oxide particle and the fire retardant is 100: (2~15):
(0.5~2).
Preferably, the polymer overmold nano zine oxide particle is prepared by surfactant- free emulsion polymerization, specific preparation side
Method is as follows:
(1) polyethylene of dispersing agent pyrrolidones is added in the suspension being configured to nano zine oxide and deionized water, stirs
It mixes after being uniformly dispersed, the pH value of suspension is adjusted to 6.5~7；
(2) after the suspension that step (1) obtains being heated to 78~82 DEG C under agitation, initiator is added；
(3) divinylbenzene is added in the suspension obtained to step (2), 1- vinyl is added dropwise after reaction 1~3 hour
Imidazoles or 1- vinyl -3- alkyl imidazo ion liquid after the reaction was continued 3~5 hours, stop reaction；
(4) it is filtered by vacuum after being cooled to room temperature the reaction solution that step (3) obtains, is dry, crushed, obtaining the polymer
Coat nano zine oxide particle.
It is noted that above-mentioned steps (1)-(4) carry out in a nitrogen atmosphere.
When preparing the polymer overmold nano zine oxide particle, nano zine oxide is evenly dispersed in suspension, causes
Agent is decomposed under heat effect generates free radical, and the monomer molecule being dissolved in suspension is initiated polymerization and forms one section with hydrophilic group
The free radical activity chain of group.Nanoparticle surface is positively charged, easily with electronegative free radical activity chain combination, to make its surface
Hydrophobicity enhancing is conducive to residual monomer in surface of nanometer zinc oxide and polymerize cladding, so that it is multiple to form nano zine oxide/high polymer
Close particle.
Preferably, the initiator is ammonium persulfate and/or potassium peroxydisulfate.
The composite material of the invention can be prepared into fiber, be yarn by fibrous woven, be then woven into mat, make
When standby fiber, the polymeric substrate preferably selects polyester, polyamide or polyacrylonitrile；The composite material can also pass through
Extrusion molding is prepared into size and the similar plastic hollow pipe of Lin's grass, and diameter is about 1mm~3mm, then uses and tatami rush
Identical weaving method is woven to mat, when preparing plastic hollow pipe, the polymeric substrate preferably select polyethylene and/or
Polypropylene.Specific weaving method belongs to the prior art in mat field, and the present invention is no longer described in detail.
The present invention also provides a kind of mat, the mat using composite material preparation fiber or plastic hollow pipe braiding and
At the composite material includes polymeric substrate and polymer overmold nano zine oxide particle, the polymer overmold nanometer
Zinc oxide fine particles are using the copolymer of divinylbenzene and 1- vinyl imidazole or 1- vinyl -3- alkyl imidazo ion liquid
Covering material.
Preferably, the composite material further includes fire retardant, and the fire retardant is phosphate ester flame retardants.
Preferably, the polymeric substrate is selected from one or more of following polymer: polyethylene, polypropylene, polyester,
Polyacrylonitrile, polyamide.
The mat of composite material preparation provided by the present invention compared with prior art, has the advantage that
(1) manufacture craft is simple, easy to operate；
(2) mat made from has excellent flame retardant property；
(3) partial size of mat good anti-bacterial effect made from, polymer overmold nano zine oxide particle is submicron order, is held very much
It easily anchors in the micropore in the microgap of fiber surface and between fiber and fiber between yarn and yarn, so that washability is held
Long, the mutual segment winding of the polymeric layer with polymeric substrate of surface of nanometer zinc oxide cladding or anchor are embedding, thus and polymer matrix
Material compatibility is preferable, not easily to fall off；
(4) copolymer of divinylbenzene and vinyl imidazole or vinyl ionic liquid has coarse micro-nano table
Face, unique meso-hole structure and single organic backbone, so that polymer overmold nano zine oxide particle is with super-hydrophobic
Characteristic, to assign mat certain hydrophobicity, also easy cleaning while making it be not easy to stain；
(5) nano zine oxide particle is compounded with phosphate ester flame retardants, is conducive to the flame retardant property for improving composite material,
Zinc oxide is big as its specific heat capacity of inorganic filler, using accumulation of heat and thermally conductive material is made to be not easy to reach thermal decomposition temperature, while oxygen
The addition for changing zinc changes the thermal-oxidative degradation process of material, generates more carbon residues, stable protection layer of charcoal is formed, thus favorably
In raising fire retardant to the fire retardancy of composite material.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Embodiment 1
A kind of polymer overmold nano zine oxide particle is provided, is made by the following method:
(1) nano zine oxide of 20 mass parts and deionized water are configured to the water slurry that mass fraction is 10%, to
The polyvinylpyrrolidone of 0.5 mass parts is added in above-mentioned water slurry, is dispersed with stirring 80min under conditions of 1500r/min,
The pH value of finely dispersed suspension is adjusted to 6.5；
(2) by suspension that step (1) obtains, agitating and heating is warming up to 78 DEG C under the conditions of 450r/min, stablizes 12min
The ammonium persulfate of 0.4 mass parts is added afterwards；
(3) divinylbenzene of 20 mass parts is added in the suspension obtained to step (2) and is added dropwise 10 after reaction 1 hour
1- vinyl -3- alkyl imidazole metal iodide ions the liquid of mass parts after the reaction was continued 3 hours, stops reaction；
(4) it is filtered by vacuum after being cooled to room temperature the reaction solution that step (3) obtains, filter cake is placed in drying box in 70 DEG C
Under the conditions of dry 30 hours, the filter cake after drying is crushed, the polymer overmold nano zine oxide particle is obtained.
