CN109456682A - A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof - Google Patents
A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof Download PDFInfo
- Publication number
- CN109456682A CN109456682A CN201811063702.9A CN201811063702A CN109456682A CN 109456682 A CN109456682 A CN 109456682A CN 201811063702 A CN201811063702 A CN 201811063702A CN 109456682 A CN109456682 A CN 109456682A
- Authority
- CN
- China
- Prior art keywords
- parts
- biology base
- gel coat
- nanometer silver
- antimicrobial gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof, it is as follows: first to prepare biology base unsaturated polyester resin and nano silver antimicrobials respectively, then in parts by weight, take 50 ~ 100 parts of biology base unsaturated polyester resin, 20 ~ 40 parts of diluent, 1 ~ 5 part of nano silver antimicrobials, 1 ~ 2h is stirred under the conditions of 10 ~ 50 DEG C, obtain resin mixture liquor, 0.1 ~ 1 part of initiator is sequentially added into above-mentioned resin mixture liquor, 10 ~ 20 parts of filler, 10 ~ 20 parts of pigment, 0.1 ~ 1 part of defoaming agent, 0.1 ~ 1 part of wetting dispersing agent, vacuum defoamation processing is carried out after continuing 1 ~ 2h of stirring, biology base nanometer silver antimicrobial gel coat can be obtained；The present invention in gel coat system by being added nano silver antimicrobials and biology base environmental protection monomer isobide, with preferable environmental requirement, there is preferable compatibility with unsaturated polyester resin system simultaneously, the heat dissipation performance and mechanical strength of gel coat surface can be improved, it has excellent performance nanometer silver antimicrobial gel coat obtained, good anti-bacterial effect.
Description
Technical field
The present invention relates to field of compound material, specifically a kind of biology base nanometer silver antimicrobial gel coat and its preparation side
Method.
Background technique
Unsaturated polyester resin, by dihydric alcohol and unsaturated dicarboxylic acid anhydride or unsaturated dicarboxylic acid, monounsaturated dicarboxylic acid
Line style prepolymer made of acid anhydride or saturated dicarboxylic acid melt polycondensation, heating, illumination, radiation and initiator effect under with second
Alkenyl monomer copolymerization, crosslinking curing are the thermosetting resin of network structure.Unsaturated polyester resin due to excellent mouldability and
Good comprehensive service performance is concerned by people for a long time, is widely used in the fields such as building, ship, automobile, electronic apparatus, is
The maximum resinoid of field of compound material dosage.But the raw material for preparing of current unsaturated polyester resin is mostly maleic anhydride and second
The dihydric alcohols such as glycol, propylene glycol, due to environmental protection pressure, the high molecular material based on renewable energy is increasingly taken seriously, special
Be not the environment-friendly materials of biology base, at present isobide as bio-based monomer polyester material, in terms of it is a large amount of
Research, is widely believed that the potential substitute of polyester synthesis raw material alcohols.
Unsaturated polyester resin is used for gel coat field, and gel coat adds thixotropic agent, pigment, flavouring box by unsaturated polyester resin
The special kinds unsaturated polyester resin that auxiliary agent is formulated, the first layer tree being coated on the die surface handled through release agent
Rouge, constitute glass fiber reinforced plastics product uses surface, has preferable hardness, glossiness, wearability is good, and thermal resistance and acid-alkali resistance performance is excellent
It is different, it is increasingly close with national economic development, national defence and daily life relationship, it is an important composition portion of surface engineering technology
Point.But gel coat is easy the attachment by all kinds of bacteriums and stains, bacterium etc. is pathogenic as a kind of direct outer surface material
Microorganism is one of primary killers of human health, and the bacterium of gel coat surface pollution and growth can be eastern to using and contacting these
The people in west brings threat.Antibacterial gel coat product is very widely used in foreign countries, with the improvement of people's living standard in our country,
The reinforcement of health perception, will be very wide using the market prospects of antibiotic property resin.But the country is to antibiotic property product
Research is weaker, although a small number of products have reached international most advanced level, because cost is too high, cannot achieve industrialization,
It is therefore desirable to develop a kind of nanometer silver antimicrobial gel coat and preparation method thereof that low cost can be mass-produced, facilitate some spies
The application demand in different field.
Summary of the invention
The purpose of the present invention is to solve the deficiency of above-mentioned technical problem, the present invention proposes that a kind of biology base nano silver is anti-
Bacterium gel coat and preparation method thereof makes the gel coat excellent in mechanical performance of preparation, and good anti-bacterial effect, environmental-protecting performance is high, preparation process letter
It is single, it is easy to process.
