CN106633364A - Antibacterial polypropylene and a preparing method thereof - Google Patents
Antibacterial polypropylene and a preparing method thereof Download PDFInfo
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- CN106633364A CN106633364A CN201510711289.2A CN201510711289A CN106633364A CN 106633364 A CN106633364 A CN 106633364A CN 201510711289 A CN201510711289 A CN 201510711289A CN 106633364 A CN106633364 A CN 106633364A
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- attapulgite
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
An antibacterial polypropylene material is disclosed. The antibacterial polypropylene material includes polypropylene resin and an antibacterial agent dispersed in the resin. The antibacterial agent is attapulgite-nanometer silver composite inorganic powder, wherein the mass ratio of the nanometer silver to the attapulgite is 10/100-100/100, and the particle diameter range of the nanometer silver is 3-100 nm. The composite antibacterial agent has advantages of a low using amount, a low cost, a simple preparing process, capability of improving mechanical performance, and the like, can improve antibacterial performance of the material, can increase material rigidity with a small using amount, and is an ideal polypropylene resin modifying auxiliary agent.
Description
Technical field
The present invention relates to field of polymer technology, further says, be related to it is a kind of with attapulgite as carrier containing receiving
Rice silver particles composite inorganic powder for antiseptic polypropylene material, the antibacterial polypropylene can be applicable to production and
The various fields of life.
Background technology
As the demand of antibacterial plastic product is continuously increased, various antiseptics and antibiotic plastic are also with development.It is anti-
Microbial inoculum is divided into inorganic antiseptic and organic antibacterial agent.Inorganic antiseptic, such as Ag, Zn etc., it is its security, resistance to
Hot, durability is preferable, in being carried on the inorganic carriers such as zeolite, glass, montmorillonite, diatomite, Ag,
Zn ions can be slowly released.Organic antibacterial agent, for example, plug bacterium spirit, Bravo, carbendazim, pyridine sulphur
Sour zinc, normal-butyl BIT (BBIT) etc., most of organic antibacterial agent hydrophily is poor, for moulding
Material may be separated out with speed faster, not wash resistant, and working life is short.
Silver ion with efficient, safety, wide sterilization spectrum, heat resistance, has no drug resistance and Gao Xuan as antiseptic
The advantages of selecting property.Silver ion has high reaction activity, but in most of practical applications, silver ion is easy to
React with biological fluid and inactivate, but these limitation can be resolved by nano silver particles.With receiving
The emergence and development of rice science and technology, Nano Silver initially enters daily life, has been widely used in now
Health care and food hygiene field.
By nano-silver loaded on different carriers, use as antibacterial additives, the anti-of Nano Silver can be improved
Bacterium effect and dispersiveness.The carrier for carrying silver is usually the inorganic mineral of meso-hole structure, including zeolite, galapectite,
Sepiolite, mesoporous silicon oxide, attapulgite etc..Wherein attapulgite is the nano-particle of loose structure, its
Main component is palygorskite (attapulgite), is a kind of clay of the magnesium silicate containing Shuifu County with chain layer structure
Mineral.Its skeleton structure is in 3 D stereo shape, octahedra mutual by sharing summit by silicon-oxy tetrahedron and magnalium
It is formed by connecting, with numerous pipes parallel to (needle-like, micro- bar-shaped or fibrous monocrystal) direction arrangement of rod crystalline substance
Shape nanoscale duct, duct run through total, from section Shang Kan ducts in it is equal in magnitude (about
0.38nm × 0.63nm) it is cellular, belong to natural monodimension nanometer material, it is with good absorption property and inexpensive,
It is ideal carrier material, therefore causes the attention of scholar and research structure.Such as Chinese patent
CN1568703A under conditions of surfactant and organic reducing agent are present, with attapulgite as carrier and nitre
Sour silver solution chemistry reacts to form complex antimicrobials；Similar, Chinese patent CN1685830A, zeolite powder
Body is immersed in silver nitrate solution so that silver ion fully adsorbs in the hole of zeolite, then in the bar of stirring
Hydrazine hydrate is added to be Nano Silver silver ion reduction under part.
Chemical reduction method prepares carrying silver antimicrobials, purity, surface nature generally to carrier etc. to have high requirements,
And also to be disperseed and be adjusted the process of pH value to carrier solution before silver nitrate solution is added.In order to subtract
Mutual reunion between few Nano silver grain, will also add considerable amount of surfactant, finally in reduction process
Also the remaining reducing agent in the inside and surfactant are fallen by continuous eccentric cleaning, preparation process is complicated, prepares
Cycle is long, limits its large-scale production application.The content of nanometer silver of such method supported on carriers is very low,
Antibacterial antiplaque agent effect is caused not to be fine, the reducing agent and surfactant remained in antiseptic has been applied to
Very big impact.
