CN106633829B - A kind of anti-bacteria nylon and preparation method thereof - Google Patents
A kind of anti-bacteria nylon and preparation method thereof Download PDFInfo
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- CN106633829B CN106633829B CN201510712775.6A CN201510712775A CN106633829B CN 106633829 B CN106633829 B CN 106633829B CN 201510712775 A CN201510712775 A CN 201510712775A CN 106633829 B CN106633829 B CN 106633829B
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a kind of anti-bacteria nylons.The anti-bacteria nylon, the antibacterial agent for including: nylon 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.Antibacterial agent of the present invention has 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, can improve the rigidity of material, be a kind of modified additive of ideal nylon resin.
Description
Technical field
The present invention relates to the field of polymers, further say, are to be related to a kind of anti-bacteria nylon and preparation method thereof, the antibacterial
Nylon material can be applied to the various fields for producing and living.
Background technique
Antibacterial plastic product in production and living using increasingly extensive, various antibacterial agents and antibiotic plastic are also with hair
Exhibition.Plastic antimicrobial agent is divided into inorganic antiseptic and organic antibacterial agent.The safety of inorganic antiseptic, heat resistance, durability are preferable,
Such as Ag, Zn etc..Organic antibacterial agent, for example, plug bacterium spirit, Bravo, carbendazim, zinc pyrithione, normal-butyl benzisothiazole
Ketone (BBIT) etc. is precipitated comparatively fast in the plastic, and not wash resistant, working life is short.
Inorganic antiseptic silver ion as antibacterial agent, have efficiently, safety, wide sterilization spectrum, heat resistance, have no drug resistance and high
The advantages that selective.By nano-silver loaded on different carriers, the antibacterial effect and dispersibility of nano silver can be improved.Carry silver
Carrier is usually inorganic mineral of meso-hole structure, including zeolite, galapectite, sepiolite, mesoporous silicon oxide, attapulgite etc..
Wherein attapulgite is the nanoparticle of porous structure, and main component is palygorskite (attapulgite), is a kind of with link layer
The aqueous rich magnesium silicate clay mineral of shape structure.Its skeleton structure is in 3 D stereo shape, by oxygen-octahedron and magnalium octahedral
Body is connected with each other by sharing vertex, is parallel to brilliant (needle-shaped, the micro- rodlike or fibrous monocrystal) direction of stick with numerous
The tubular nanometer grade duct of arrangement, duct run through total, from the section duct Shang Kan in it is equal in magnitude (about 0.38nm ×
0.63nm) honeycomb belongs to natural monodimension nanometer material, has good absorption property and inexpensive, is ideal carrier
Material, therefore cause the attention of scholar and research structure.As Chinese patent CN1568703A surfactant and it is organic also
Under the conditions of former agent is existing, chemically react to form complex antimicrobials by carrier and silver nitrate solution of attapulgite；Similar, in
State patent CN1685830A, zeolite powder is immersed in silver nitrate solution, so that silver ion is sufficiently adsorbed on the hole of zeolite
In, 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.The content of nanometer silver of supported on carriers
Very low, leading to antibacterial antiplaque agent effect not is very well, and remaining reducing agent and surfactant have been applied to very in antibacterial agent
Big influence.
Nylon resin is most important engineering plastics, which is widely used, and almost covers each field, is five
Most widely used kind in large-engineering plastics.In order to better meet many requirements of application etc., people are constantly studied respectively
Kind method improves the performance of nylon.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of attapulgite-nano silver composite inorganic powder
Modification of nylon and preparation method thereof.It, will be through spraying without adding any reducing agent using cheap attapulgite and silver nitrate as raw material
Melt blending in nylon is added in powder after mist is dry, obtains anti-bacteria nylon (the attapulgite clay compounded nothing of carrying nano silver
Machine powder modification nylon).Present invention process is simple, environmentally protective.The use of organic solvent is avoided, and reduces environmental pollution
The discharge of object.
An object of the present invention is to provide a kind of anti-bacteria nylon, comprising: nylon resin and is dispersed in the resin
Antibacterial agent, the antibacterial agent be attapulgite-nano silver composite inorganic powder, wherein the quality of nano silver and attapulgite
Than being 3-100nm for the particle size range of 10/100-100/100, nano silver.