Present invention deficiency to solve above-mentioned technical problem and the technical solution adopted is that:
A kind of biology base nanometer silver antimicrobial gel coat, is made of the raw material of following parts by weight: biology base unsaturated polyester (UP) 50 ~
100 parts, 10 ~ 20 parts of filler, 10 ~ 20 parts of pigment, 20 ~ 40 parts of diluent, 1 ~ 5 part of nano silver antimicrobials, 0.1 ~ 1 part of defoaming agent,
0.1 ~ 1 part of Ricinate；The biology base unsaturated polyester (UP) include in parts by weight 25 ~ 45 parts of dicarboxylic acids, 25 ~ 45 parts it is different
Sorbierite, 10 ~ 30 parts of fillers, 30 ~ 50 parts of diluents, 5 ~ 20 parts of fire retardants, 3 ~ 5 parts of negative ion powders and 0.5 ~ 2 part of initiator.
A kind of preparation method of biology base nanometer silver antimicrobial gel coat, comprising the following steps:
(1) in parts by weight, 25 ~ 45 parts of dicarboxylic acids and isobide are taken respectively, and esterification occurs at 150 ~ 250 DEG C,
25 ~ 100 DEG C, and the moisture in elimination reaction system are cooled to system after reaction, unsaturated polyester (UP) is made；
(2) in parts by weight, by 50 ~ 90 parts of unsaturated polyester (UP)s, 10 ~ 30 parts of fillers, 30 ~ 50 parts of diluents, 5 ~ 20 parts of fire retardants,
3 ~ 5 parts of negative ion powders and 0.5 ~ 2 part of initiator, are stirred 1 ~ 5h under the conditions of 10 ~ 50 DEG C, biology base insatiable hunger can be obtained
And polyester resin；
(3) silver nitrate and polyvinylpyrrolidone are added in ethylene glycol, the mass ratio of silver nitrate and polyvinylpyrrolidone is
1:0.5 ~ 1 stops heating after heating 1 ~ 2h under the conditions of 150 ~ 160 DEG C of oil baths, and acetone is added and is centrifuged, powder after drying
Wear into the dry powder of 40 ~ 500nm, as nano silver antimicrobials；
(4) in parts by weight, 50 ~ 100 parts of biology base unsaturated polyester resin are taken, 20 ~ 40 parts of diluent, nano silver antimicrobials 1 ~
5 parts, it is stirred 1 ~ 2h under the conditions of 10 ~ 50 DEG C, obtains resin mixture liquor；Initiation is sequentially added into above-mentioned resin mixture liquor
0.1 ~ 1 part of agent, 10 ~ 20 parts of filler, 10 ~ 20 parts of pigment, 0.1 ~ 1 part of defoaming agent, 0.1 ~ 1 part of wetting dispersing agent, continue stirring 1 ~
Vacuum defoamation processing is carried out after 2h, and biology base nanometer silver antimicrobial gel coat can be obtained.
Further, the filler includes one or more of carbon fiber, carbon nanotube or graphene.
Further, the diluent includes one or more of styrene, methyl methacrylate or acrylate.
Further, the defoaming agent is organic silicon defoaming agent.
Further, the wetting dispersing agent is polyacrylate.
Further, the fire retardant includes one of nano-grade aluminum hydroxide micro mist or nanometric magnesium hydroxide micro mist
Or two kinds.
Further, the initiator includes methyl ethyl ketone peroxide, cyclohexanone peroxide, the tertiary fourth of perbenzoic acid
One or more of ester, benzoyl peroxide, azodiisobutyronitrile, lauryl peroxide.
Further, the filler passes through modification, the method is as follows:
(1) graphene and carbon nanotube are weighed by the mass ratio of 1:2 ~ 4, is placed in 2 ~ 4h of immersion in nitration mixture, centrifugal filtration, washing are dried
After dry, the graphene of acidification and the mixed powder of carbon nanotube are obtained, wherein powder gross mass and the volume ratio of nitration mixture are
1g: 50 ~ 80mL, the concentrated nitric acid that nitration mixture is the concentrated sulfuric acid that concentration is 98% and concentration is 80% are mixed to prepare at 1: 1 by volume；
(2) compound concentration is the La(NO of 0.05 ~ 0.1mol/L3)3Earth solution, in the ratio of 200~500mg/mL to acidification
Treated graphene and earth solution is added in the mixed powder of carbon nanotube, added after ultrasonic disperse mass concentration 80 ~
85% hydrazine hydrate solution is restored；Drying obtains the graphene and carbon nanotube mixed powder through rare-earth surface modification；
(3) it is poured into ball grinder to the mixed solution of step (2), and nano aluminium oxide is added, at 100 ~ 110 DEG C after 4 ~ 8h of ball milling
Under the conditions of dry, obtain mixture, mixture be placed in high temperature furnace, under the conditions of 400 ~ 500 DEG C be sintered 1 ~ 2h, can be prepared by
Graphene and carbon nanotube after modification.
Further, the nano-grade aluminum hydroxide micro mist or nanometric magnesium hydroxide micro mist by fatty acid treatment or
Siloxane treated.
