CN106633364B - A kind of antibacterial polypropylene and preparation method thereof - Google Patents
A kind of antibacterial polypropylene and preparation method thereof Download PDFInfo
- Publication number
- CN106633364B CN106633364B CN201510711289.2A CN201510711289A CN106633364B CN 106633364 B CN106633364 B CN 106633364B CN 201510711289 A CN201510711289 A CN 201510711289A CN 106633364 B CN106633364 B CN 106633364B
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- antibacterial
- nano silver
- polypropylene material
- silver
- 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.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
- C08K9/00—Use of pretreated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of antibacterial polypropylene materials.The antibacterial polypropylene material, the antibacterial agent for including: acrylic resin and being dispersed in the resin, the antibacterial agent are attapulgite-nano silver composite inorganic powder, wherein, the mass ratio of nano silver and attapulgite is 10/100-100/100, and the particle size range of nano silver is 3-100nm.Complex antimicrobials of the present invention have dosage few, and price is low, and preparation process is simple, improves the advantages that mechanical property, while improving material anti-microbial property, under lesser dosage, the rigidity of material can be improved, is a kind of modified additive of ideal acrylic resin.
Description
Technical field
The present invention relates to the field of polymers, further say, are to be related to a kind of using attapulgite being carrier containing nano silver
The composite inorganic powder of particle is the polypropylene material of antibacterial agent, which can be applied to the various necks for producing and living
Domain.
Background technique
As the demand of antibacterial plastic product is continuously increased, various antibacterial agents and antibiotic plastic are also with development.Antibacterial agent
It is divided into inorganic antiseptic and organic antibacterial agent.Inorganic antiseptic, such as Ag, Zn etc., safety, heat resistance, durability are preferable, will
It is carried in the inorganic carriers such as zeolite, glass, montmorillonite, diatomite, Ag, and Zn ion can slowly release.Organic anti-bacterial
Agent, for example, plug bacterium spirit, Bravo, carbendazim, zinc pyrithione, normal-butyl benzoisothiazolinone (BBIT) etc., largely have
Machine antibacterial agent hydrophily is poor, may be precipitated for plastics with faster speed, not wash resistant, working life is short.
Silver ion as antibacterial agent, have efficiently, safety, wide sterilization spectrum, heat resistance, have no drug resistance with it is highly selective etc. excellent
Point.Silver ion has high reaction activity, but in most of practical applications, silver ion is easy to react and lose with biological fluid
It is living, but these limitations can be resolved by nano silver particles.With the emergence and development of nanosecond science and technology, nano silver is opened
Begin to enter daily life, has been widely used in health care and food hygiene field now.
By nano-silver loaded on different carriers, come as antibacterial additives using the antibacterial that nano silver can be improved is imitated
Fruit and dispersibility.The carrier for carrying silver is usually the inorganic mineral of meso-hole structure, including zeolite, galapectite, sepiolite, mesoporous dioxy
SiClx, attapulgite etc..Wherein attapulgite is the nanoparticle of porous structure, and main component is palygorskite (concave convex rod
Stone), it is a kind of aqueous rich magnesium silicate clay mineral with chain layer structure.Its skeleton structure is in 3 D stereo shape, by silicon
Oxygen tetrahedron and magnalium octahedron are connected with each other by sharing vertex, have it is numerous be parallel to stick it is brilliant (it is needle-shaped, micro- rodlike or
Fibrous monocrystal) direction arrangement tubular nanometer grade duct, duct run through total, from the section duct Shang Kan be in size phase
Deng (about 0.38nm × 0.63nm) honeycomb, belong to natural monodimension nanometer material, there are good absorption property and inexpensive, right and wrong
Normal ideal carrier material, therefore cause the attention of scholar and research structure.As Chinese patent CN1568703A is living on surface
Property agent and organic reducing agent it is existing under the conditions of, be that carrier with silver nitrate solution chemically reacts to form composite antibacterial using attapulgite
Agent；Similar, Chinese patent CN1685830A is immersed in zeolite powder in silver nitrate solution, so that silver ion sufficiently adsorbs
In the hole of zeolite, it is nano silver that hydrazine hydrate is then added under stirring conditions silver ion reduction.