Above-mentioned steps (1)-(4) carry out in a nitrogen atmosphere.
Composite material is prepared using polymer overmold nano zine oxide particle made from embodiment 1: by 100 mass parts
High density polyethylene (HDPE), 10 mass parts polymer overmold nano zine oxide particle and 0.5 mass parts fire retardant BDP mixing after
It is added in extruder, the master batch of composite material is made, the examination of corresponding size is then prepared using the master batch of the composite material
Sample is tested for the property.
Embodiment 2
A kind of polymer overmold nano zine oxide particle is provided, is made by the following method:
(1) nano zine oxide of 20 mass parts and deionized water are configured to the water slurry that mass fraction is 10%, to
The polyvinylpyrrolidone of 0.5 mass parts is added in above-mentioned water slurry, is dispersed with stirring 80min under conditions of 1500r/min,
The pH value of finely dispersed suspension is adjusted to 6.5；
(2) by suspension that step (1) obtains, agitating and heating is warming up to 78 DEG C under the conditions of 450r/min, stablizes 12min
The ammonium persulfate of 0.4 mass parts is added afterwards；
(3) divinylbenzene of 20 mass parts is added in the suspension obtained to step (2) and is added dropwise 10 after reaction 1 hour
The 1- vinyl imidazole of mass parts after the reaction was continued 3 hours, stops reaction；
(4) it is filtered by vacuum after being cooled to room temperature the reaction solution that step (3) obtains, filter cake is placed in drying box in 70 DEG C
Under the conditions of dry 30 hours, the filter cake after drying is crushed, the polymer overmold nano zine oxide particle is obtained.
Above-mentioned steps (1)-(4) carry out in a nitrogen atmosphere.
Composite material is prepared using polymer overmold nano zine oxide particle made from embodiment 2: by 100 mass parts
High density polyethylene (HDPE), 10 mass parts polymer overmold nano zine oxide particle and 0.5 mass parts fire retardant BDP mixing after
It is added in extruder, the master batch of composite material is made, the examination of corresponding size is then prepared using the master batch of the composite material
Sample is tested for the property.
Comparative example 3
Composite material directly is prepared using uncoated nano zine oxide: by the high density polyethylene (HDPE) of 100 mass parts, 10 matter
It is added in extruder after measuring the nano zine oxide particle of part and the fire retardant BDP mixing of 0.5 mass parts, composite material is made
Then master batch is tested for the property using the sample that the master batch of the composite material prepares corresponding size.
Embodiment 4
A kind of polymer overmold nano zine oxide particle is provided, is made by the following method:
(1) nano zine oxide of 20 mass parts and deionized water are configured to the water slurry that mass fraction is 10%, to
The polyvinylpyrrolidone of 0.5 mass parts is added in above-mentioned water slurry, is dispersed with stirring 80min under conditions of 1500r/min,
The pH value of finely dispersed suspension is adjusted to 6.5；
(2) by suspension that step (1) obtains, agitating and heating is warming up to 78 DEG C under the conditions of 450r/min, stablizes 12min
The ammonium persulfate of 0.4 mass parts is added afterwards；
(3) divinylbenzene of 20 mass parts is added in the suspension obtained to step (2), after reaction 3 hours, stops anti-
It answers；
(4) it is filtered by vacuum after being cooled to room temperature the reaction solution that step (3) obtains, filter cake is placed in drying box in 70 DEG C
Under the conditions of dry 30 hours, the filter cake after drying is crushed, the polymer overmold nano zine oxide particle is obtained.
Above-mentioned steps (1)-(4) carry out in a nitrogen atmosphere.
Composite material is prepared using polymer overmold nano zine oxide particle made from embodiment 4: by 100 mass parts
High density polyethylene (HDPE), 10 mass parts polymer overmold nano zine oxide particle and 0.5 mass parts fire retardant BDP mixing after
It is added in extruder, the master batch of composite material is made, the examination of corresponding size is then prepared using the master batch of the composite material
Sample is tested for the property.
Embodiment 5
The preparation method of the polymer overmold nano-oxide particle of embodiment 5 is the same as embodiment 2.
The polymer overmold nano zine oxide particle made from embodiment 5 prepares composite material: by the highly dense of 100 mass parts
It is added in extruder after degree polyethylene and the mixing of the polymer overmold nano zine oxide particle of 10 mass parts, composite material is made
Master batch, be then tested for the property using the sample that the master batch of the composite material prepares corresponding size.