The beneficial effects of the present invention are:
The present invention is to provide a kind of biology base nanometer silver antimicrobial gel coats and preparation method thereof, are directly added into and receive in gel coat system
Rice silver antibacterial agent and auxiliary agent have preferable compatibility with unsaturated polyester resin system, make the nanometer silver antimicrobial gel coat of preparation
With preferable antibacterial effect, the bacterium stained on resin can be killed within a certain period of time or inhibited its breeding, keep
Itself clean state, reduces the bacterial cross-infection occurred because using resin, and antibacterial agent is quick to some microorganism height
Sense, the chemical substance of material antimicrobial properties can be assigned by being added in material on a small quantity；Since antibacterial agent is nano silver powder
Particle, while can effectively improve the wearability of the unsaturated polyester resin, to increase the use of the nanometer silver antimicrobial gel coat
Service life；
Unsaturated polyester resin of the invention due to joined biology base environmental protection monomer isobide there is preferable environmental protection to want
It asks, has expanded the potential using value of unsaturated polyester (UP) significantly；In addition, the present invention is by being added some fillers, and to filler into
Gone modification: the graphene as one of filler ingredient has the performances such as excellent electronics, mechanics, calorifics, so often quilt
The reinforced phase and function phase being used as in composite material, the carbon nano-tube material of another ingredient as filler is as one-dimentional structure material
Material has that flexibility is good, draw ratio is high and the characteristics such as high thermal conductivity, using the high heat conductance of graphene and carbon nanotube, and leads to
It crosses nano aluminium oxide and rare earth is modified it, obtain the modified graphene and carbon nanotube with uniformity and stability, can mention
The heat dissipation performance and mechanical strength of high gel coat surface keep Mechanical Properties of Products obtained excellent, good anti-bacterial effect.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below.
Embodiment 1:
A kind of biology base nanometer silver antimicrobial gel coat, is made of the raw material of following parts by weight: biology base unsaturated polyester (UP) 50
Part, 10 parts of filler, 10 parts of pigment, 20 parts of styrene, 1 part of nano silver antimicrobials, 0.1 part of organic silicon defoaming agent, polyacrylic acid
0.1 part of esters dispersing agent；The present invention is directly added into nano silver antimicrobials and auxiliary agent in gel coat system, with unsaturated polyester resin
System has preferable compatibility, so that the nanometer silver antimicrobial gel coat of preparation is had preferable antibacterial effect, can will stain and set
Bacterium on rouge kills within a certain period of time or inhibits its breeding, keeps itself clean state, reduces due to using resin
The bacterial cross-infection of generation, antibacterial agent are highly sensitive to some microorganisms, and material can be assigned by, which being added in material on a small quantity, resists
The chemical substance of microbial performance；Since antibacterial agent is nano silver powder particle, while it can effectively improve the unsaturated polyester (UP)
The wearability of resin, to increase the service life of the nanometer silver antimicrobial gel coat；
The biology base unsaturated polyester (UP) includes 25 parts of dicarboxylic acids, 25 parts of isobides, 10 parts of fillers, 30 parts in parts by weight
Styrene, 5 parts of nano-grade aluminum hydroxide micro mists；Unsaturated polyester resin of the invention is different due to joined biology base environmental protection monomer
Sorbierite has preferable environmental requirement, has expanded the potential using value of unsaturated polyester (UP) significantly.
A kind of preparation method of biology base nanometer silver antimicrobial gel coat, comprising the following steps:
(1) in parts by weight, 25 parts of dicarboxylic acids and isobide are taken respectively, esterification occur at 150 DEG C, after reaction
System is cooled to 25 DEG C, and the moisture in elimination reaction system, and unsaturated polyester (UP) is made；
(2) in parts by weight, by 50 parts of unsaturated polyester (UP)s, 10 parts of fillers, 30 parts of styrene, 5 parts of nano-grade aluminum hydroxide micro mists,
3 parts of negative ion powders and 0.5 part of methyl ethyl ketone peroxide, are stirred 1h under the conditions of 10 DEG C, and biology base unsaturation can be obtained
Polyester resin；
(3) silver nitrate and polyvinylpyrrolidone are added in ethylene glycol, the mass ratio of silver nitrate and polyvinylpyrrolidone is
1:0.5 stops heating after heating 1h under the conditions of 150 DEG C of oil baths, and acetone is added and is centrifuged, grinding is at 40nm after drying
Dry powder, as nano silver antimicrobials；
(4) in parts by weight, 50 parts of biology base unsaturated polyester resin are taken, 20 parts of styrene, 1 part of nano silver antimicrobials, 10
It is stirred 1h under the conditions of DEG C, obtains resin mixture liquor；Methyl ethyl ketone peroxide 0.1 is sequentially added into above-mentioned resin mixture liquor
Part, 10 parts of filler, 10 parts of pigment, 0.1 part of organic silicon defoaming agent, 0.1 part of polyacrylate dispersing agent, continue 1 ~ 2h of stirring
Vacuum defoamation processing is carried out afterwards, and biology base nanometer silver antimicrobial gel coat can be obtained.