Chemical reduction method prepares carrying silver antimicrobials, usually has high requirements to the purity of carrier, surface nature etc., and
Also to be dispersed and be adjusted the processing of pH value before addition silver nitrate solution to carrier solution.In order to reduce between Nano silver grain
Mutually reunite, considerable amount of surfactant to be also added in reduction process, in finally also falling by continuous eccentric cleaning
The reducing agent and surfactant of face remnants, preparation process is complicated, and long preparation period limits its large-scale production application.
The content of nanometer silver of such method supported on carriers is very low, leads to antibacterial antiplaque agent effect not and be very well, remaining in antibacterial agent
Reducing agent and surfactant are applied to have a great impact.
Polypropylene is a kind of thermoplastic being widely used, and cheap and comprehensive performance is good, but its antibacterial changes
Property, it is also necessary to continue to study.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of attapulgite-nano silver composite inorganic powder
Modified polypropene (antibacterial polypropylene material) and preparation method thereof, improves anti-microbial property and mechanical property.With cheap bumps
Stick soil and silver nitrate are raw material, without adding any reducing agent, will be spray-dried after powder after calcination process (such as 200-
500 DEG C of roastings) it is added in acrylic resin and is blended, the attapulgite clay compounded inorganic powder for obtaining the carrying nano silver is modified poly-
Propylene (antibacterial polypropylene material).Present invention process is simple, environmentally protective.The use of organic solvent is avoided, and reduces ring
The discharge of border pollutant.
An object of the present invention is to provide a kind of antibacterial polypropylene material (i.e. attapulgite-nano silver composite inorganic powder
Last modified polypropene) comprising: acrylic resin and the antibacterial agent being dispersed in the resin, the antibacterial agent are bumps
Stick soil-nano silver composite inorganic powder.Wherein the mass ratio of silver and attapulgite is 10/100-100/100, the partial size of nano silver
Range is 3-100nm.
According to the present invention, the attapulgite in rodlike or fibrous structure and have hollow nanoscale duct,
The stick crystalline substance diameter of attapulgite is between 10-80nm.There are the nano-Ag particles of partial size 3-100nm in attapulgite's surface load.
Nano-Ag particles are spherical shape.It is preferred that the mass ratio of the nano silver and attapulgite is 30/100-80/100.
Antibacterial polypropylene material according to the present invention, the attapulgite-nano silver composite inorganic powder and poly- third
The weight ratio of olefine resin is (0.01-1): 100, preferably (0.01-0.1): 100.
Antibacterial polypropylene material according to the present invention, wherein silver-colored simple substance is adsorbed on attapulgite table in the form of nano silver
Face, and nano-Ag particles and attapulgite are firmly combined.Nano silver active is big, can slowly release with antibacterial effect
Silver ion.And attapulgite-nano silver composite inorganic powder size is small, is nanoscale auxiliary agent, has in acrylic resin
Good dispersion performance can reach nano-dispersion, improve the rigidity and antibacterial effect of material.Attapulgite-nano silver
The small size and bigger serface of composite inorganic powder can make it under a small amount of additive amount, can also play preferable modified effect
Fruit.
The second object of the present invention is to provide a kind of antibacterial polypropylene material (i.e. attapulgite-nano silver composite inorganic powder
Last modified polypropene) preparation method.The described method includes:
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred at a certain temperature
It mixes；
(3) attapulgite suspension after step (2) stirring is spray-dried, obtains composite powder；
(4) then the composite powder is roasted, obtains attapulgite-nano silver composite inorganic powder；
(5) attapulgite-nano silver composite inorganic powder is blended with acrylic resin, obtains described resist
Bacterium polypropylene material.
A preferred embodiment according to the present invention, in step (1), the attapulgite be preferably thermal activation and/
Or the attapulgite of decentralized processing, to improve the dispersibility of attapulgite.It is living that conventional heat can be used in the thermal activation treatment
Change method can such as use roasting method, and maturing temperature is 200-450 DEG C, calcining time 5-60min.Point of the attapulgite
Scattered processing method can use common method in the prior art, such as: ultrasonic wave dispersion, mechanical stirring dispersion (such as ball milling point
Scattered, high-speed stirred dispersion etc.) etc..In a specific embodiment, in the attapulgite suspension, the quality of attapulgite
Concentration is no more than 10%, preferably 1-10wt%.The attapulgite is handled without acid.