Polypropylene is a kind of thermoplastic being widely used, and cheap and combination property is good, but it is anti-
Bacterium is modified, in addition it is also necessary to continue to study.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of attapulgite-Nano Silver composite inorganic
Powder modification polypropylene (antibacterial polypropylene material) and preparation method thereof, improves anti-microbial property and mechanical property.
With cheap attapulgite and silver nitrate as raw material, without the need for adding any reducing agent, will be spray-dried after powder
End adds in acrylic resin (such as 200-500 DEG C of roasting) after calcination process and is blended, and obtains described load and receives
The attapulgite clay compounded inorganic powder modified polypropene (antibacterial polypropylene material) of meter Yin.Present invention process is simple,
Environmental protection.The use of organic solvent is avoided, and reduces the discharge of environmental contaminants.
An object of the present invention is to provide a kind of antibacterial polypropylene material, and (i.e. attapulgite-Nano Silver is combined nothing
Machine powder modification polypropylene), it includes：Acrylic resin and the antiseptic being dispersed in the resin, institute
Antiseptic is stated for attapulgite-Nano Silver composite inorganic powder.Wherein silver is with the mass ratio of attapulgite
10/100-100/100, the particle size range of Nano Silver is 3-100nm.
According to the present invention, the attapulgite has in bar-shaped or filamentary structure and has hollow nano grade pore
Road, the rod crystalline substance diameter of attapulgite is between 10-80nm.Particle diameter 3-100nm is loaded with attapulgite's surface
Nano-Ag particles.Nano-Ag particles are spherical.It is preferred that the Nano Silver is with the mass ratio of attapulgite
30/100-80/100。
According to antibacterial polypropylene material of the present invention, the attapulgite-Nano Silver composite inorganic powder with it is poly-
The weight ratio of allyl resin is (0.01-1):100, preferably (0.01-0.1):100.
Antibacterial polypropylene material of the invention, wherein silver-colored simple substance is adsorbed in attapulgite in the form of Nano Silver
Surface, and nano-Ag particles and attapulgite be firmly combined with.Nano silver active is big, can slowly release tool
There is the silver ion of antibacterial effect.And the size of attapulgite-Nano Silver composite inorganic powder is little, is nanoscale auxiliary agent,
There is good dispersive property in acrylic resin, nanoscale dispersion can be reached, improve the rigidity of material
And antibacterial effect.The small size and bigger serface of attapulgite-Nano Silver composite inorganic powder can make it a small amount of
Addition under, can also play preferable modified effect.
The second object of the present invention is to provide a kind of antibacterial polypropylene material, and (i.e. attapulgite-Nano Silver is combined nothing
Machine powder modification polypropylene) preparation method.Methods described includes：
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in the attapulgite suspension described in step (1), is then carried out certain
At a temperature of stir；
(3) attapulgite suspension after step (2) stirring is spray-dried, is obtained composite powder；
(4) and then by the composite powder roasting is carried out, obtains attapulgite-Nano Silver composite inorganic powder；
(5) attapulgite-Nano Silver composite inorganic powder is blended with acrylic resin, is obtained institute
The antibacterial polypropylene material stated.
A preferred embodiment of the invention, in step (1), the attapulgite is preferably heat
Activation and/or the attapulgite of decentralized processing, so as to improve the dispersiveness of attapulgite.The thermal activation treatment can
Using conventional process of thermal activation, roasting method can be such as adopted, sintering temperature is 200-450 DEG C, roasting time
5-60min.The decentralized approach of the attapulgite can adopt common method of the prior art, for example：
Ultrasonic wave dispersion, mechanical agitation dispersion (such as ball milling dispersion, high-speed stirred dispersion) etc..It is specific at one
In embodiment, in the attapulgite suspension, the mass concentration of attapulgite is less than 10%, preferably
1-10wt%.The attapulgite is without acid treatment.
A preferred embodiment of the invention, in step (2), in the Nano Silver for preparing the present invention
During attapulgite clay compounded powder, by attapulgite suspension and silver nitrate solution mixing through in a constant temperature
Stirring under degree (be higher than room temperature), the carbanion in attapulgite in carbonate can be promoted to dissolve and with silver
Ionic reaction generates silver carbonate and adsorbs in attapulgite's surface.The temperature of the stirring is higher than 50 DEG C, preferably
50-90℃.The time of the stirring is more than 1h, preferably 1h-10h.The silver nitrate and attapulgite
Mass ratio is 17/100-170/100, preferred 50/100-135/100.