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.
Anti-bacteria nylon according to the present invention, the attapulgite-nano silver composite inorganic powder and nylon resin weight
Than for (0.01-1): 100, preferably (0.01-0.1): 100.
Anti-bacteria nylon according to the present invention wherein silver-colored simple substance is adsorbed on attapulgite's surface in the form of nano silver, and is received
Rice Argent grain and attapulgite are firmly combined.Nano silver active is big, can slowly release the silver ion with antibacterial effect.
And attapulgite-nano silver composite inorganic powder size is small, is nanoscale auxiliary agent, has good dispersibility in nylon
Can, nano-dispersion can be reached, improve the rigidity and antibacterial effect of material.Attapulgite-nano silver composite inorganic powder
Small size and bigger serface can make it under a small amount of additive amount, can also play preferable modified effect.
The second object of the present invention is to provide a kind of anti-bacteria nylon (attapulgite-nano silver composite inorganic powder modification Buddhist nun
Dragon) 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 attapulgite clay compounded powder；
(4) composite powder obtained in step (3) and nylon resin are subjected to melt blending, obtain the antibacterial Buddhist nun
Dragon.
A preferred embodiment according to the present invention, in the step (1), the attapulgite is without acid processing step
Suddenly.And the preferably described attapulgite is the attapulgite of thermal activation and/or decentralized processing.The thermal activation and/or decentralized processing,
It is for improving dispersibility of the attapulgite in suspension.The thermal activities and decentralized processing can be used in the prior art
Common method.For example, the thermal activation treatment can use roasting method, maturing temperature is 200-450 DEG C, calcining time 5-
60min.The decentralized approach of the attapulgite is for example: ultrasonic wave dispersion, mechanical stirring dispersion (such as ball milling dispersion, high speed
It is dispersed with stirring) etc..In the attapulgite suspension, the concentration of attapulgite is no more than 10wt%；It is preferred that 1-10wt%.
A preferred embodiment according to the present invention, in step (2), the quality of the silver nitrate and attapulgite it
Than for 17/100-170/100, preferred mass ratio is 50/100-135/100.The whipping temp is 50 DEG C or more, preferably
50-90℃.The mixing time is 1h or more, preferably 1h-10h.Inventors believe that recessed preparing nano silver of the invention
During convex stick soil composite powder, attapulgite suspension and silver nitrate solution are mixed by (being higher than room under certain temperature
Temperature) stirring, the carbanion in attapulgite in carbonate can be promoted to dissolve and reacted with silver ion to generate silver carbonate absorption
In attapulgite's surface.
One specific embodiment of the method provided according to the present invention, in step (3), the temperature of the spray drying is
150-200℃.Using other such as filterings and the method dry with convection oven, identical skill can not be obtained and is spray-dried
Art effect.In patent application CN201510262409.5, in relation to preparing the content of attapulgite clay compounded powder in step (1)-(3)
Portion is introduced into herein.And further 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.
A specific embodiment of providing method according to the present invention, in step (4), described be blended is melt blending,
It is preferred that the temperature of the blending is 200-260 DEG C, preferably 220-260 DEG C.The attapulgite clay compounded powder is blended with nylon,
As conventional method, such as the progress of mixer, single screw extrusion machine, double screw extruder can be used in melt blending.The bumps
The weight fraction ratio of stick soil composite inorganic powder and nylon resin is (0.01-1): 100, preferably (0.01-0.1): 100, wherein
The parts by weight of attapulgite clay compounded inorganic powder are to calculate basis namely the attapulgite with attapulgite-silver therein
Silver carbonate in composite inorganic powder is in terms of silver element.
A specific embodiment of providing method according to the present invention, in step (4), by the compound nothing of attapulgite-silver
Machine powder is added in nylon resin, during blending (such as melt blending processing), since temperature is higher (200-260 DEG C),
And the decomposition temperature of silver carbonate is lower, therefore silver carbonate is decomposed into silver-colored simple substance, is finally equably supported in the form of nano silver
Attapulgite's surface.Namely during melt blending, in-situ preparation nano-Ag particles.It is able to verify that, is obtained by wide-angle XRD
To anti-bacteria nylon in silver element be elemental silver.This anti-bacteria nylon is analyzed using transmission electron microscope (TEM), nano silver
Particle size range is 3-100nm.In finally obtained anti-bacteria nylon, the attapulgite-nano silver composite inorganic powder is as anti-
Microbial inoculum is dispersed in the nylon resin, wherein the mass ratio of nano silver and attapulgite is 10/100-100/100, nano silver
Particle size range be 3-100nm, the mass ratio of the preferably described nano silver and attapulgite is 30/100-80/100.