A preferred embodiment according to the present invention is preparing nano silver attapulgite of the invention in step (2)
During composite powder, attapulgite suspension and silver nitrate solution are mixed by under certain temperature (being higher than room temperature)
Stirring, carbanion in attapulgite in carbonate can be promoted to dissolve and react with silver ion generation silver carbonate be adsorbed on it is recessed
Convex stick soil surface.The temperature of the stirring is higher than 50 DEG C, preferably 50-90 DEG C.The time of the stirring is 1h or more, preferably
1h-10h.The mass ratio of the silver nitrate and attapulgite is 17/100-170/100, preferably 50/100-135/100.
A preferred embodiment according to the present invention, in step (3), the temperature of the spray drying is 150-200
℃.In spray-drying process, unreacted silver nitrate solution and evenly dispersed attapulgite in the solution are in heating air-flow
Under effect, it can be reacted with further occurrence and generate silver carbonate.The methods for for example being filtered using others and being dried with convection oven,
It can not obtain and be spray-dried identical technical effect.
A preferred embodiment according to the present invention, in step (4), the roasting can be conventional method of roasting, example
Such as by attapulgite clay compounded powder in Muffle kiln roasting.The maturing temperature is 200-500 DEG C.Maturing temperature is excessively high can make it is recessed
Convex stick soil duct collapses so as to cause adsorption capacity variation, and attapulgite is easy to cause to reunite, and temperature is too low, is unable to get
Nano silver simple substance.The calcining time is 5 minutes or more, preferably 5-180min.The roasting back loading is in attapulgite's surface
Nano silver particles partial size be 3-100nm.The mass ratio of silver and attapulgite is 10/100-100/100, preferably 30/100-80/
100.Step (1)-(4) in the present invention are the step of preparing the attapulgite-nano silver composite inorganic powder.Patent application
In CN201510262409.5, it is fully incorporated in relation to attapulgite-nano silver composite inorganic powder content herein.And lead to
Crossing wide-angle XRD further confirms, in the attapulgite clay compounded powder obtained after spray drying, silver nitrate end of reaction,
What is obtained is silver carbonate.
A preferred embodiment according to the present invention, in step (5), described be blended is melt blending.It is preferred that described
The temperature of blending is 180-230 DEG C.The attapulgite-nano silver composite inorganic powder and acrylic resin weight fraction ratio
For (0.01-1): 100, preferably (0.01-0.1): 100.The attapulgite-nano silver composite inorganic powder and acrylic resin
Blending conventional method, such as mixer, single screw extrusion machine, double screw extruder can be used.When use twin-screw extrusion
When machine is blended, the temperature of the double screw extruder is 180-230 DEG C.
Antibacterial polypropylene material prepared according to the methods of the invention, the attapulgite-nano silver composite inorganic powder are made
It is dispersed in acrylic resin for antibacterial agent.
A specific embodiment of the preparation method according to the present invention comprising following steps.
(1) attapulgite and water are hybridly prepared into attapulgite suspension.The attapulgite be preferably thermal activation and
The attapulgite of decentralized processing.Attapulgite is handled without acid.Method of roasting can be used in the thermal activation treatment, wherein roasting
Temperature is preferably 200-450 DEG C, and calcining time is preferably 5-60min；Concave convex rod soil property amount is dense in the attapulgite suspension
Degree is no more than 10%；The decentralized processing of the attapulgite can use conventional method in the prior art, such as: ultrasound point
It dissipates, mechanical stirring disperses (such as ball milling dispersion, high-speed stirred dispersion) etc..
(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred；The nitric acid
The mass ratio of silver and attapulgite is 17/100-170/100, and preferred mass ratio is 50/100-135/100；The temperature of the stirring
Degree is 50 DEG C or more, and preferably 50-90 DEG C, the time of the stirring is 1h or more.
(3) will through step (2), treated, and attapulgite suspension is spray-dried, obtain composite powder；The spray
The dry temperature of mist is preferably 150-200 DEG C.
(4) then the composite powder is roasted, obtains composite inorganic powder (the i.e. attapulgite-containing nano silver
Nano silver composite inorganic powder)；Wherein, the calcining time is 5min or more, preferably 5-180min；The roasting back loading
It is 3-100nm in the partial size of the nano silver particles of attapulgite's surface.
(5) it by the attapulgite-nano silver composite inorganic powder, is processed, is added by melt blending with acrylic resin
Work temperature range is 180-230 DEG C, and attapulgite-nano silver composite inorganic powder content is 0.01-1wt% (based on poly- third
Olefine resin).