A preferred embodiment of the invention, in step (3), the temperature of the spray drying is
150-200℃.In spray-drying process, unreacted silver nitrate solution and dispersed concave convex rod in the solution
In the presence of thermal current is added, can further react soil generation silver carbonate.For example filtered using other
And the method being dried with convection oven, it is impossible to obtain and be spray-dried identical technique effect.
A preferred embodiment of the invention, in step (4), the roasting can be conventional roasting
Method, such as by attapulgite clay compounded powder in Muffle kiln roasting.The sintering temperature is 200-500 DEG C.
Sintering temperature is too high to make attapulgite duct cave in so as to cause adsorption capacity to be deteriorated, and is easily caused concave convex rod
Mass of soil gathers, and temperature is too low, cannot obtain Nano Silver simple substance.The roasting time is more than 5 minutes, preferably
5-180min.The roasting back loading is 3-100nm in the nano silver particles particle diameter of attapulgite's surface.Silver with
The mass ratio of attapulgite is 10/100-100/100, preferred 30/100-80/100.Step (1) in the present invention
The step of-(4) are to prepare the attapulgite-Nano Silver composite inorganic powder.Patent application
In CN201510262409.5, about the content of attapulgite-Nano Silver composite inorganic powder this is fully incorporated
Wen Zhong.And be further characterized by by wide-angle XRD, in the attapulgite clay compounded powder obtained after spray drying,
Silver nitrate reacts and finishes, and what is obtained is silver carbonate.
A preferred embodiment of the invention, in step (5), the blending is melt blending.
It is preferred that the temperature of the blending is 180-230 DEG C.The attapulgite-Nano Silver composite inorganic powder and polypropylene
The ratio of weight and number of resin is (0.01-1):100, preferably (0.01-0.1):100.Attapulgite-the nanometer
Silver-colored composite inorganic powder can adopt conventional method, such as banbury, Single screw extrusion with the blending of acrylic resin
Machine, double screw extruder etc..When being blended using double screw extruder, the temperature of the double screw extruder is
180-230℃。
Antibacterial polypropylene material prepared according to the methods of the invention, the attapulgite-Nano Silver composite inorganic powder
It is dispersed in acrylic resin as antiseptic.
According to a specific embodiment of preparation method of the present invention, it is comprised the following steps.
(1) attapulgite and water are hybridly prepared into attapulgite suspension.The attapulgite is preferably heat
Activation and the attapulgite of decentralized processing.Attapulgite is without acid treatment.The thermal activation treatment can adopt roasting
Method, wherein, sintering temperature is preferably 200-450 DEG C, and roasting time is preferably 5-60min；The concave convex rod
Concave convex rod soil mass concentration is less than 10% in native suspension；The decentralized processing of the attapulgite can be adopted
Conventional method of the prior art, for example：Ultrasonic disperse, mechanical agitation dispersion are (such as ball milling dispersion, high-speed stirring
Mix dispersion etc.) etc..
(2) silver nitrate is added in the attapulgite suspension described in step (1), is then stirred；
The silver nitrate is 17/100-170/100 with the mass ratio of attapulgite, and preferred mass ratio is
50/100-135/100；The temperature of the stirring be more than 50 DEG C, preferably 50-90 DEG C, the time of the stirring
For more than 1h.
(3) attapulgite suspension Jing after step (2) process is spray-dried, is obtained composite powder；
The temperature of the spray drying is preferably 150-200 DEG C.
(4) and then by the composite powder roasting is carried out, the composite inorganic powder obtained containing Nano Silver is (i.e. recessed
Convex rod soil-Nano Silver composite inorganic powder)；Wherein, the roasting time is more than 5min, preferably
5-180min；The roasting back loading is 3-100nm in the particle diameter of the nano silver particles of attapulgite's surface.
(5) by the attapulgite-Nano Silver composite inorganic powder, added by melt blending with acrylic resin
Work, processing temperature scope is 180-230 DEG C, and the content of attapulgite-Nano Silver composite inorganic powder is
0.01-1wt% (is based on acrylic resin).