Further, the nano-grade aluminum hydroxide micro mist passes through fatty acid treatment or siloxane treated.
Further, the filler pass through modification, as one of filler ingredient graphene have excellent electronics,
The performances such as mechanics, calorifics, so being often used as the reinforced phase and function phase in composite material, the carbon of another ingredient as filler
Nano-tube material has that flexibility is good, draw ratio is high and the characteristics such as high thermal conductivity as one-dimentional structure material, using graphene and
The high heat conductance of carbon nanotube, and being modified by nano aluminium oxide and rare earth to it, obtaining has changing for uniformity and stability
Property graphene and carbon nanotube, the heat dissipation performance and mechanical strength of gel coat surface can be improved, keep Mechanical Properties of Products obtained excellent
It is different, good anti-bacterial effect；Method is as follows:
(1) graphene and carbon nanotube are weighed by the mass ratio of 1:2, is placed in nitration mixture and impregnates 2h, centrifugal filtration, washing and drying
Afterwards, the graphene of acidification and the mixed powder of carbon nanotube are obtained, wherein powder gross mass and the volume ratio of nitration mixture are 1g
: 50mL, the concentrated nitric acid that nitration mixture is the concentrated sulfuric acid that concentration is 98% and concentration is 80% are mixed to prepare at 1: 1 by volume；
(2) compound concentration is the La(NO of 0.05mol/L3)3Earth solution, in the ratio of 200mg/mL to the stone after acidification
Earth solution is added in black alkene and the mixed powder of carbon nanotube, the hydrazine hydrate that mass concentration 80% is added after ultrasonic disperse is molten
Liquid is restored；Drying obtains the graphene and carbon nanotube mixed powder through rare-earth surface modification；
(3) it is poured into ball grinder to the mixed solution of step (2), and nano aluminium oxide is added, after ball milling 4h under the conditions of 100 DEG C
Drying, obtains mixture, mixture is placed in high temperature furnace, 1h is sintered under the conditions of 400 DEG C, after can be prepared by modification
Graphene and carbon nanotube.
Embodiment 2:
A kind of biology base nanometer silver antimicrobial gel coat, is made of the raw material of following parts by weight: biology base unsaturated polyester (UP) 70
Part, 15 parts of filler, 15 parts of pigment, 30 parts of methyl methacrylate, 3 parts of nano silver antimicrobials, 0.5 part of organic silicon defoaming agent,
0.5 part of polyacrylate dispersing agent；The present invention is directly added into nano silver antimicrobials and auxiliary agent in gel coat system, with unsaturation
Polyester resin system has preferable compatibility, and the nanometer silver antimicrobial gel coat of preparation is made to have preferable antibacterial effect, can incite somebody to action
It stains the bacterium on resin and kills or inhibit its breeding within a certain period of time, keep itself clean state, reduce because using tree
Grease article and the bacterial cross-infection occurred, antibacterial agent are highly sensitive to some microorganisms, being added in material on a small quantity can assign
Give the chemical substance of material antimicrobial properties；Since antibacterial agent is nano silver powder particle, while it can effectively improve this not
The wearability of saturated polyester resin, to increase the service life of the nanometer silver antimicrobial gel coat；
The biology base unsaturated polyester (UP) includes 25 parts of dicarboxylic acids, 25 parts of isobides, 10 parts of fillers, 30 parts in parts by weight
Methyl methacrylate, 5 parts of nanometric magnesium hydroxide micro mists；Unsaturated polyester resin of the invention is due to joined biological basic ring
Declaration form body isobide has preferable environmental requirement, has expanded the potential using value of unsaturated polyester (UP) significantly.
A kind of preparation method of biology base nanometer silver antimicrobial gel coat, comprising the following steps:
(1) in parts by weight, 25 parts of dicarboxylic acids and isobide are taken respectively, esterification occur at 200 DEG C, after reaction
System is cooled to 60 DEG C, and the moisture in elimination reaction system, and unsaturated polyester (UP) is made；
(2) in parts by weight, by 70 parts of unsaturated polyester (UP)s, 15 parts of fillers, 40 parts of methyl methacrylates, 15 parts of nanoscale hydrogen-oxygens
Change magnesium micro mist, 4 parts of negative ion powders and 1 part of peroxidized t-butyl perbenzoate, is stirred 3h under the conditions of 30 DEG C, can be obtained
Biology base unsaturated polyester resin；
(3) silver nitrate and polyvinylpyrrolidone are added in ethylene glycol, the mass ratio of silver nitrate and polyvinylpyrrolidone is
1:0.8, under the conditions of 155 DEG C of oil baths heat 1.5h after stop heating, be added acetone be centrifuged, after drying grinding at
200nm dries powder, as nano silver antimicrobials；
(4) in parts by weight, 70 parts of biology base unsaturated polyester resin are taken, 30 parts of methyl methacrylate, nano silver antimicrobials 3
Part, it is stirred 1.5h under the conditions of 30 DEG C, obtains resin mixture liquor；Benzoyl peroxide is sequentially added into above-mentioned resin mixture liquor
0.5 part of t-butyl formate, 15 parts of filler, 15 parts of pigment, 0.5 part of organic silicon defoaming agent, polyacrylate dispersing agent 0.5
Part, continue to carry out vacuum defoamation processing after stirring 1.5h, biology base nanometer silver antimicrobial gel coat can be obtained.