According to the present invention, after silver nitrate and attapulgite being stirred at a certain temperature, need to pass through spray drying
Mode obtain composite powder to be roasted.Using other such as filterings and the method dry with convection oven, can not obtain
The identical technical effect with spray drying.Inventors believe that in the mistake for preparing the attapulgite clay compounded powder of nano silver of the invention
Attapulgite suspension and silver nitrate solution are mixed, by heating stirring, can be promoted in attapulgite in carbonate by Cheng Zhong
Carbanion, which dissolves and reacts generation silver carbonate with silver ion, is adsorbed on attapulgite's surface.In spray-drying process, not
The silver nitrate solution of reaction and evenly dispersed attapulgite in the solution can be with further occurrences under the action of heating air-flow
Reaction generates silver carbonate.And confirmed by wide-angle XRD, in the attapulgite clay compounded powder obtained after spray drying, silver nitrate
End of reaction, what is obtained is silver carbonate.During subsequent baking heat, silver carbonate is decomposed into silver-colored simple substance, finally
Attapulgite's surface is equably supported in the form of nano silver.The present invention is mixed by stirring attapulgite and silver nitrate solution
It closes uniformly, is then spray-dried, is finally roasted, prepare attapulgite-nano silver using attapulgite as carrier
Processing is blended with polypropylene fusion for composite inorganic powder, is made modified polypropene (antibacterial polypropylene material).Due to attapulgite-
The composite powder particle of nano silver dispersibility in acrylic resin preferably, can improve the antibacterial of material under lesser dosage
Performance and rigidity.
According to the present invention, attapulgite is natural monodimension nanometer material, has very big specific surface area, absorption property and change
The nano effects such as reactivity are learned, allow the nano silver formed after roasting to be firmly adsorbed on attapulgite's surface, in this way
Equally distributed nanoscale Argent grain is formed in attapulgite's surface.Although by the method that directly heats calcining by silver nitrate
Also available nano silver simple substance is decomposed, but its decomposition temperature is high, energy consumption is high, and the nano silver particles of preparation are easy to happen group
Poly-, partial size is bigger.By heating stirring, then spray drying is so that carbonate contained by inside silver nitrate and attapulgite is abundant
Then reaction can be prepared by nano silver lower than roasting under silver nitrate decomposition temperature, not only avoid using reducing agent or its
He chemically reacts bring environmental pollution, and since the decomposition temperature of silver carbonate is relatively low, roasts at relatively low temperatures
It burns and produces silver-colored simple substance.Silver-colored simple substance is equably adsorbed on attapulgite's surface in the form of nano silver, this to be adsorbed on bumps
The nano silver active on stick soil surface is very big, can slowly release the silver ion with antibacterial effect, and nano-Ag particles with
Attapulgite is firmly combined.Modeling can be preferably improved applied to the nano-Ag particles in polypropylene, being adsorbed on attapulgite's surface
The anti-microbial property of material, and attapulgite can also play the role of increasing just for material.
According to the present invention, by largely testing discovery, by silver ion with it is attapulgite clay compounded, so that it may so that preparation contain
The attapulgite clay compounded powder size of Nano silver grain reduces, to reach better dispersion effect, in the plastic with considerably less
Additive amount can reach good antibacterial effect.Meanwhile the nano-dispersion of attapulgite, make it under smaller dosage,
The rigidity of plastics can be improved.It is this to use AgNO3(attapulgite-is received with the attapulgite clay compounded antibacterial agent prepared
The silver-colored composite inorganic powder of rice), auxiliary dosage is few, and antimicrobial efficiency is higher, greatly reduces the processing cost of antibiotic plastic, and improve
The rigidity of material.
The third object of the present invention is to provide antibacterial polypropylene material or the antibacterial polypropylene material of above method preparation exists
Application in antibacterial product.Antibacterial polypropylene material in the present invention, anti-microbial property is good, and rigidity is good, has in antibacterial product field
There is wide application prospect.
Detailed description of the invention
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
Below with reference to embodiment and attached drawing, the present invention will be further described, but does not constitute to any limit of the invention
System.
In embodiment it is raw materials used be it is commercially available, the diameter of the single stick crystalline substance of attapulgite used is in 30- in embodiment
Between 80nm.
Attapulgite thermal activation and decentralized processing are as follows:
A certain amount of attapulgite is put into Muffle furnace, roasts 30min at 400 DEG C；Weigh a certain amount of above-mentioned processing
Attapulgite, be configured to the suspension that attapulgite mass concentration is 5%, first mechanical stirring 1h, then surpass after distilled water is added
Sonicated 30min；Then the suspension handled well is centrifuged at 12000r/min by centrifuge；Finally discard
Layer clear liquid is to get thermal activation and the attapulgite of decentralized processing.