According to the present invention, silver nitrate and attapulgite are stirred at a certain temperature after mixing, needed by spraying
Dry mode obtains treating the composite powder of roasting.Using other sides for example filtered and be dried with convection oven
Method, it is impossible to obtain and be spray-dried identical technique effect.Inventors believe that in the Nano Silver for preparing the present invention
During attapulgite clay compounded powder, attapulgite suspension and silver nitrate solution are mixed, stirred through heating
Mix, the carbanion in attapulgite in carbonate can be promoted to dissolve and silver carbonate suction is generated with silver ion reaction
It is attached to attapulgite's surface.In spray-drying process, unreacted silver nitrate solution and solution is dispersed in
In attapulgite plus thermal current in the presence of can further react generation silver carbonate.And by wide-angle
XRD confirms that in the attapulgite clay compounded powder obtained after spray drying, silver nitrate reacts and finishes, obtains
To be silver carbonate.During follow-up baking heat, silver carbonate is decomposed into silver-colored simple substance, finally with nanometer
The form of silver is equably supported on attapulgite's surface.The present invention is by the way that attapulgite and silver nitrate solution are stirred
It is well mixed, is then spray-dried, finally carry out roasting, prepares concavo-convex with attapulgite as carrier
Rod soil-Nano Silver composite inorganic powder and polypropylene fusion blending processing, are obtained modified polypropene (antibacterial polypropylene
Material).Due to attapulgite-Nano Silver composite powder particle in acrylic resin dispersiveness preferably, compared with
The anti-microbial property and rigidity of material can be just improved under little consumption.
According to the present invention, attapulgite is natural monodimension nanometer material, with very big specific surface area, adsorptivity
The nano effect such as energy and chemical reactivity so that the Nano Silver formed after roasting can be firmly adsorbed on concavo-convex
Rod soil surface, so forms equally distributed nano level Argent grain in attapulgite's surface.Although by direct
The method of heating and calcining decomposes silver nitrate can also obtain Nano Silver simple substance, but its decomposition temperature is high, energy consumption
Height, the nano silver particles of preparation are susceptible to reunite, and particle diameter is than larger.By heating stirring, then spray dry
It is dry so that the contained carbonate of silver nitrate and attapulgite the inside fully reacts, then less than silver nitrate decomposition temperature
Lower roasting can be prepared by Nano Silver, not only avoid the environment dirt brought using reducing agent or other chemical reactions
Dye, and because the decomposition temperature of silver carbonate is relatively low, roasting at relatively low temperatures can generate silver list
Matter.Silver-colored simple substance is equably adsorbed in attapulgite's surface in the form of Nano Silver, and this absorption is in attapulgite table
The nano silver active in face is very big, can slowly release the silver ion with antibacterial effect, and nano-Ag particles
It is firmly combined with attapulgite.In being applied to polypropylene, absorption can be more in the nano-Ag particles of attapulgite's surface
The anti-microbial property of plastics is improved well, and attapulgite also can play increasing just effect for material.
According to the present invention, found by substantial amounts of test, by silver ion with it is attapulgite clay compounded, so that it may so that system
The attapulgite clay compounded powder size of standby silver nanoparticle-containing reduces, so as to reach preferably dispersion in the plastic
Effect, with considerably less addition good antibacterial effect can be just reached.Meanwhile, the nanoscale of attapulgite
Dispersion so as under less consumption, can just improve the rigidity of plastics.This employing AgNO3It is multiple with attapulgite
The antibacterial agent (attapulgite-Nano Silver composite inorganic powder) that conjunction is prepared, auxiliary dosage is few, antibacterial effect
Rate is higher, greatly reduces the processing cost of antibiotic plastic, and improves the rigidity of material.
The third object of the present invention is to provide antibacterial polypropylene material prepared by antibacterial polypropylene material or said method
Application of the material in antibacterial product.Antibacterial polypropylene material in the present invention, anti-microbial property is good, and rigidity is good,
Antibacterial product field has broad application prospect.
Description of the drawings
Fig. 1 shows the transmission electron microscope photo of antibacterial polypropylene material according to an embodiment of the invention；
Fig. 2 shows the transmission electron microscope photo of antibacterial polypropylene material according to an embodiment of the invention；
Fig. 3 shows the transmission electron microscope photo of antibacterial polypropylene material according to an embodiment of the invention.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention will be further described, but does not constitute to any of the present invention
Limit.
Raw materials used in embodiment to be commercially available, the brilliant diameter of the single rod of attapulgite used exists in embodiment
Between 30-80nm.
Attapulgite thermal activation and decentralized processing are as follows：
A certain amount of attapulgite is put into Muffle furnace, the roasting 30min at 400 DEG C；Weigh on a certain amount of
The attapulgite of process is stated, to be added and be configured to the suspension that attapulgite mass concentration is 5% after distilled water, first
Mechanical agitation 1h, then ultrasonication 30min；Then the suspension handled well is existed by centrifuge
It is centrifuged under 12000r/min；Supernatant liquor is finally discarded, the attapulgite of thermal activation and decentralized processing is obtained final product.