Comparative example 6
Fire retardant is only added in polymeric substrate and prepares composite material: by the high density polyethylene (HDPE) of 100 mass parts and 0.5
It is added in extruder after the fire retardant BDP mixing of mass parts, the master batch of composite material is made, then utilizes the composite material
Master batch prepare the sample of corresponding size and be tested for the property.
Comparative example 7
Comparative example 7 is blank assay, is tested for the property using high density polyethylene (HDPE) preparation respective samples.
Table 1 is the test result of the main performance of the sample of embodiment and comparative example 1-7.The wherein test reference of contact angle
Standard GB/T/T 30693-2014 test sample Static water contact angles.The test reference standard GB/T 2406- of oxygen index (OI)
93.The test reference standard FZ/T01021-92 of bacteriostasis rate.
Table 1
For comparative example 3 compared with Examples 1 and 2, hydrophobic performance is poor, and the nano zine oxide particle after illustrating cladding assigns multiple
The preferable hydrophobic performance of condensation material；And the anti-microbial property of comparative example 3 is decreased obviously after repeatedly washing, after illustrating cladding
Nano zine oxide particle is added in polymeric substrate, has more longlasting washability.Nano zine oxide is coated in embodiment 4
Polymer does not have copolymerizable vinyl groups imidazoles or vinyl iminazole ionic liquid, and the hydrophobicity and cladding of composite material are nano oxidized
The washability of zinc particle is all poorer than Examples 1 and 2.The composite material of embodiment 5 does not add fire retardant, and flame retardant property is more real
It applies example 2 and has and significantly decline.Embodiment 6 and the comparison of embodiment 2 can be found that the addition for coating nano zine oxide particle, are conducive to
Improve the flame retardant property of composite material.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (6)
1. a kind of antimicrobial composite material, is used to prepare mat, which is characterized in that the composite material include polymeric substrate and
Polymer overmold nano zine oxide particle, the polymer overmold nano zine oxide particle use divinylbenzene and 1- vinyl
The copolymer of imidazoles is covering material, or the copolymer using divinylbenzene and 1- vinyl -3- alkyl imidazo ion liquid
For covering material.
2. composite material according to claim 1, which is characterized in that the composite material further includes fire retardant, the resistance
Combustion agent is phosphate ester flame retardants.
3. composite material according to claim 2, which is characterized in that the polymeric substrate is in following polymer
It is one or more of: polyethylene, polypropylene, polyester, polyacrylonitrile, polyamide.
4. a kind of mat, which is characterized in that the mat is woven using the fiber or plastic hollow pipe of composite material preparation,
The composite material includes that polymeric substrate and polymer overmold nano zine oxide particle, the polymer overmold are nano oxidized
Zinc particle is covering material using the copolymer of divinylbenzene and 1- vinyl imidazole, or uses divinylbenzene and 1- ethylene
The copolymer of base -3- alkyl imidazo ion liquid is covering material.
5. mat according to claim 4, which is characterized in that the composite material further includes fire retardant, the fire retardant
For phosphate ester flame retardants.
6. mat according to claim 5, which is characterized in that the polymeric substrate is selected from one of following polymer
It is or several: polyethylene, polypropylene, polyester, polyacrylonitrile, polyamide.
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| CN201610543476.9A CN106084406B (en) | 2016-07-06 | 2016-07-06 | A kind of antimicrobial composite material and the mat of composite material preparation |
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| CN106084406B true CN106084406B (en) | 2019-01-22 |
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| CN107586458A (en) * | 2017-09-01 | 2018-01-16 | 浙江夏远信息技术有限公司 | A kind of composite silicone rubber insulating materials and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486813A (en) * | 2009-02-17 | 2009-07-22 | 大连爱瑞克包装制品有限公司 | Food flexible packing material with antibacterial function and use thereof |
| CN101724284A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Anti-bacterial thermoplastic composite and preparation method thereof |
| CN101914235A (en) * | 2010-08-03 | 2010-12-15 | 王维东 | Preparation method of nano antibacterial plastic product |
| CN102363661A (en) * | 2011-08-30 | 2012-02-29 | 常熟市江顺塑料制品有限公司 | Preparation technology of antibacterial plastic |
| CN105482569A (en) * | 2015-11-27 | 2016-04-13 | 宁波双人新材料有限公司 | Water-in-water colorful coating and preparation method thereof |
-
2016
- 2016-07-06 CN CN201610543476.9A patent/CN106084406B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724284A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Anti-bacterial thermoplastic composite and preparation method thereof |
| CN101486813A (en) * | 2009-02-17 | 2009-07-22 | 大连爱瑞克包装制品有限公司 | Food flexible packing material with antibacterial function and use thereof |
| CN101914235A (en) * | 2010-08-03 | 2010-12-15 | 王维东 | Preparation method of nano antibacterial plastic product |
| CN102363661A (en) * | 2011-08-30 | 2012-02-29 | 常熟市江顺塑料制品有限公司 | Preparation technology of antibacterial plastic |
| CN105482569A (en) * | 2015-11-27 | 2016-04-13 | 宁波双人新材料有限公司 | Water-in-water colorful coating and preparation method thereof |
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