Embodiment 1
The a certain amount of attapulgite (AT) through thermal activation and decentralized processing is weighed, being configured to attapulgite mass concentration is
5% water slurry, then by silver nitrate solution (AgNO3/ AT=17/100) it is added in attapulgite suspension, at 70 DEG C
Under, magnetic agitation 2h, then attapulgite suspension is spray-dried at 175 DEG C, it collects spray-dried obtained multiple
Powder is closed, it is multiple to get attapulgite-nano silver that obtained composite powder is finally roasted to 30min in Muffle furnace at 400 DEG C
Close inorganic powder.
Embodiment 2
In addition to the temperature of magnetic agitation is adjusted to 50 DEG C after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step is same as Example 1.
Embodiment 3
The a certain amount of attapulgite (AT) through thermal activation and decentralized processing is weighed, being configured to attapulgite mass concentration is
1% water slurry, then by silver nitrate solution (AgNO3/ AT=17/100) it is added in attapulgite suspension, at 50 DEG C
Under, magnetic agitation 1h, then attapulgite suspension is spray-dried at 200 DEG C, it collects spray-dried obtained multiple
Powder is closed, it is multiple to get attapulgite-nano silver that obtained composite powder is finally roasted to 30min in Muffle furnace at 500 DEG C
Close inorganic powder.
Embodiment 4
In addition to the temperature of magnetic agitation is adjusted to 70 DEG C after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step is same as Example 3.
Embodiment 5
In addition to the temperature of magnetic agitation is adjusted to 90 DEG C after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step is same as Example 1.
Embodiment 6
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, it is dense that addition distilled water is configured to attapulgite quality
The suspension that degree is 10%, then silver nitrate solution (AgNO3/ AT=170/100) it is added in attapulgite suspension, 60
At DEG C, 1h is stirred, then attapulgite suspension is spray-dried in 150 DEG C, collects spray-dried composite powder obtained
End, finally by obtained composite powder in 200 DEG C of roasting 10min to get attapulgite-nano silver composite inorganic powder.
Embodiment 7
In addition to the time of magnetic agitation is adjusted to 2h after mix silver nitrate solution and attapulgite suspension, other techniques
Step is same as Example 6 with characterizing method, and the particle size range of nano silver is 3-100nm.
Embodiment 8
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, is configured to attapulgite quality after distilled water is added
The suspension that concentration is 5%, then silver nitrate solution (AgNO3/ AT=135/100) it is added in attapulgite suspension,
At 90 DEG C, then magnetic agitation 3h is spray-dried in 170 DEG C, is collected spray-dried composite powder obtained, finally will
Obtained composite powder is in 200 DEG C of roasting 15min to get attapulgite-nano silver composite inorganic powder.
Embodiment 9
Except will spray drying after powder maturing temperature be adjusted to 300 DEG C in addition to, other processing steps are same as Example 8.
Embodiment 10
Except will spray drying after powder maturing temperature be adjusted to 400 DEG C in addition to, other processing steps are same as Example 8.
Embodiment 11
Except will spray drying after powder maturing temperature be adjusted to 500 DEG C in addition to, other processing steps are same as Example 8.
Embodiment 12
The a certain amount of attapulgite through thermal activation and decentralized processing is weighed, is configured to attapulgite quality after distilled water is added
The suspension that concentration is 3%, then silver nitrate solution (AgNO3/ AT=50/100) it is added in attapulgite suspension, 70
At DEG C, then magnetic agitation 2h is spray-dried at 170 DEG C, collects the composite powder after being spray-dried, and finally will
Obtained composite powder roasts 5min at 350 DEG C to get attapulgite-nano silver composite inorganic powder.
Embodiment 13
Except will it is spray-dried after powder calcining time be adjusted to 20min in addition to, other processing steps and characterizing method are equal
It is identical as embodiment 12.
Embodiment 14
Except will it is spray-dried after powder calcining time be adjusted to 60min in addition to, other processing steps and characterizing method are equal
It is identical as embodiment 12.
Embodiment 15
Except will it is spray-dried after powder calcining time be adjusted to 180min in addition to, other processing steps and characterization
Method is identical as embodiment 12.