Embodiment 1
The attapulgite (AT) of a certain amount of Jing thermal activations and decentralized processing is weighed, attapulgite quality is configured to dense
The water slurry for 5% is spent, then by silver nitrate solution (AgNO3/ AT=17/100) it is added to attapulgite suspension
In liquid, at 70 DEG C, magnetic agitation 2h, then attapulgite suspension is spray-dried at 175 DEG C,
Collect spray-dried obtained composite powder, finally by the composite powder for obtaining in Muffle furnace at 400 DEG C
Roasting 30min, obtains final product attapulgite-Nano Silver composite inorganic powder.
Embodiment 2
Except by silver nitrate solution and attapulgite suspension mixing after magnetic agitation temperature be adjusted to 50 DEG C in addition to, its
Its processing step is same as Example 1.
Embodiment 3
The attapulgite (AT) of a certain amount of Jing thermal activations and decentralized processing is weighed, attapulgite quality is configured to dense
The water slurry for 1% is spent, then by silver nitrate solution (AgNO3/ AT=17/100) it is added to attapulgite suspension
In liquid, at 50 DEG C, magnetic agitation 1h, then attapulgite suspension is spray-dried at 200 DEG C,
Collect spray-dried obtained composite powder, finally by the composite powder for obtaining in Muffle furnace at 500 DEG C
Roasting 30min, obtains final product attapulgite-Nano Silver composite inorganic powder.
Embodiment 4
Except by silver nitrate solution and attapulgite suspension mixing after magnetic agitation temperature be adjusted to 70 DEG C in addition to, its
Its processing step is same as Example 3.
Embodiment 5
Except by silver nitrate solution and attapulgite suspension mixing after magnetic agitation temperature be adjusted to 90 DEG C in addition to, its
Its processing step is same as Example 1.
Embodiment 6
The attapulgite of a certain amount of Jing thermal activations and decentralized processing is weighed, adds distilled water to be configured to concave convex rod soil property
Amount concentration is 10% suspension, then silver nitrate solution (AgNO3/ AT=170/100) it is added to attapulgite
In suspension, at 60 DEG C, 1h is stirred, then attapulgite suspension is spray-dried in 150 DEG C, received
The spray-dried obtained composite powder of collection, finally by the composite powder for obtaining in 200 DEG C of roasting 10min, i.e.,
Obtain attapulgite-Nano Silver composite inorganic powder.
Embodiment 7
Except by silver nitrate solution and attapulgite suspension mixing after magnetic agitation time be adjusted to 2h in addition to, its
Its processing step is same as Example 6 with characterizing method, and the particle size range of Nano Silver is 3-100nm.
Embodiment 8
The attapulgite of a certain amount of Jing thermal activations and decentralized processing is weighed, to be added and be configured to attapulgite after distilled water
Mass concentration is 5% suspension, then silver nitrate solution (AgNO3/ AT=135/100) it is added to concave convex rod
In native suspension, at 90 DEG C, then magnetic agitation 3h is spray-dried in 170 DEG C, collects Jing sprayings
Obtained composite powder is dried, finally the composite powder for obtaining concave convex rod is obtained final product into 200 DEG C of roasting 15min
Soil-Nano Silver composite inorganic powder.
Embodiment 9
In addition to the sintering temperature of powder is adjusted to 300 DEG C after by spray drying, other processing steps and embodiment 8
It is identical.
Embodiment 10
In addition to the sintering temperature of powder is adjusted to 400 DEG C after by spray drying, other processing steps and embodiment 8
It is identical.
Embodiment 11
In addition to the sintering temperature of powder is adjusted to 500 DEG C after by spray drying, other processing steps and embodiment 8
It is identical.
Embodiment 12
The attapulgite of a certain amount of Jing thermal activations and decentralized processing is weighed, to be added and be configured to attapulgite after distilled water
Mass concentration is 3% suspension, then silver nitrate solution (AgNO3/ AT=50/100) it is added to attapulgite
In suspension, at 70 DEG C, then magnetic agitation 2h is spray-dried at 170 DEG C, and collection is sprayed
The dried composite powder of mist, finally by the composite powder for obtaining at 350 DEG C roasting 5min, obtain final product concave convex rod
Soil-Nano Silver composite inorganic powder.
Embodiment 13
In addition to the roasting time of spray-dried rear powder is adjusted into 20min, other processing steps and sign side
Method is identical with embodiment 12.
Embodiment 14
In addition to the roasting time of spray-dried rear powder is adjusted into 60min, other processing steps and sign side
Method is identical with embodiment 12.
Embodiment 15
In addition to the roasting time of spray-dried rear powder is adjusted into 180min, other processing steps and sign
Method is identical with embodiment 12.