A specific embodiment according to the present invention, the preparation method of the anti-bacteria nylon include the following steps.
(1) attapulgite and water are hybridly prepared into attapulgite suspension.The attapulgite is not necessarily to acid treatment step.
Attapulgite is preferably the attapulgite of thermal activation and decentralized processing.Method of roasting can be used in the thermal activation treatment, wherein roasting
Burning temperature is preferably 200-450 DEG C, and calcining time is preferably 5-60min；Concave convex rod soil property amount in the attapulgite suspension
Concentration is no more than 10%.The decentralized processing of the attapulgite can use conventional method in the prior art, such as: ultrasound
Dispersion, mechanical stirring dispersion (such as ball milling dispersion, high-speed stirred dispersion) etc..Attapulgite in the attapulgite suspension
Mass concentration is no more than 10%；Such as 1-10wt%.
(2) silver nitrate is added in attapulgite suspension described in step (1), then at temperatures greater than room temperature
It is stirred.The mass ratio of the silver nitrate and attapulgite is 17/100-170/100, and preferred mass ratio is 50/100-135/
100.The temperature of the stirring is 50 DEG C or more, and preferably 50-90 DEG C, the time of the stirring is 1h or more.
It (3) will treated that attapulgite suspension is spray-dried to obtain attapulgite clay compounded powder through step (2)；
The temperature of the spray drying is preferably 150-200 DEG C.
(4) it by attapulgite clay compounded powder made from step (3), is processed with by melt blending, processing temperature range is
200-260 DEG C, it is based on nylon resin, the content of attapulgite clay compounded powder is 0.01-1wt%.
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.Using other such as filterings and the method dry with convection oven, it can not obtain and do by spraying
Dry identical technical effect.Inventors believe that during preparing nano silver of the invention attapulgite clay compounded powder, it will
Heating stirring is passed through in attapulgite suspension and silver nitrate solution mixing, can promote carbonate in attapulgite in carbonate from
Son, which dissolves and reacts generation silver carbonate with silver ion, is adsorbed on attapulgite's surface.In spray-drying process, unreacted nitre
Sour silver solution and evenly dispersed attapulgite in the solution can be reacted under the action of heating air-flow with further occurrence to be generated
Silver carbonate.It adds it in nylon resin, during melt-processed, since temperature is higher, silver carbonate can be decomposed into silver-colored single
Matter is finally equably supported on attapulgite's surface in the form of nano silver, is made modification of nylon (anti-bacteria nylon).Due to bumps
Stick soil and nano-Ag particles in nylon dispersibility preferably, can be improved under lesser dosage material anti-microbial property and just
Property.
Attapulgite is natural monodimension nanometer material, has very big specific surface area, absorption property and chemical reactivity
Equal nano effects, the nano silver that spray drying is formed after high-temperature fusion is processed again are firmly adsorbed on attapulgite table
Face forms equally distributed nanoscale Argent grain in attapulgite's surface in this way.Although the method by directly heating calcining
Silver nitrate is decomposed into also available nano silver simple substance, but its decomposition temperature is high, energy consumption is high, and the nano silver particles of preparation are easy
Reunite, partial size is bigger.By heating stirring, then spray drying is so that carbonic acid contained by inside silver nitrate and attapulgite
Root sufficiently reacts, and then can be prepared by nano silver lower than melting heating under silver nitrate decomposition temperature, is not only avoiding using also
Former agent or other chemical reaction bring environmental pollutions, and the decomposition temperature of silver carbonate is relatively low, in the processing of nylon
At a temperature of produce 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
The nano silver active of attapulgite's surface is very big, can slowly release the silver ion with antibacterial effect, and nano silver
Grain is firmly combined with attapulgite.Antibacterial agent produced by the present invention is applied in nylon, is adsorbed on attapulgite's surface
Nano-Ag particles can preferably improve the anti-microbial property of plastics, and since attapulgite can disperse more preferably, also can be material
Play the role of increasing rigid.