Further, the nanometric magnesium hydroxide micro mist passes through fatty acid treatment or siloxane treated.
Further, the filler pass through modification, as one of filler ingredient graphene have excellent electronics,
The performances such as mechanics, calorifics, so being often used as the reinforced phase and function phase in composite material, the carbon of another ingredient as filler
Nano-tube material has that flexibility is good, draw ratio is high and the characteristics such as high thermal conductivity as one-dimentional structure material, using graphene and
The high heat conductance of carbon nanotube, and being modified by nano aluminium oxide and rare earth to it, obtaining has changing for uniformity and stability
Property graphene and carbon nanotube, the heat dissipation performance and mechanical strength of gel coat surface can be improved, keep Mechanical Properties of Products obtained excellent
It is different, good anti-bacterial effect；Method is as follows:
(1) graphene and carbon nanotube are weighed by the mass ratio of 1:3, is placed in nitration mixture and impregnates 3h, centrifugal filtration, washing and drying
Afterwards, the graphene of acidification and the mixed powder of carbon nanotube are obtained, wherein powder gross mass and the volume ratio of nitration mixture are 1g
: 70mL, the concentrated nitric acid that nitration mixture is the concentrated sulfuric acid that concentration is 98% and concentration is 80% are mixed to prepare at 1: 1 by volume；
(2) compound concentration is the La(NO of 0.08mol/L3)3Earth solution, in the ratio of 400mg/mL to the stone after acidification
Earth solution is added in black alkene and the mixed powder of carbon nanotube, the hydrazine hydrate that mass concentration 83% is added after ultrasonic disperse is molten
Liquid is restored；Drying obtains the graphene and carbon nanotube mixed powder through rare-earth surface modification；
(3) it is poured into ball grinder to the mixed solution of step (2), and nano aluminium oxide is added, after ball milling 6h under the conditions of 105 DEG C
Drying, obtains mixture, mixture is placed in high temperature furnace, 1.5h is sintered under the conditions of 450 DEG C, after can be prepared by modification
Graphene and carbon nanotube.
Embodiment 3:
A kind of biology base nanometer silver antimicrobial gel coat, is made of the raw material of following parts by weight: biology base unsaturated polyester (UP) 100
Part, 20 parts of filler, 20 parts of pigment, 40 parts of acrylate, 5 parts of nano silver antimicrobials, 1 part of organic silicon defoaming agent, polyacrylic acid
1 part of esters dispersing agent；The present invention is directly added into nano silver antimicrobials and auxiliary agent in gel coat system, with unsaturated polyester resin body
System has preferable compatibility, so that the nanometer silver antimicrobial gel coat of preparation is had preferable antibacterial effect, can will stain in resin
On bacterium kill or inhibit its breeding within a certain period of time, keep itself clean state, reduction is sent out because using resin
Raw bacterial cross-infection, antibacterial agent are highly sensitive to some microorganisms, be added in material on a small quantity can assign material resist it is micro-
The chemical substance of biological property；Since antibacterial agent is nano silver powder particle, while it can effectively improve the unsaturated polyester (UP) tree
The wearability of rouge, to increase the service life of the nanometer silver antimicrobial gel coat；
The biology base unsaturated polyester (UP) includes 45 parts of dicarboxylic acids, 45 parts of isobides, 30 parts of fillers, 50 parts in parts by weight
Acrylate, 20 parts of nanometric magnesium hydroxide micro mists；Unsaturated polyester resin of the invention is single due to joined biology base environmental protection
Body isobide has preferable environmental requirement, has expanded the potential using value of unsaturated polyester (UP) significantly.