Embodiment 16
Except silver nitrate and attapulgite mass ratio are adjusted into 135:Outside 100, other processing steps and sign side
Method is same as Example 3.
Comparative example 1
Except by silver nitrate solution and attapulgite suspension mixing after magnetic agitation temperature be adjusted to room temperature in addition to, its
Its processing step is same as Example 3 with characterizing method.
Comparative example 2
Except after silver nitrate solution and attapulgite suspension are well mixed without heating magnetic agitation, directly spray
Outside mist is dried, other processing steps are same as Example 6 with characterizing method.
Comparative example 3
Except by silver nitrate solution and attapulgite suspension mixing after magnetic agitation time be adjusted to 30min in addition to,
Other processing steps are same as Example 6 with characterizing method.
Comparative example 4
In addition to the sintering temperature of powder is adjusted to 150 DEG C after by spray drying, other processing steps and embodiment 8
It is identical.
Comparative example 5
In addition to the roasting time of spray-dried rear powder is adjusted into 2min, other processing steps and sign side
Method is identical with embodiment 12.
Table 1.
Embodiment 17：
Adopt Ag prepared by embodiment 1 and attapulgite part by weight for 17/100 1# auxiliary agents proportionally
With polypropylene powder (Beijing Chemical Research Institute production, melt flow rate (MFR) 5.5g/10min), antioxidant 1010 and
168 (Switzerland vapour Ba Jiaji is produced, the two is used in mixed way with 1/1 ratio) mixes, its concrete composition：Poly- third
100 parts of alkene, 0.01 part of 1# Antibacterial accessory ingredients, 0.4 part of antioxidant 1010/168 mixture (wherein each component content
In terms of parts by weight), in high speed agitator (Beijing's English spy's plastics machinery head factory, model GH-10DY)
Middle mixing one minute, the ZSK-25 twin-screw extrusion systems with German Werner and Pleiderer companies are (long
Compare 30 in footpath：1st, diameter 25mm) blending granulation, each section of temperature of extruder be respectively 180 DEG C, 200 DEG C, 200 DEG C,
200 DEG C, 200 DEG C, 190 DEG C (head temperature), gained pellet Jing injectors (ningbo of china Hai Tian companies produce,
Model HTF110X/1J) injection, make sample standard batten.
What Fig. 1-3 showed is the electron microscopic picture of this embodiment sample.It can be seen that in polypropylene 1
In matrix, the attapulgite-favorable dispersibility of Nano Silver composite inorganic powder 2 can reach nanoscale dispersion.And
Attapulgite 4 and nano-Ag particles 3 are nano-grade size.Silver-colored simple substance 3 is uniformly inhaled in the form of Nano Silver
The surface of bar-shaped attapulgite 4 is attached to, mutually isolated structure, this absorption receiving in attapulgite's surface is formed
Rice silver activity is very big, can slowly release the silver ion with antibacterial effect.Attapulgite of the invention
The polypropylene (i.e. antibacterial polypropylene material) of-Nano Silver composite inorganic powder modification, adsorbs in attapulgite's surface
Nano-Ag particles can preferably improve the anti-microbial property of plastics, and attapulgite also can play increasing and just make for material
With.Antibacterial polypropylene material of the invention, in the addition of a small amount of attapulgite-Nano Silver composite inorganic powder
Under amount, it becomes possible to reach good antibacterial effect and significantly improve the rigidity of material.
Embodiment 18：
By more 0.05 part of 0.01 part of 1# Antibacterial accessory ingredients in embodiment 17, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Embodiment 19：
By more 0.1 part of 0.01 part of 1# Antibacterial accessory ingredients in embodiment 17, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Embodiment 20：
By 0.01 part of the 1# Antibacterial accessory ingredients more 2# Antibacterial accessory ingredients in embodiment 17, remaining each component ratio is not
Become, blending is uniform, remaining operation and extrusion, injecting condition are with embodiment 17.
Embodiment 21：
By more 0.05 part of 0.01 part of 2# Antibacterial accessory ingredients in embodiment 20, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Embodiment 22
By more 0.1 part of 0.01 part of 2# Antibacterial accessory ingredients in embodiment 20, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Comparative example 6:
By 100 parts of COPP powder and 0.4 part of mix of antioxidant, remaining operates and extrudes, injection
Condition is with embodiment 17.
Comparative example 7:
By 100 parts of COPP powder, 0.01 part of attapulgite, 0.4 part of mix of antioxidant, remaining
Operation and extrusion, injecting condition are with embodiment 17.
Comparative example 8:
Attapulgite part in comparative example 7 is changed into 0.05 part, remaining operation and extrusion, injecting condition are with real
Apply example 17.