According to the present invention, by silver ion with it is attapulgite clay compounded, so that it may so that preparation attapulgite clay compounded powder size
Reduce, to reach better dispersion effect in the plastic, good antibacterial effect can be reached with considerably less additive amount.
Meanwhile the nano-dispersion of attapulgite, it can be further improved the rigidity of plastics.It is this to use AgNO3With it is attapulgite clay compounded
The antibacterial agent (i.e. attapulgite-nano silver composite inorganic powder) prepared, antimicrobial efficiency is higher, greatly reduces antibacterial
The processing cost of plastics, and improve the rigidity of material.
The third object of the present invention is to provide the anti-bacteria nylon of above-mentioned anti-bacteria nylon or above method preparation in antibacterial system
Application in product.Anti-bacteria nylon in the present invention, anti-microbial property is good, and rigidity is good, has wide application in antibacterial product field
Prospect.
Detailed description of the invention
Fig. 1 shows transmission electron microscope picture according to an embodiment of the invention；
Fig. 2 shows transmission electron microscope picture according to an embodiment of the invention.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Raw materials used in embodiment is commercially available, attapulgite used in embodiment, and the diameter of single stick crystalline substance is in 30-80nm
Between.
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
Close 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
Close 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.
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 characterization result is listed in table 1.
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, In
At 90 DEG C, then magnetic agitation 3h is spray-dried in 170 DEG C, collects spray-dried composite powder obtained.
Embodiment 9
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.
It is confirmed using wide-angle XRD, the silver in sample obtained in embodiment 1-9 is silver carbonate, is obtained in comparative example 1-3
It is silver nitrate.
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.
Table 1.
Embodiment 10:
Use Ag prepared by embodiment 1 and attapulgite weight ratio for 3/20 1# auxiliary agent proportionally with nylon 6
(Sinopec Ba Ling branch company), antioxidant 1010 and 168 (Switzerland vapour Ba Jiaji production, the two are used in mixed way with 1/1 ratio)
Mix, concrete composition: 100 parts of nylon, 0.01 part of 1# Antibacterial accessory ingredient, antioxidant 1010/0.4 part of 168 mixture is (wherein
Each component content is based on parts by weight), in high speed agitator (Beijing's English spy's plastics machinery head factory, model GH-10DY)
Mixing one minute, it is (draw ratio 30:1, straight with the ZSK-25 twin-screw extrusion system of German Werner and Pleiderer company
Diameter 25mm) it is blended and is granulated, extruder temperature of each section is respectively 230 DEG C, and 235 DEG C, 235 DEG C, 235 DEG C, 235 DEG C, 220 DEG C of (heads
Temperature), sample standard is made through injector (ningbo of china Hai Tian company produces, model HTF110X/1J) injection molding in gained pellet
Batten.
The sample in this embodiment is analyzed using transmission electron microscope (TEM), picture is shown in Fig. 1 and Fig. 2.Attapulgite-
Nano silver composite inorganic powder 2 is uniformly distributed in nylon resin 1, dispersion of this composite inorganic powder 2 in nylon resin 1
Property it is good, reach nanoscale dispersion.In the attapulgite-nano silver composite inorganic powder 2, nano-Ag particles 3 are adsorbed
It,, can be with so that the activity of nano silver 3 on 4 surface of attapulgite is very big between attapulgite on the surface of attapulgite 4
The silver ion with antibacterial effect is slowly released, and nano-Ag particles are firmly combined with attapulgite.It attapulgite and receives
Rice Argent grain dispersibility in nylon preferably, can improve the anti-microbial property and rigidity of material under lesser dosage.
It can also be learnt from Fig. 1 and Fig. 2, during the melt blending of step 4) of the invention, due to melt blending
Temperature is higher (200-260 DEG C), and the silver carbonate decomposition in situ in composite powder can be made to restore, and generates silver-colored simple substance, silver-colored simple substance with
The form of nano-Ag particles is equably adsorbed on attapulgite's surface.