A kind of preparation method of biology base nanometer silver antimicrobial gel coat, comprising the following steps:
(1) in parts by weight, 45 parts of dicarboxylic acids and isobide are taken respectively, esterification occur at 250 DEG C, after reaction
System is cooled to 100 DEG C, and the moisture in elimination reaction system, and unsaturated polyester (UP) is made；
(2) in parts by weight, by 90 parts of unsaturated polyester (UP)s, 30 parts of fillers, 50 parts of acrylate, 20 parts of nanometric magnesium hydroxides are micro-
Powder, 5 parts of negative ion powders and 2 parts of azodiisobutyronitriles, are stirred 5h under the conditions of 50 DEG C, and biology base unsaturation can be obtained
Polyester resin；
(3) silver nitrate and polyvinylpyrrolidone are added in ethylene glycol, the mass ratio of silver nitrate and polyvinylpyrrolidone is
1:1 stops heating after heating 2h under the conditions of 160 DEG C of oil baths, and acetone is added and is centrifuged, grinding is at 500nm after drying
Dry powder, as nano silver antimicrobials；
(4) in parts by weight, 100 parts of biology base unsaturated polyester resin are taken, 40 parts of acrylate, 5 parts of nano silver antimicrobials,
It is stirred 2h under the conditions of 50 DEG C, obtains resin mixture liquor；Azodiisobutyronitrile 1 is sequentially added into above-mentioned resin mixture liquor
Part, 20 parts of filler, 20 parts of pigment, 1 part of organic silicon defoaming agent, 1 part of polyacrylate, it is de- to continue progress vacuum after stirring 2h
Bubble processing, can be obtained biology base nanometer silver antimicrobial gel coat.
Further, the nanometric magnesium hydroxide micro mist passes through fatty acid treatment or siloxane treated.
Further, the filler pass through modification, as one of filler ingredient graphene have excellent electronics,
The performances such as mechanics, calorifics, so being often used as the reinforced phase and function phase in composite material, the carbon of another ingredient as filler
Nano-tube material has that flexibility is good, draw ratio is high and the characteristics such as high thermal conductivity as one-dimentional structure material, using graphene and
The high heat conductance of carbon nanotube, and being modified by nano aluminium oxide and rare earth to it, obtaining has changing for uniformity and stability
Property graphene and carbon nanotube, the heat dissipation performance and mechanical strength of gel coat surface can be improved, keep Mechanical Properties of Products obtained excellent
It is different, good anti-bacterial effect；Method is as follows:
(1) graphene and carbon nanotube are weighed by the mass ratio of 1:4, is placed in nitration mixture and impregnates 4h, centrifugal filtration, washing and drying
Afterwards, the graphene of acidification and the mixed powder of carbon nanotube are obtained, wherein powder gross mass and the volume ratio of nitration mixture are 1g
: 80mL, the concentrated nitric acid that nitration mixture is the concentrated sulfuric acid that concentration is 98% and concentration is 80% are mixed to prepare at 1: 1 by volume；
(2) compound concentration is the La(NO of 0.1mol/L3)3Earth solution, in the ratio of 500mg/mL to the stone after acidification
Earth solution is added in black alkene and the mixed powder of carbon nanotube, the hydrazine hydrate that mass concentration 85% is added after ultrasonic disperse is molten
Liquid is restored；Drying obtains the graphene and carbon nanotube mixed powder through rare-earth surface modification；
(3) it is poured into ball grinder to the mixed solution of step (2), and nano aluminium oxide is added, after ball milling 8h under the conditions of 110 DEG C
Drying, obtains mixture, mixture is placed in high temperature furnace, 2h is sintered under the conditions of 500 DEG C, after can be prepared by modification
Graphene and carbon nanotube.
The foregoing description of the disclosed embodiments, only for can be realized professional and technical personnel in the field or use this
Invention.Various modifications to these embodiments will be readily apparent to those skilled in the art, institute herein
The General Principle of definition can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore,
The present invention will not be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent widest scope of point.
Claims (10)
1. a kind of biology base nanometer silver antimicrobial gel coat, which is characterized in that be made of the raw material of following parts by weight: biology base
50 ~ 100 parts of unsaturated polyester (UP), 10 ~ 20 parts of filler, 10 ~ 20 parts of pigment, 20 ~ 40 parts of diluent, 1 ~ 5 part of nano silver antimicrobials, disappear
0.1 ~ 1 part of infusion, 0.1 ~ 1 part of Ricinate；The biology base unsaturated polyester (UP) includes 25 ~ 45 parts of binary carboxylics in parts by weight
Acid, 25 ~ 45 parts of isobides, 10 ~ 30 parts of fillers, 30 ~ 50 parts of diluents, 5 ~ 20 parts of fire retardants, 3 ~ 5 parts of negative ion powders and
0.5 ~ 2 part of initiator.