Comparative example 9：
Attapulgite part in comparative example 7 is changed into 0.1 part, remaining operation and extrusion, injecting condition are with real
Apply example 17.
Comparative example 10：
By the 17# auxiliary agents in the more comparative example 1 of the 1# Antibacterial accessory ingredients in embodiment 17, remaining each component ratio is equal
Constant, blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Comparative example 11：
By more 0.05 part of 0.01 part of 17# Antibacterial accessory ingredients in comparative example 10, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Comparative example 12：
By more 0.1 part of 0.01 part of 17# Antibacterial accessory ingredients in comparative example 10, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Comparative example 13：
By the 20# auxiliary agents in the more comparative example 4 of the 1# Antibacterial accessory ingredients in embodiment 17, remaining each component ratio is equal
Constant, blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Comparative example 14：
By more 0.05 part of 0.01 part of 20# Antibacterial accessory ingredients in comparative example 13, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Comparative example 15：
By more 0.1 part of 0.01 part of 20# Antibacterial accessory ingredients in comparative example 13, remaining each component ratio is constant,
Blending is uniform, and remaining operation and extrusion, injecting condition are with embodiment 17.
Test：
The standard batten for respectively obtaining embodiment 17-22 and comparative example 6-15 injections is by ISO178 testing standards
Performance test is curved, by QB/TQ 2591-2003A《Antibiotic plastic Anti-microbial Performance Tests method and antibacterial
Effect》, detect and use bacterium：Escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus
(Staphylococcus aureus) testing standards of ATCC 6538 carry out anti-microbial property test, the result row for obtaining
In table 2.
As can be seen from the table, embodiment 17-22 using prepared Ag and attapulgite clay compounded auxiliary agent with
Pure attapulgite is compared, and is had to polypropylene and is preferably increased firm effect, and gives material preferable anti-microbial property.
The formula and performance of the antibacterial polypropylene of table 2.
Any numerical value mentioned in the present invention, if simply had between any minimum and any of the highest value
The interval of two units, then include all values of one unit of each increase from minimum to peak.For example,
If a kind of amount of component of life, or the value of the state-variable such as temperature, pressure, time is 50-90,
It means that specifically listing the number such as 51-89,52-88 ... and 69-71 and 70-71 in this specification
Value.For non-integral value, can with due regard to 0.1,0.01,0.001 or 0.0001 as a unit.This
Only it is some special examples for indicating.In this application, in a similar manner, cited minimum and peak
Between the combination that is possible to of numerical value be considered to disclose.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of antibacterial polypropylene material, including：Acrylic resin and the antibacterial being dispersed in the resin
Agent, the antiseptic is attapulgite-Nano Silver composite inorganic powder, wherein, the matter of Nano Silver and attapulgite
Than being 10/100-100/100, the particle size range of Nano Silver is 3-100nm to amount.
2. antibacterial polypropylene material according to claim 1, it is characterised in that the Nano Silver with it is concavo-convex
The mass ratio of rod soil is 30/100-80/100.
3. antibacterial polypropylene material according to claim 1 and 2, it is characterised in that the attapulgite
- Nano Silver composite inorganic powder is (0.01-1) with the ratio of weight and number of acrylic resin:100, preferably
(0.01-0.1):100。
4. a kind of method for preparing antibacterial polypropylene material, comprises the following steps：
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in the attapulgite suspension described in step (1), then in uniform temperature
Lower stirring；
(3) attapulgite suspension after step (2) stirring is spray-dried, is obtained composite powder；
(4) composite powder is carried out into roasting, obtains attapulgite-Nano Silver composite inorganic powder；
(5) attapulgite-Nano Silver composite inorganic powder is blended with acrylic resin, is obtained institute
The antibacterial polypropylene material stated.
5. method according to claim 4, it is characterised in that in the step (1) is described outstanding
In supernatant liquid, the concentration of attapulgite is less than 10wt%, preferably 1-10wt%.
6. the method according to claim 4 or 5, it is characterised in that in the step (2), institute
The temperature for stating stirring is higher than 50 DEG C, preferably 50-90 DEG C；The time of the stirring is more than 1h, preferably
1h-10h；And/or, the silver nitrate is 17/100-170/100 with the mass ratio of attapulgite, preferably
50/100-135/100。
7. the method according to any one in claim 4-6, it is characterised in that in step (3),
The temperature of the spray drying is 150-200 DEG C；And/or, in step (4), the temperature of the roasting is
200-500 DEG C, the time of the roasting is more than 5min, preferred 5-180min.