Embodiment 11:
By more 0.05 part of 0.01 part of 1# Antibacterial accessory ingredient in embodiment 10, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Embodiment 12:
By more 0.1 part of 0.01 part of 1# Antibacterial accessory ingredient in embodiment 10, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Embodiment 13:
By 0.01 part of the 1# Antibacterial accessory ingredient more 2# Antibacterial accessory ingredient in embodiment 10, remaining each component ratio is constant, altogether
Be mixed it is even, remaining operation and squeeze out, injecting condition is the same as embodiment 10.
Embodiment 14:
By more 0.05 part of 0.01 part of 2# Antibacterial accessory ingredient in embodiment 13, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Embodiment 15
By more 0.1 part of 0.01 part of 2# Antibacterial accessory ingredient in embodiment 13, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Comparative example 4:
By 100 parts of copolymer nylon powder and 0.4 part of mix of antioxidant, remaining operation and extrusion, injecting condition are same
Embodiment 10.
Comparative example 5:
By 0.4 part of 100 parts of copolymer nylon powder, 0.01 part of attapulgite, antioxidant mix, remaining operates and squeezes
Out, injecting condition is the same as embodiment 10.
Comparative example 6:
Attapulgite in comparative example 5 is changed to 0.05 part, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Comparative example 7:
Attapulgite in comparative example 5 is changed to 0.1 part, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Comparative example 8:
By the more 10# auxiliary agent of the 1# Antibacterial accessory ingredient in embodiment 10, remaining each component ratio is constant, is blended uniformly,
Remaining operation and extrusion, injecting condition are the same as embodiment 10.
Comparative example 9:
By more 0.05 part of 0.01 part of 10# auxiliary agent in comparative example 8, remaining each component ratio is constant, is blended uniformly,
Remaining operation and extrusion, injecting condition are the same as embodiment 10.
Comparative example 10:
By more 0.1 part of 0.01 part of 10# Antibacterial accessory ingredient in comparative example 8, remaining each component ratio is constant, is blended equal
Even, remaining operation and extrusion, injecting condition are the same as embodiment 10.
Test:
The standard batten for being respectively molded embodiment 10-15 and comparative example 4-10 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.
The formula and performance of 2. anti-bacteria nylon of table
Mechanical performance data can be seen that embodiment 10-15 using prepared composite assistant and pure concave convex rod from table 2
Soil is compared, and is had to nylon and is preferably increased rigid effect, and assigns material preferable anti-microbial property.Comparative example shows the use of attapulgite
Amount is increased to 0.05 part by 0.01 part, and the inflexible target of nylon improves without further substantially, but after using composite nucleating agent,
Composite assistant as contained only 0.05 part in embodiment 11 and 14, but its inflexible target is but higher than the sample using attapulgite
Product illustrate using binary composite assistant of the present invention have using high-cost organic nucleating agent more merely even more ideal
Raising nylon rigidity effect.By the sample in embodiment 10-15 pass through wide-angle XRD it is known that silver carbonate all decompose,
Silver-colored simple substance is obtained, silver-colored partial size is 3-80nm.
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, temperature, pressure, when
Between the values of equal state-variables be 50-90, in the present specification it means that specifically listing 51-89,52-88 ... and
The numerical value such as 69-71 and 70-71.It, can be with due regard to 0.1,0.01,0.001 or 0.0001 for one for the value of non-integer
Unit.This is only some special examples indicated.In this application, in a similar manner, cited minimum and peak it
Between all possible combinations of numerical value be 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 (15)
1. a kind of anti-bacteria nylon, comprising: nylon 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 nano silver and attapulgite is 10/100-100/100, nano silver
Particle size range be 3-100nm；
The preparation method of the anti-bacteria nylon the following steps are included:
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in attapulgite suspension described in step (1), then 50 DEG C or more at a temperature of stir
The time of 1h or more；
(3) attapulgite suspension after step (2) stirring is spray-dried, obtains attapulgite clay compounded powder；
(4) composite inorganic powder obtained in step (3) and nylon resin are subjected to melt blending, obtain the antibacterial Buddhist nun
Dragon.