2. a kind of preparation method of biology base nanometer silver antimicrobial gel coat as described in claim 1, which is characterized in that including following
Step:
(1) in parts by weight, 25 ~ 45 parts of dicarboxylic acids and isobide are taken respectively, and esterification occurs at 150 ~ 250 DEG C,
25 ~ 100 DEG C, and the moisture in elimination reaction system are cooled to system after reaction, unsaturated polyester (UP) is made；
(2) in parts by weight, by 50 ~ 90 parts of unsaturated polyester (UP)s, 10 ~ 30 parts of fillers, 30 ~ 50 parts of diluents, 5 ~ 20 parts of fire retardants,
3 ~ 5 parts of negative ion powders and 0.5 ~ 2 part of initiator, are stirred 1 ~ 5h under the conditions of 10 ~ 50 DEG C, biology base insatiable hunger can be obtained
And polyester resin；
(3) silver nitrate and polyvinylpyrrolidone are added in ethylene glycol, the mass ratio of silver nitrate and polyvinylpyrrolidone is
1:0.5 ~ 1 stops heating after heating 1 ~ 2h under the conditions of 150 ~ 160 DEG C of oil baths, and acetone is added and is centrifuged, powder after drying
Wear into the dry powder of 40 ~ 500nm, as nano silver antimicrobials；
(4) in parts by weight, 50 ~ 100 parts of biology base unsaturated polyester resin are taken, 20 ~ 40 parts of diluent, nano silver antimicrobials 1 ~
5 parts, it is stirred 1 ~ 2h under the conditions of 10 ~ 50 DEG C, obtains resin mixture liquor；Initiation is sequentially added into above-mentioned resin mixture liquor
0.1 ~ 1 part of agent, 10 ~ 20 parts of filler, 10 ~ 20 parts of pigment, 0.1 ~ 1 part of defoaming agent, 0.1 ~ 1 part of wetting dispersing agent, continue stirring 1 ~
Vacuum defoamation processing is carried out after 2h, and biology base nanometer silver antimicrobial gel coat can be obtained.
3. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 2, which is characterized in that the filler includes carbon fiber
One or more of dimension, carbon nanotube or graphene.
4. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 2, which is characterized in that the diluent includes benzene second
One or more of alkene, methyl methacrylate or acrylate.
5. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 2, which is characterized in that the defoaming agent is organic
Silicon class defoaming agent.
6. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 2, which is characterized in that the wetting dispersing agent is
Polyacrylate.
7. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 2, which is characterized in that the fire retardant includes nanometer
Grade one or both of aluminium hydroxide micro powder or nanometric magnesium hydroxide micro mist.
8. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 2, which is characterized in that the initiator included
Methyl Ethyl Ketone Oxidation, cyclohexanone peroxide, peroxidized t-butyl perbenzoate, benzoyl peroxide, azodiisobutyronitrile, lauryl mistake
One or more of oxide.
9. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 3, which is characterized in that the filler passes through at modified
Reason, the method is as follows:
(1) graphene and carbon nanotube are weighed by the mass ratio of 1:2 ~ 4, is placed in 2 ~ 4h of immersion in nitration mixture, centrifugal filtration, washing are dried
After dry, the graphene of acidification and the mixed powder of carbon nanotube are obtained, wherein powder gross mass and the volume ratio of nitration mixture are
1g: 50 ~ 80mL, the concentrated nitric acid that nitration mixture is the concentrated sulfuric acid that concentration is 98% and concentration is 80% are mixed to prepare at 1: 1 by volume；
(2) compound concentration is the La(NO of 0.05 ~ 0.1mol/L3)3Earth solution, in the ratio of 200~500mg/mL at acidification
Graphene after reason and earth solution is added in the mixed powder of carbon nanotube, added after ultrasonic disperse mass concentration 80 ~
85% hydrazine hydrate solution is restored；Drying obtains the graphene and carbon nanotube mixed powder through rare-earth surface modification；
(3) it is poured into ball grinder to the mixed solution of step (2), and nano aluminium oxide is added, at 100 ~ 110 DEG C after 4 ~ 8h of ball milling
Under the conditions of dry, obtain mixture, mixture be placed in high temperature furnace, under the conditions of 400 ~ 500 DEG C be sintered 1 ~ 2h, can be prepared by
Graphene and carbon nanotube after modification.