8. the method according to any one in claim 4-7, it is characterised in that in the attapulgite
In-Nano Silver composite inorganic powder, the particle diameter of silver is 3-100nm；And/or silver is with the mass ratio of attapulgite
10/100-100/100, preferred 30/100-80/100.
9. the method according to any one in claim 4-8, it is characterised in that in step (5),
The blending is melt blending, and preferably the temperature of the blending is 180-230 DEG C；And/or the attapulgite-
Nano Silver composite inorganic powder is (0.01-1) with the ratio of weight and number of acrylic resin:100, preferably
(0.01-0.1):100。
10. appoint in the antibacterial polypropylene material or claim 4-9 according to any one in claim 1-3
The application of antibacterial polypropylene material prepared by one methods described of meaning in antibacterial product.
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| CN107163622A (en) * | 2017-06-27 | 2017-09-15 | 长兴大地新型材料有限公司 | A kind of preparation method of the inorganic modified nano-calcium carbonate of durable antibiotic |
| CN107163377A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of Antibacterial polypropylene composition and preparation method thereof, application |
| CN109197627A (en) * | 2018-10-25 | 2019-01-15 | 杭州渔森农业技术开发有限公司 | A kind of livestock crib |
| CN110205016A (en) * | 2019-06-24 | 2019-09-06 | 李文森 | A kind of Antibacterial finish paint for redwood furniture |
| CN111117076A (en) * | 2019-12-25 | 2020-05-08 | 界首市天路包装材料有限公司 | Special modified material with mildew-proof function for coating bucket |
| CN111206295A (en) * | 2020-02-03 | 2020-05-29 | 深圳市沃尔核材股份有限公司 | Special material for sterilization mask, sterilization net, sterilization mask and preparation method of sterilization mask |
| CN111410510A (en) * | 2020-04-21 | 2020-07-14 | 福建省泉州达盛窑陶瓷有限公司 | Manufacturing process of antibacterial dark-red enameled pottery |
| CN111548550A (en) * | 2020-06-23 | 2020-08-18 | 陈志益 | Antibacterial HDPE (high-density polyethylene) plastic chair suitable for outdoor and preparation method thereof |
| CN112341854A (en) * | 2020-11-16 | 2021-02-09 | 湖南加美乐素新材料股份有限公司 | Nano-modified antibacterial organosilicon waterproofing agent and preparation method thereof |
| CN114561130A (en) * | 2021-12-20 | 2022-05-31 | 佛山市高明区首邦化工有限公司 | Weather-resistant latex paint and production equipment thereof |
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| CN107163377A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of Antibacterial polypropylene composition and preparation method thereof, application |
| CN107163377B (en) * | 2017-05-19 | 2018-10-09 | 勤业工业（龙南）有限公司 | A kind of Antibacterial polypropylene composition and preparation method thereof, application |
| CN107163622A (en) * | 2017-06-27 | 2017-09-15 | 长兴大地新型材料有限公司 | A kind of preparation method of the inorganic modified nano-calcium carbonate of durable antibiotic |
| CN109197627A (en) * | 2018-10-25 | 2019-01-15 | 杭州渔森农业技术开发有限公司 | A kind of livestock crib |
| CN110205016A (en) * | 2019-06-24 | 2019-09-06 | 李文森 | A kind of Antibacterial finish paint for redwood furniture |
| CN111117076A (en) * | 2019-12-25 | 2020-05-08 | 界首市天路包装材料有限公司 | Special modified material with mildew-proof function for coating bucket |
| CN111206295A (en) * | 2020-02-03 | 2020-05-29 | 深圳市沃尔核材股份有限公司 | Special material for sterilization mask, sterilization net, sterilization mask and preparation method of sterilization mask |
| CN111410510A (en) * | 2020-04-21 | 2020-07-14 | 福建省泉州达盛窑陶瓷有限公司 | Manufacturing process of antibacterial dark-red enameled pottery |
| CN111548550A (en) * | 2020-06-23 | 2020-08-18 | 陈志益 | Antibacterial HDPE (high-density polyethylene) plastic chair suitable for outdoor and preparation method thereof |
| CN111548550B (en) * | 2020-06-23 | 2023-12-22 | 陈志益 | Antibacterial HDPE plastic chair suitable for outdoor use and preparation method thereof |
| CN112341854A (en) * | 2020-11-16 | 2021-02-09 | 湖南加美乐素新材料股份有限公司 | Nano-modified antibacterial organosilicon waterproofing agent and preparation method thereof |
| CN114561130A (en) * | 2021-12-20 | 2022-05-31 | 佛山市高明区首邦化工有限公司 | Weather-resistant latex paint and production equipment thereof |
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