2. anti-bacteria nylon according to claim 1, which is characterized in that the mass ratio of the nano silver and attapulgite is
30/100-80/100。
3. anti-bacteria nylon according to claim 1 or 2, which is characterized in that the attapulgite-nano silver composite inorganic powder
The weight ratio of end and nylon resin is (0.01-1): 100.
4. anti-bacteria nylon according to claim 3, which is characterized in that the attapulgite-nano silver composite inorganic powder
Weight ratio with nylon resin is (0.01-0.1): 100.
5. a kind of method for preparing anti-bacteria nylon described in any one of claim 1-4, 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), then 50 DEG C or more at a temperature of stir
The time of 1h or more；
(3) attapulgite suspension after step (2) stirring is spray-dried, obtains attapulgite clay compounded powder；
(4) composite inorganic powder obtained in step (3) and nylon resin are subjected to melt blending, obtain the antibacterial Buddhist nun
Dragon.
6. according to the method described in claim 5, it is characterized in that, in the step (1), in the suspension, concave convex rod
The concentration of soil is no more than 10wt%.
7. according to the method described in claim 6, it is characterized in that, in the step (1), in the suspension, concave convex rod
The concentration of soil is 1-10wt%.
8. according to the method described in claim 5, it is characterized in that, in the step (2), the silver nitrate and attapulgite
Mass ratio be 17/100-170/100.
9. according to the method described in claim 8, it is characterized in that, the temperature of the stirring is 50- in the step (2)
90℃；The time of the stirring is 1h-10h；And/or the mass ratio of the silver nitrate and attapulgite is 50/100-135/
100。
10. according to the method described in claim 5, it is characterized in that, in step (3), the temperature of the spray drying is
150-200℃。
11. the method stated according to claim 5, which is characterized in that in step (4), the temperature of the blending is 200-260
℃；And/or the weight fraction ratio of the attapulgite clay compounded powder and nylon resin is (0.01-1): 100, the attapulgite
The parts by weight of composite inorganic powder are calculating benchmark with attapulgite-silver therein.
12. according to the method for claim 11, which is characterized in that in step (4), the temperature of the blending is 220-
260℃；And/or the weight fraction ratio of the attapulgite clay compounded powder and nylon resin is (0.01-0.1): 100.
13. the method according to any one of claim 5-12, which is characterized in that described in the anti-bacteria nylon
Attapulgite-nano silver composite inorganic powder is dispersed in nylon resin as antibacterial agent, the quality of nano silver and attapulgite
Than being 3-100nm for the particle size range of 10/100-100/100, nano silver.
14. according to the method for claim 13, which is characterized in that the mass ratio of the nano silver and attapulgite is 30/
100-80/100。
15. side described in any one of anti-bacteria nylon described in any one of -4 or claim 5-14 according to claim 1
Application of the anti-bacteria nylon of method preparation in antibacterial product.
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| CN106633829B true CN106633829B (en) | 2019-11-12 |
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| CN111020739B (en) * | 2019-12-24 | 2022-10-14 | 广州市中诚新型材料科技有限公司 | Functional acid-oxidation-resistant polyamide fiber and preparation method thereof |
| CN112921441A (en) * | 2021-01-27 | 2021-06-08 | 深圳市信德缘珠宝首饰有限公司 | Silver and fiber combination method |
| CN114196011B (en) * | 2021-12-13 | 2022-09-06 | 浙江新力新材料股份有限公司 | Long-acting antibacterial bio-based nylon resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300981A (en) * | 2008-05-15 | 2008-11-12 | 兰州大学 | Nano silver-carrying concave-convex stick anti-bacteria agent and preparation thereof |
| CN104004349A (en) * | 2014-06-06 | 2014-08-27 | 宁波伊德尔新材料有限公司 | Antibacterial nylon/nano composite material and preparation method thereof |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300981A (en) * | 2008-05-15 | 2008-11-12 | 兰州大学 | Nano silver-carrying concave-convex stick anti-bacteria agent and preparation thereof |
| CN104004349A (en) * | 2014-06-06 | 2014-08-27 | 宁波伊德尔新材料有限公司 | Antibacterial nylon/nano composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 凹凸棒石抗菌复合材料制备及其抗菌试验研究;李宏伟;《中国优秀硕士学位论文全文数据库—工程科技I辑》;20050621;28、29、33、35页 * |
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