Embodiment 16
In addition to silver nitrate and attapulgite mass ratio are adjusted to 135:100, other processing steps and characterizing method are equal
It is same as Example 3.
Comparative example 1
In addition to the temperature of magnetic agitation is adjusted to room temperature after mix silver nitrate solution and attapulgite suspension, Qi Tagong
Skill step and characterizing method are same as Example 3.
Comparative example 2
Except by silver nitrate solution and attapulgite suspension, after mixing without heating magnetic agitation, Direct spraying is dry
Dry outer, other processing steps and characterizing method are same as Example 6.
Comparative example 3
It is other in addition to the time of magnetic agitation is adjusted to 30min after mix silver nitrate solution and attapulgite suspension
Processing step is same as Example 6 with characterizing method.
Comparative example 4
Except will spray drying after powder maturing temperature be adjusted to 150 DEG C in addition to, other processing steps are same as Example 8.
Comparative example 5
Except will it is spray-dried after powder calcining time be adjusted to 2min in addition to, other processing steps and characterizing method with
Embodiment 12 is identical.
Table 1.
Embodiment 17:
Using Ag prepared by embodiment 1 and attapulgite weight ratio is 17/100 1# auxiliary agent proportionally with poly- third
(Switzerland's vapour bar adds for alkene powder (Beijing Chemical Research Institute's production, melt flow rate (MFR) 5.5g/10min), antioxidant 1010 and 168
Base production, the two are used in mixed way with 1/1 ratio) mix, concrete composition: 100 parts of polypropylene, 1# Antibacterial accessory ingredient 0.01
Part, antioxidant 1010/0.4 part of 168 mixture (wherein each component content based on parts by weight), in high speed agitator (Beijing
City's English spy's plastics machinery head factory, model GH-10DY) middle mixing one minute, with German Werner and Pleiderer company
ZSK-25 twin-screw extrusion system (draw ratio 30:1, diameter 25mm), which is blended, to be granulated, and extruder temperature of each section is respectively 180 DEG C,
200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (head temperature), (ningbo of china Hai Tian company is raw through injector for gained pellet
Produce, model HTF110X/1J) injection molding, sample standard batten is made.
What Fig. 1-3 was shown is the electron microscopic picture of this embodiment sample.It can be seen from the figure that in 1 matrix of polypropylene,
Attapulgite -2 favorable dispersibility of nano silver composite inorganic powder, can reach nano-dispersion.And attapulgite 4 and nano silver
Particle 3 is nano-grade size.Silver-colored simple substance 3 is uniformly adsorbed on rodlike 4 surface of attapulgite in the form of nano silver, forms phase
The structure being mutually isolated, this nano silver active for being adsorbed on attapulgite's surface is very big, can slowly release and imitate with antibacterial
The silver ion of fruit.Attapulgite according to the present invention-nano silver composite inorganic powder modification polypropylene (i.e. antibacterial polypropylene material
Material), the nano-Ag particles for being adsorbed on attapulgite's surface can preferably improve the anti-microbial property of plastics, and attapulgite also can be
Material plays the role of increasing rigid.Antibacterial polypropylene material according to the present invention, in a small amount of attapulgite-nano silver composite inorganic powder
Additive amount under, it will be able to reach and 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 ingredient in embodiment 17, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Embodiment 19:
By more 0.1 part of 0.01 part of 1# Antibacterial accessory ingredient in embodiment 17, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Embodiment 20:
By 0.01 part of the 1# Antibacterial accessory ingredient more 2# Antibacterial accessory ingredient in embodiment 17, remaining each component ratio is constant, altogether
Be mixed it is even, remaining operation and squeeze out, injecting condition is the same as embodiment 17.
Embodiment 21:
By more 0.05 part of 0.01 part of 2# Antibacterial accessory ingredient in embodiment 20, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Embodiment 22
By more 0.1 part of 0.01 part of 2# Antibacterial accessory ingredient in embodiment 20, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 6:
By 100 parts of copolymer polypropylene powder and 0.4 part of mix of antioxidant, remaining operation and extrusion, injecting condition are equal
With embodiment 17.
Comparative example 7:
By 0.4 part of 100 parts of copolymer polypropylene powder, 0.01 part of attapulgite, antioxidant mix, remaining operates and squeezes
Out, injecting condition is the same as embodiment 17.