10. a kind of biology base nanometer silver antimicrobial gel coat as claimed in claim 7, which is characterized in that the nanoscale hydroxide
Aluminium micro mist or nanometric magnesium hydroxide micro mist pass through fatty acid treatment or siloxane treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063702.9A CN109456682A (en) | 2018-09-12 | 2018-09-12 | A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063702.9A CN109456682A (en) | 2018-09-12 | 2018-09-12 | A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109456682A true CN109456682A (en) | 2019-03-12 |
Family
ID=65606610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811063702.9A Pending CN109456682A (en) | 2018-09-12 | 2018-09-12 | A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109456682A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111231379A (en) * | 2020-02-12 | 2020-06-05 | 山东源仕新材料有限公司 | FRP (fiber reinforced plastic) antibacterial glass fiber reinforced plastic and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3001967A (en) * | 1957-08-27 | 1961-09-26 | Basf Ag | Method of copolymerizing polyester, ethylenically unsaturated monomer and metal salt of acid half ester of alpha, beta-ethylenically unsaturated dicarboxylic acid and a monohydric alcohol and copolymers thereof |
| CN1712476A (en) * | 2005-08-08 | 2005-12-28 | 常州天马集团有限公司 | Gel coating resin and production thereof |
| CN102775587A (en) * | 2012-07-06 | 2012-11-14 | 南京工业大学 | Polyfumaric acid isosorbide ester and preparation method thereof |
| CN106892427A (en) * | 2017-04-10 | 2017-06-27 | 河南科技大学 | A kind of method of rare-earth surface modification Graphene |
-
2018
- 2018-09-12 CN CN201811063702.9A patent/CN109456682A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3001967A (en) * | 1957-08-27 | 1961-09-26 | Basf Ag | Method of copolymerizing polyester, ethylenically unsaturated monomer and metal salt of acid half ester of alpha, beta-ethylenically unsaturated dicarboxylic acid and a monohydric alcohol and copolymers thereof |
| CN1712476A (en) * | 2005-08-08 | 2005-12-28 | 常州天马集团有限公司 | Gel coating resin and production thereof |
| CN102775587A (en) * | 2012-07-06 | 2012-11-14 | 南京工业大学 | Polyfumaric acid isosorbide ester and preparation method thereof |
| CN106892427A (en) * | 2017-04-10 | 2017-06-27 | 河南科技大学 | A kind of method of rare-earth surface modification Graphene |
Non-Patent Citations (4)
| Title |
|---|
| [加]GEORGE WYPYCH: "《填料手册》", 31 October 2002, 中国石化出版社 * |
| 余家会等: "《纳米生物医药》", 31 December 2011, 华东理工大学出版社 * |
| 张丹慧等: "《贵金属/石墨烯纳米复合材料的合成及性能》", 31 December 2015, 国防工业出版社 * |
| 郑水林等: "《粉体表面改性》", 30 September 2011, 中国建材工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111231379A (en) * | 2020-02-12 | 2020-06-05 | 山东源仕新材料有限公司 | FRP (fiber reinforced plastic) antibacterial glass fiber reinforced plastic and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104277495B (en) | Functional materials and preparation method thereof, organic LED display panel | |
| CN102212265B (en) | Preparation method for electroconductive polyurethane complex with anion releasing function | |
| CN102304316B (en) | Polyacrylate/nanometer ZnO composite finishing agent and preparation method thereof | |
| CN103910997B (en) | A kind of permanent anti-static, antimicrobial polyamide 6/PP composite material | |
| WO2004087794A1 (en) | Compound powder, its preparation method and use | |
| CN109627680A (en) | A kind of graphene modified plastics and preparation method thereof | |
| CN102942719B (en) | Magnetic composite material for multistage magnetic encoder and preparation method thereof | |
| CN107501695B (en) | Antibacterial polyethylene pipe and preparation method thereof | |
| TW201203292A (en) | Composition for producing magnetic or magnetizable moldings, and process for producing the same | |
| CN107189335A (en) | A kind of computer mouse case material and preparation method thereof | |
| CN109456682A (en) | A kind of biology base nanometer silver antimicrobial gel coat and preparation method thereof | |
| CN109486142A (en) | A kind of polylactic acid-polycaprolactone composite material and preparation method thereof for 3D printing | |
| CN105440547A (en) | High-strength heat-resistant polyethylene tube material | |
| CN109265934A (en) | Intercalation modifying graphene oxide modified filler and the method for preparing PBT composite | |
| CN106634514A (en) | Preparation method of hollow aluminum oxide ceramic microsphere modified polyurethane coating | |
| CN105778386A (en) | Preparation method for organic silicone modified unsaturated polyester ternary nano-composite material | |
| CN105418972B (en) | A kind of organic antibacterial agent intercalation modifying montmorillonite and its application | |
| CN109456583B (en) | Nanowire modified unsaturated polyester resin reinforced material and preparation method thereof | |
| Chang et al. | Multifunctional soy protein gels with excellent initial adhesion and bonding strength based on a mussel-inspired redox self-catalytic and oyster-inspired organic-inorganic hybrid dual-bionic strategy | |
| CN105038047B (en) | A kind of antibacterial non-stick pot handle and preparation method thereof | |
| CN110255513B (en) | Hydrophilic modified white graphene and preparation method thereof | |
| CN110922661B (en) | Inorganic nano antibacterial plastic, preparation method thereof and application thereof in water supply pipe | |
| CN103214780B (en) | Modified ABS (acrylonitrile-butadine-styrene) special material for electric bicycle and preparation method for same | |
| WO2003032734A1 (en) | Inorganic antimicrobial agent, antimicrobial molded resin articles using the same and process for the production thereof | |
| CN108410139A (en) | A kind of high molecular polymer antibacterial plastic concentrate and preparation method thereof based on nanometer Cu/C composite materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190312 |