Comparative example 8:
Attapulgite part in comparative example 7 is changed to 0.05 part, remaining operation and extrusion, the same embodiment of injecting condition
17。
Comparative example 9:
Attapulgite part in comparative example 7 is changed to 0.1 part, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 10:
By the 17# auxiliary agent in the more comparative example 1 of the 1# Antibacterial accessory ingredient in embodiment 17, remaining each component ratio is constant,
It is blended uniformly, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 11:
By more 0.05 part of 0.01 part of 17# Antibacterial accessory ingredient in comparative example 10, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 12:
By more 0.1 part of 0.01 part of 17# Antibacterial accessory ingredient in comparative example 10, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 13:
By the 20# auxiliary agent in the more comparative example 4 of the 1# Antibacterial accessory ingredient in embodiment 17, remaining each component ratio is constant,
It is blended uniformly, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 14:
By more 0.05 part of 0.01 part of 20# Antibacterial accessory ingredient in comparative example 13, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Comparative example 15:
By more 0.1 part of 0.01 part of 20# Antibacterial accessory ingredient in comparative example 13, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 17.
Test:
The standard batten for being respectively molded embodiment 17-22 and comparative example 6-15 is carried out curved by ISO178 testing standard
Bent performance test, by QB/TQ 2591-2003A " antibiotic plastic test method of antibacterial performance and antibacterial effect ", bacterium is used in detection: big
Enterobacteria (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus aureus) ATCC
6538 testing standards carry out anti-microbial property test, and obtained result is listed in table 2.
As can be seen from the table, embodiment 17-22 is using prepared Ag and attapulgite clay compounded auxiliary agent and pure bumps
Stick soil is compared, and is had to polypropylene and is preferably increased rigid effect, and assigns material preferable anti-microbial property.
The formula and performance of 2. antibacterial polypropylene of table
Any numerical value mentioned in the present invention, if between any minimum and any highest value be there are two
The interval of unit then includes each all values for increasing a unit from minimum to peak.For example, if life is a kind of
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (11)
1. a kind of antibacterial polypropylene material, comprising: acrylic resin and the antibacterial agent being dispersed in the resin, the antibacterial
Agent is attapulgite-nano silver composite inorganic powder, wherein the mass ratio of nano silver and attapulgite is 10/100-100/
100, the particle size range of nano silver is 3-100nm,
The method for preparing the antibacterial polypropylene material, comprising the following steps:
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in attapulgite suspension described in step (1), is then stirred at a temperature of 50-90 DEG C；
(3) attapulgite suspension after step (2) stirring is spray-dried, obtains composite powder；
(4) composite powder is roasted, obtains attapulgite-nano silver composite inorganic powder；
(5) attapulgite-nano silver composite inorganic powder is blended with acrylic resin, it is poly- obtains the antibacterial
Propylene material,
Wherein, in the step (1), in the suspension, the concentration of attapulgite is no more than 10wt%,
In the step (2), the time of the stirring is 1h or more；In step (3), the temperature of the spray drying is
150-200℃；With in step (4), the temperature of the roasting is 200-500 DEG C, and the time of the roasting is 5min or more.
2. antibacterial polypropylene material according to claim 1, which is characterized in that the quality of the nano silver and attapulgite
Than for 30/100-80/100.
3. antibacterial polypropylene material according to claim 1 or 2, which is characterized in that the attapulgite-nano silver is compound
The weight fraction ratio of inorganic powder and acrylic resin is (0.01-1): 100.
4. antibacterial polypropylene material according to claim 3, which is characterized in that the compound nothing of attapulgite-nano silver
The weight fraction ratio of machine powder and acrylic resin is (0.01-0.1): 100.
5. antibacterial polypropylene material according to claim 1, which is characterized in that in the step (1), the suspension
In, the concentration of attapulgite is 1-10wt%.
6. antibacterial polypropylene material according to claim 1 or 5, which is characterized in that in the step (2), the nitre
The mass ratio of sour silver and attapulgite is 17/100-170/100.
7. antibacterial polypropylene material according to claim 6, which is characterized in that in the step (2), the stirring
Time is 1h-10h；And/or the mass ratio of the silver nitrate and attapulgite is 50/100-135/100.
8. antibacterial polypropylene material according to claim 1, which is characterized in that in step (4), the time of the roasting
For 5-180min.
9. antibacterial polypropylene material according to claim 1 or 5, which is characterized in that in step (5), the blending is
Melt blending, the temperature of the blending are 180-230 DEG C；And/or the attapulgite-nano silver composite inorganic powder and poly- third
The weight fraction ratio of olefine resin is (0.01-1): 100.
10. antibacterial polypropylene material according to claim 9, which is characterized in that the compound nothing of attapulgite-nano silver
The weight fraction ratio of machine powder and acrylic resin is (0.01-0.1): 100.
11. application of the antibacterial polypropylene material described in any one of -10 in antibacterial product according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510711289.2A CN106633364B (en) | 2015-10-28 | 2015-10-28 | A kind of antibacterial polypropylene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510711289.2A CN106633364B (en) | 2015-10-28 | 2015-10-28 | A kind of antibacterial polypropylene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106633364A CN106633364A (en) | 2017-05-10 |
| CN106633364B true CN106633364B (en) | 2019-08-20 |
Family
ID=58815935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510711289.2A Active CN106633364B (en) | 2015-10-28 | 2015-10-28 | A kind of antibacterial polypropylene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106633364B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111206295B (en) * | 2020-02-03 | 2023-05-02 | 深圳市沃尔核材股份有限公司 | Material special for sterilizing mask, sterilizing net, sterilizing mask and preparation method of sterilizing 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 |
| CN111548550B (en) * | 2020-06-23 | 2023-12-22 | 陈志益 | Antibacterial HDPE plastic chair suitable for outdoor use and preparation method thereof |
| CN112341854B (en) * | 2020-11-16 | 2022-08-26 | 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250639C (en) * | 2001-11-23 | 2006-04-12 | 成都正光科技股份有限公司 | Special material for nano polypropylene tubing material |
| CN101089038B (en) * | 2007-06-08 | 2010-12-22 | 深圳市科聚新材料有限公司 | Antibacterial polypropylene material and its preparation process |
-
2015
- 2015-10-28 CN CN201510711289.2A patent/CN106633364B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106633364A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106633364B (en) | A kind of antibacterial polypropylene and preparation method thereof | |
| CN100450677C (en) | Plant reduction method for preparing silver Nano granules and gold Nano granules | |
| CN107326470B (en) | A kind of processing method of the lasting modified polyester fiber of antibacterial | |
| CN103172989B (en) | Environment-friendly antibacterial polyester material and preparation method thereof | |
| CN101347124B (en) | Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent | |
| CN105038090B (en) | A kind of preparation method of antibacterial electronic cigarette appearance material | |
| CN106270479B (en) | A kind of attapulgite-nano silver composite inorganic powder and preparation method | |
| CN108659525B (en) | Method for preparing PA 6/mesoporous nanomaterial @ Ag composite antibacterial fiber based on in-situ polymerization method | |
| WO2017092233A1 (en) | Antibacterial polyester fiber based on silver-containing zirconium phosphate, and method for preparation thereof | |
| CN102644162A (en) | Method for preparing antibacterial non-woven fabrics based on nano-silver monoatomic antibacterial agent | |
| CN102391573B (en) | Modified polypropylene plastic and preparation method and use thereof | |
| CN105332086B (en) | A kind of preparation method of Mesoporous zirconium phosphate loading nano silvery antibacterial polylactic acid fiber | |
| CN106046756A (en) | Graphene modified and enhanced polyurethane composite material for 3D printing | |
| CN101999414A (en) | Copper ion-loaded halloysite nanotube antimicrobial agent and preparation method thereof | |
| CN106633829B (en) | A kind of anti-bacteria nylon and preparation method thereof | |
| CN1861095A (en) | Load type super-fine copper-powder copper-complementary agent, its prepn. method and use | |
| CN108084544A (en) | Composite antibacterial membrane material and preparation method thereof | |
| CN105506767B (en) | A kind of Mesoporous zirconium phosphate loading nano silvery antibacterial polypropylene fiber and preparation method thereof | |
| CN105332084A (en) | Preparation method for copper oxide-loaded mesoporous zirconium phosphate antibacterial polylactic acid fiber | |
| CN103305063A (en) | Preparation method for curdlan-nano-copper compound antibacterial gel | |
| CN101836660A (en) | Preparation method of composite nano-antibacterial, as well as antibacterial NL latex and antibacterial TPI rubber | |
| CN106609400B (en) | A kind of preparation method of multi-functional acid fiber by polylactic | |
| CN109836803A (en) | A kind of waterproof breathable membrane material with antibacterial functions | |
| CN103772807B (en) | A kind of preparation method of antibacterial, hydrophilic polypropylene particle | |
| CN105131336A (en) | Antibacterial agent, preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |