CN106280218B - A kind of preparation method of the composition for being used to prepare antimicrobial composite material and antimicrobial composite material - Google Patents
A kind of preparation method of the composition for being used to prepare antimicrobial composite material and antimicrobial composite material Download PDFInfo
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Abstract
Present disclose provides a kind of method for preparing antimicrobial composite material and the compositions for being used to prepare antimicrobial composite material, this method comprises the following steps: (1) carrying out padding processing to bamboo filament using the solution containing nano silver material, obtain nano silver-bamboo fibre composite fibre；(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing, obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface；(3) so that the chopped bamboo fibre composite fibre of acrylonitrile-butadiene-styrene copolymer, chemical modifier and the nano silver-is carried out melting extrusion granulation, obtain the antimicrobial composite material.The preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and the antimicrobial composite material being prepared has significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, while bamboo fibre surface and resin matrix are modified, improves the mechanical property of antimicrobial composite material.
Description
Technical field
This disclosure relates to fibrous composite field, and in particular, to a kind of combination for being used to prepare antimicrobial composite material
The preparation method of object and antimicrobial composite material.
Background technique
In recent years, the development of auto industry has brought great convenience, and the appearance of new-energy automobile is further
The predicament of Current resource shortage is alleviated, while also growing day by day to the requirement of automotive light weight technology.For reply automotive light weight technology
Demand, fibre reinforced composites are as one of main solution, and proportion constantly increases in automotive material.It is fine at present
Dimension enhancing composite material is mainly formed by glass fibre, carbon fiber etc. with plastic composition, and the processing of waste is more difficult, produces ring
Border is severe, and very big burden is brought to environment.As people's environmental protection consciousness constantly enhances, processing performance is excellent, by with
In the plastics pollution on the environment of various industrial products has become general concern the problem of.Therefore, natural fiber is as increasing
Strong material is attracted attention for production environment friendly composite material.
Compound research is carried out with longer history, currently, bio-based materials exist using plant fiber and synthetic resin
Application in terms of automobile has begun, as natural fiber replaces glass fiber reinforcement；Japanese Toyota Company is in the car exhibition of Chicago
Illustrate the I/X plug-in hybrid concept car of flaxen fiber bio-based materials roof；Ford is shown in the model U
The rear baffle and seat foam of soy resins support；And plant fiber enhancing PP material manufacture instrument disc assembly shell is used to have become
Mainstream, a kind of smell is small, non-aging, low-density and the plant fiber enhancing PP material for having better environmental suitability,
It applies on car；The polypropylene automotive component of the 45% wood-fibred enhancing occurred on German market, wood-fibred enhancing subtract
Shake the products such as calendared sheet.The states such as India, Japan are using jute, sisal hemp, flax fiber and hemp as reinforcing material and heat
Thermoplastic polymer is made natural plant fibre polymer composite product and has also started engineer application.Natural fiber increases at home
Strong composite material is at the early-stage, and the research in this field really realizes that the product of volume production goes out not yet still in its infancy
It is existing.
China's bamboo wood yield ranks first in the world, accounts for 30% of the world or more, and cheap, is largely distributed in
The mountain areas such as Hunan, Anhui, Zhejiang.Bamboo fiber has good biodegradable and reproducibility simultaneously, utilizes this fibre
Compound the developed material of thermoplastic resins such as dimension and low-melting point polyester and polypropylene, intensity, specific modulus are relatively high, are suitable for
Make the reinforcement of the composite material of automobile；Reinforced phase can be made mutually to separate with matrix by melt process simultaneously, effectively reached
The purpose of recycling, to embody the feature of environmental protection and sustainable developability of material application.Bamboo fiber reinforcement thermoplastic
Composite processing energy consumption is few, and process equipment loss is small, is conducive to energy saving.The maximum feature of bamboo fibre is the height of cross section
Spend natural hollow.It is covered with ellipse gap on bamboo fibre section, gap is in quincunx arrangement, this makes bamboo fibre and its product
Moisture absorption, moisture releasing, wet transmitting performance are splendid, and expert is referred to as " fiber that can be breathed ".Bamboo has natural antibacterial, fungi-proofing, protection function
Can, free from insect pests, nothing are rotted in its growth course.These antibacterial materials not will receive destruction, day in the process of production and processing
Right antibiotic property will not cause any reaction to human body, and can also health-care and skin-care, the antibacterial agent that effect is added after being much better than.Bamboo
Fiber reinforced thermoplastics composite material has broad application prospects in fields such as automobile, electromechanics, interior decorations.
Nano silver particles partial size has high-specific surface area, unique physico-chemical property, efficiently generally in 25-50 ran
Antibacterial activity, have strong inhibition and killing to the tens of kinds of pathogenic microorganisms such as Escherichia coli, gonococcus, chlamydia trachomatis
Effect.It is found by researches that nano silver can kill 650 various bacterias in several minutes, the cell wall of nano-Ag particles and pathogen/
After film combines, thallus can be directly entered, rapidly with the combination of the sulfydryl (- SH) of oxygen metabolism enzyme, inactivate enzyme, respiratory metabolism is blocked to make
It is choked to death.Unique sterilization mechanism so that nano-Ag particles can kill rapidly pathogenic bacteria in low concentration, and will not produce
Raw drug resistance does not find any stimulate the reaction to skin without any toxic reaction yet.
Vehicle air conditioning outlet is the exhaust apparatus for automotive interior heating, ventilating and air conditioning system, is car room
Outer air intercommunication, the necessary place of circulation also need to guarantee that air is circulating other than meeting the requirements in various mechanical properties
Cleaning is kept in the process, not by the pollution of mould etc., protects the respiratory health of rider.And most composite material exists at present
In the biggish situation of air humidity, generation mould that can be different degrees of brings hidden danger to human health to pollute air；
Meanwhile the compatibility of bamboo fibre and plastics is bad in existing bamboo fiber composite material, has seriously affected the performance of composite material.
Summary of the invention
Purpose of this disclosure is to provide a kind of method for preparing antimicrobial composite material, the antimicrobial composite materials of this method preparation
The composite material that existing method can be overcome to prepare is easy to produce mould, and fiber and resin compatible difference influence composite material
The technical issues of energy.
Another object of the present disclosure is to provide a kind of composition for being used to prepare antimicrobial composite material, and the composition can be with
It solves existing composite material and is easy to produce mould, and the technology that fiber influences composite property with resin compatible difference is asked
Topic.
To achieve the goals above, the disclosure provides a kind of preparation method of antimicrobial composite material, and this method includes as follows
Step:
(1) bamboo filament is carried out to pad processing using the solution containing the nano silver material, obtains nano silver-bamboo
Fiber composite fiber；
(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing,
Obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface；
(3) make acrylonitrile-butadiene-styrene copolymer, chemical modifier and the chopped bamboo fibre of the nano silver-compound
Fiber carries out melting extrusion granulation, obtains the antimicrobial composite material.
Through the above technical solutions, the preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, it is prepared
Antimicrobial composite material have significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, while to bamboo fibre table
Face and resin matrix are modified, and improve the mechanical property of antimicrobial composite material.
The disclosure also provides a kind of composition for being used to prepare antimicrobial composite material, and the composition includes acrylic nitrile-butadiene two
Alkene-styrol copolymer, be chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein relative to 100 parts by weight
Acrylonitrile-butadiene-styrene copolymer, the content of the chopped bamboo fibre are 5-60 parts by weight, the nano silver material
Content is 0.01-2 parts by weight, and the content of the coupling agent is 0.1-10 parts by weight, and the content of the chemical modifier is 0.1-
20 parts by weight；The coupling agent is silane coupling agent and/or titante coupling agent；The chemical modifier is selected from aluminic acid
At least one of ester, ethylene bis-fatty acid amides and chromium picolinate.
Through the above technical solutions, containing bamboo fibre and nano silver material in the composition and antimicrobial composite material of the disclosure
Material has significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, while to bamboo fibre surface and resin matrix
It is modified, improves the mechanical property of antimicrobial composite material.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of preparation method of antimicrobial composite material, and this method comprises the following steps:
(1) bamboo filament is carried out to pad processing using the solution containing the nano silver material, obtains nano silver-bamboo
Fiber composite fiber；
(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing,
Obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface；
(3) make acrylonitrile-butadiene-styrene copolymer, chemical modifier and the chopped bamboo fibre of the nano silver-compound
Fiber carries out melting extrusion granulation, obtains the antimicrobial composite material.
The preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and the antimicrobial composite material being prepared has
Significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, while bamboo fibre surface and resin matrix are changed
Property, improve the mechanical property of antimicrobial composite material.
Wherein, the method for padding processing is well known to those skilled in the art, can be with reference to sizing fabric process
Method for sizing is carried out using the cooperation of compregnate roller and sizing roller.Specifically processing method can for second dipping and rolling, it is double leaching three pressure or
Double four pressures of leaching etc., preferably second dipping and rolling method.
According to the disclosure, the dosage of each raw material component can change in very large range, can be field of compound material skill
Dosage commonly used by art personnel, for example, be chopped bamboo fibre relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer
Dosage can be 5-60 parts by weight, the dosage of nano silver material can be 0.01-2 parts by weight, and the dosage of coupling agent can be
0.1-10 parts by weight, the dosage of chemical modifier can be 0.1-20 parts by weight；Coupling agent can for silane coupling agent and/or
Titante coupling agent；Chemical modifier can in Aluminate, ethylene bis-fatty acid amides and chromium picolinate extremely
Few one kind.
In order to further increase the antibacterial effect and mechanical property of the antimicrobial composite material by above method preparation, preferably feelings
Under condition, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage for the bamboo fibre that is chopped can be 15-35 weight
Part is measured, the dosage of nano silver material can be 0.01-0.5 parts by weight, and the dosage of coupling agent can be 0.5-5 parts by weight, chemistry
The dosage of modifying agent can be 0.5-10 parts by weight.
According to the disclosure, the acrylonitrile-butadiene-styrene copolymer (ABS resin) is those skilled in the art institute
Known, the relative amount of acrylonitrile unit therein member, butadiene structural units and styrol structural unit is not important to
It asks, can be the conventional selection of field of compound material, for example, in acrylonitrile-butadiene-styrene copolymer, acrylonitrile structure
The weight ratio of unit, butadiene structural units and styrol structural unit can be 1:(0.15-2): (1-4).Above-mentioned acrylonitrile-
Butadiene-styrene copolymer can be commercial products, such as can for purchased from Japan Electric chemistry ABS resin GR-4000,
ABS Magnum800 purchased from Si Tailong company of the U.S., ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft,
KR2885,828P or 846L etc..
In the preparation method according to the disclosure, coupling agent can be used for carrying out surface to chopped bamboo fibre being modified, described
Chemical modifier can be used for being modified resin matrix, and the two is used cooperatively for improving acrylonitrile-butadiene-styrene (ABS)
The interface compatibility of copolymer and chopped bamboo fibre, to improve the interface bond strength of the two.In above-mentioned preparation method each group
Divide in amount ranges, in order to further increase the interface cohesion of acrylonitrile-butadiene-styrene copolymer and chopped bamboo fibre
The amount ratio of power, coupling agent and chemical modifier can be preferably 1:(0.5-2.5).
Coupling agent is used to carry out the method for surface coating processing also for art technology to nano silver-bamboo fibre composite fibre
Known to personnel, for example, nano silver-bamboo fibre composite fibre can be dispersed in containing the anhydrous of 0.2-10% (wt) coupling agent
In ethyl alcohol, HCl is added and adjusts pH value to 4-5, ultrasonic disperse reacts 1-2 hours at 50 DEG C.After reaction, nano silver-is taken out
Bamboo fibre composite fibre, it is extremely neutral wash with distilled water, it is dried 2-5 hours at 100-120 DEG C, obtains the modified nanometer in surface
Silver-bamboo fibre composite fibre.
According to the disclosure, coupling agent can be silane coupling agent or titante coupling agent, specifically, silanes coupling
Agent can be selected from γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, vinyltriethoxysilane, ethylene
Base trimethoxy silane, double-(γ-triethoxy silicon substrate propyl) tetrasulfide, γ-methacryloxypropyl trimethoxy
One or more of silane, triphenyl silicol, wherein in order to make the processed fiberglass surfacing of silane coupling agent with
Active force between cyclic olefin polymer interface is stronger, under preferable case, selects the coupling agent containing olefin group, such as ethylene
Ethyl triethoxy silicane alkane, vinyltrimethoxysilane or γ-methacryloxypropyl trimethoxy silane；Titanate ester
Coupling agent can be for selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy)
Titanate esters, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters
The chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine and bis- (two octyloxy pyrophosphoric acid ester groups) second
Support at least one of titanate esters.
Aluminate can be for selected from three isopropyl ester of aluminic acid, three benzyl ester of aluminic acid；Ethylene bis-fatty acid amides can be double for ethylene
The double oleamides of stearic amide, ethylene, ethylene double at least one of palmitamides and ethylene dilaurate amide.
According to the disclosure, nano silver material can be any form containing nano silver particles, for example, nano silver material can
Think and contain only nano silver particles, can also disperse on the carrier particles, the type and content present invention of carrier granular is not spy
Other requirement, as long as meeting, nano silver particles are evenly distributed in nano silver material and content is suitable for.In order to improve nanometer
The compatibility of silver particles and resin matrix under preferable case, can choose the knot with acrylonitrile-butadiene-styrene copolymer
Structure unit is identical or structure similar in carrier granular of the polymer as nano silver particles, for example, nano silver material can contain
Nano silver particles and polystyrene.
In nano silver material, the relative amount of polystyrene and nano silver particles can change in very large range, preferably
In the case of, the weight ratio of the nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, by this public affairs
Nano silver particles content in the antimicrobial composite material that the preparation method opened is prepared is suitable for, and nano silver particles and propylene
Nitrile-butadiene-styrene copolymer resin matrix compatibility is good, is conducive to the antibacterial effect for improving composite material.
In nano silver material, the carrier granulars such as nano silver particles and polystyrene may be constructed nano particle, the nanometer
The size of grain can change in very large range, wherein in order to improve the antibacterial effect and compatibility of nano silver particles, preferably
Ground, the partial size of nano particle can be 10-80nm in nano silver material.
According to the disclosure, nano silver material can be dispersed to obtain by the substance containing nano silver particles, can also be by chemistry
Reaction obtains.In the disclosure preferably a kind of embodiment, polystyrene and nanometer silver granuel can be contained in nano silver material
Son can be obtained by kayexalate with silver nitrate solution progress redox reaction described containing the molten of nano silver material
Liquid, shown in chemical equation such as following formula (1),
Reaction condition can change in very large range, for example, reaction temperature can be 20-100 DEG C, the reaction time can be with
For 5-60min, it is preferable that reaction temperature can be 50-90 DEG C, and the reaction time can be 10-40min.It is above-mentioned to contain nano silver
The solution that the solution of material can be formed for aqueous solution or other suitable solvents.In this one preferred embodiment, it aoxidizes
The nano silver particles that reduction reaction obtains can be with uniform adsorption on granules of polystyrene, to improve point of nano silver particles
Dissipate uniformity, at the same by with granules of polystyrene absorption can be further improved nano silver particles and copolymer resin matrix and
The compatibility of bamboo fibre.
It can also be changed in very large range according to the length of the disclosure, the bamboo fibre that is chopped, as long as meeting the bamboo fibre that is chopped
Humidification is played, and can be uniformly dispersed in the composite material.Under preferable case, the length for the bamboo fibre that is chopped can
Think 2-5mm.In above-mentioned preferred length range, be chopped bamboo fibre and acrylonitrile butadiene styrene resin base
The compatibility of body is good, and obvious to the humidification of composite material.
According to the disclosure, in order to further increase modification of the chemical modifier to acrylonitrile-butadiene-styrene copolymer
Effect improves the compatibility of copolymer resin matrix and chopped bamboo fibre, under preferable case, this method comprises: making acrylic nitrile-butadiene
Diene-styrene copolymer and chemical modifier are carried out with the chopped bamboo fibre composite fibre of the nano silver-again after mixing
Melting extrusion is granulated, and obtains the antimicrobial composite material.
It is highly preferred that in order to further increase the comprehensive of the composite material prepared by antimicrobial composite material preparation method
Can, antimicrobial composite material preparation method may include: to make in heat stabilizer, processing aid, ultraviolet absorber and antioxidant extremely
Be chopped with the nano silver-bamboo again after one kind is mixed with the acrylonitrile-butadiene-styrene copolymer and chemical modifier less
Fiber composite fiber carries out melting extrusion granulation, obtains the antimicrobial composite material；
Wherein, the specific type of antioxidant, heat stabilizer, ultraviolet absorber and processing aid can be those skilled in the art
Conventional kind known to member, for example, antioxidant can be for selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid positive 18
At least one of double octadecyls of carbon alcohol ester, 2- (1,1- dimethyl ethyl) -6- methyl-phenol, thio-2 acid；Thermostabilization
Agent can be for selected from least one of maleic acid tin octylate or carboxylic acid tin, Methyl stannum mercaptide and sulfydryl ester group tin；UV absorption
Agent can be for selected from 2,4 dihydroxyl benzophenone, ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol
Ketone, 2- (2 '-hydroxyls -3 ', 5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis
(4- t-octyl phenol oxygroup) nickel, (1,2,2,6,6- pempidine base) phosphite ester, 4- benzoyloxy -2,2,6,6- tetramethyl
At least one of piperidines；Processing aid can be for selected from calcium stearate, modified ethylene bis stearamide, polyethylene wax, ethylene
At least one of double stearic amides.
In the another embodiment of the disclosure, in order to improve the compatibility of bamboo fibre Yu copolymer resin matrix, resist
Bacterium composite material and preparation method thereof may include: to make the nano silver-bamboo fibre composite fibre after being chopped and the painting of coupling agent surface
After covering processing, with compatilizer and/or dispersant, the modified nano silver-bamboo fibre composite fibre in surface is obtained；Wherein, phase
Holding agent can be to connect selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride and ABS
At least one of branch maleic anhydride；Dispersing agent can be for selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, dodecyl sulphur
Sour sodium or at least one of fatty acid and macrogol ester.
As the disclosure, preferably a kind of embodiment, antimicrobial composite material preparation method include: to make the nano silver-bamboo
Fiber composite fiber, with compatilizer and dispersant, it is modified to obtain surface after being chopped and after the coating processing of coupling agent surface
Nano silver-bamboo fibre composite fibre；
Also, make heat stabilizer, processing aid, ultraviolet absorber and antioxidant and the acrylonitrile-butadiene-styrene (ABS)
The bamboo fibre composite fibre that is chopped again with the nano silver-after copolymer and chemical modifier mixing carries out melting extrusion granulation, obtains
To the antimicrobial composite material；
Above-mentioned compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid specific type can be with
As hereinbefore；Compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid amount ranges can be
Variation in very wide range, it is preferable that relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of compatilizer
It can be 0.5-5 parts by weight, the dosage of antioxidant can be 0.2-2 parts by weight, and the dosage of heat stabilizer can be 0.2-2 weight
Part, the dosage of dispersing agent can be 0.1-2 parts by weight, and the dosage of ultraviolet absorber can be 0.2-2 parts by weight, processing aid
Dosage can be 0.2-4 parts by weight.In this one preferred embodiment, by the antioxygen of the antimicrobial composite material of this method preparation
The comprehensive performances such as the property changed, weatherability and thermal stability are obviously improved.
According to the disclosure, in above-mentioned preparation process, the method that melting extrusion is granulated is well known to those skilled in the art, institute
Stating melting extrusion granulation can carry out on extrusion equipment, such as screw extruder, and the screw extruder can be single screw rod
Extruder or double screw extruder, the present invention do not do special requirement.
Wherein, the reaction condition that melting extrusion is granulated may be as it is known to those skilled in the art that can be according to matrix
The type and property of resin accordingly adjust.Under preferable case, in order to improve the melting mixing effect of each raw material component, melting extrusion
The temperature of granulation can be 210-250 DEG C.
The disclosure also provides a kind of composition for being used to prepare antimicrobial composite material, and the composition includes acrylic nitrile-butadiene two
Alkene-styrol copolymer, be chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein relative to 100 parts by weight
Acrylonitrile-butadiene-styrene copolymer, the content of the chopped bamboo fibre are 5-60 parts by weight, the nano silver material
Content is 0.01-2 parts by weight, and the content of the coupling agent is 0.1-10 parts by weight, and the content of the chemical modifier is 0.1-
20 parts by weight；The coupling agent is silane coupling agent and/or titante coupling agent；The chemical modifier is selected from aluminic acid
At least one of ester, ethylene bis-fatty acid amides and chromium picolinate.
Contain bamboo fibre and nano silver material in the composition and antimicrobial composite material of the disclosure, there is significant antibacterial to kill
Bacterium effect；Coupling agent and chemical modifier are combined, while bamboo fibre surface and resin matrix are modified, improves antibacterial
The mechanical property of composite material.
According to the disclosure, in order to further increase the antibacterial effect and power of the antimicrobial composite material prepared by the composition
Performance is learned, under preferable case, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the content for the bamboo fibre that is chopped
It can be 15-35 parts by weight, the content of nano silver material can be 0.01-0.5 parts by weight, and the content of coupling agent can be 0.5-
5 parts by weight, the content of chemical modifier can be 0.5-10 parts by weight.
According to the disclosure, the acrylonitrile-butadiene-styrene copolymer (ABS resin) is those skilled in the art institute
Known, the relative amount of acrylonitrile unit therein member, butadiene structural units and styrol structural unit is not important to
It asks, can be the conventional selection of field of compound material, for example, in acrylonitrile-butadiene-styrene copolymer, acrylonitrile structure
The weight ratio of unit, butadiene structural units and styrol structural unit can be 1:(0.15-2): (1-4).Above-mentioned acrylonitrile-
Butadiene-styrene copolymer can be commercial products, such as can for purchased from Japan Electric chemistry ABS resin GR-4000,
ABS Magnum800 purchased from Si Tailong company of the U.S., ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft,
KR2885,828P or 846L etc..
In the composition according to the disclosure, coupling agent can be used for carrying out surface to chopped bamboo fibre being modified, institute
Stating chemical modifier can be used for being modified resin matrix, and the two is used cooperatively for improving acrylonitrile-butadiene-benzene second
The interface compatibility of alkene copolymer and chopped bamboo fibre, to improve the interface bond strength of the two.In containing for above-mentioned composition
It measures in range, it is even in order to further increase the interface binding power of acrylonitrile-butadiene-styrene copolymer and chopped bamboo fibre
The amount ratio for joining agent and chemical modifier can be preferably 1:(0.5-2.5).
According to the disclosure, coupling agent can be silane coupling agent or titante coupling agent, specifically, silanes coupling
Agent can be selected from γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, vinyltriethoxysilane, ethylene
Base trimethoxy silane, double-(γ-triethoxy silicon substrate propyl) tetrasulfide, γ-methacryloxypropyl trimethoxy
One or more of silane, triphenyl silicol, wherein in order to make the processed fiberglass surfacing of silane coupling agent with
Active force between cyclic olefin polymer interface is stronger, under preferable case, selects the coupling agent containing olefin group, such as ethylene
Ethyl triethoxy silicane alkane, vinyltrimethoxysilane or γ-methacryloxypropyl trimethoxy silane；Titanate ester
Coupling agent can be for selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy)
Titanate esters, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters
The chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine and bis- (two octyloxy pyrophosphoric acid ester groups) second
Support at least one of titanate esters.
Aluminate can be for selected from three isopropyl ester of aluminic acid, three benzyl ester of aluminic acid；Ethylene bis-fatty acid amides can be double for ethylene
The double oleamides of stearic amide, ethylene, ethylene double at least one of palmitamides and ethylene dilaurate amide.
According to the disclosure, nano silver material can be any form containing nano silver particles, for example, nano silver material can
Think and contain only nano silver particles, can also disperse on the carrier particles, the type and content present invention of carrier granular is not spy
Other requirement, as long as meeting, nano silver particles are evenly distributed in nano silver material and content is suitable for.In order to improve nanometer
The compatibility of silver particles and resin matrix under preferable case, can choose the knot with acrylonitrile-butadiene-styrene copolymer
Structure unit is identical or structure similar in carrier granular of the polymer as nano silver particles, for example, can contain in nano silver material
There are nano silver particles and polystyrene.
In nano silver material, the relative amount of polystyrene and nano silver particles can change in very large range, preferably
In the case of, the weight ratio of the nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, by described
Nano silver particles content in the antimicrobial composite material of composition preparation is suitable for, and nano silver particles and acrylonitrile-butadiene-benzene
The compatibility of ethylene copolymer resin matrix is good, is conducive to the antibacterial effect for improving composite material.
In nano silver material, the carrier granulars such as nano silver particles and polystyrene may be constructed nano particle, the nanometer
The size of grain can change in very large range, wherein in order to improve the antibacterial effect and compatibility of nano silver particles, preferably
Ground, the partial size of nano particle can be 10-80nm in nano silver material.
According to the disclosure, the length of the chopped bamboo fibre composite fibre of nano silver-can also change in very large range, as long as
Meet the bamboo fibre that is chopped and play humidification, and can be uniformly dispersed in the composite material.Under preferable case, nanometer
The length of the chopped bamboo fibre composite fibre of silver-can be 2-5mm.In above-mentioned preferred length range, the chopped bamboo of nano silver-is fine
The compatibility for tieing up composite fibre and acrylonitrile butadiene styrene resin matrix is good, and makees to the enhancing of composite material
With obvious.
According to the disclosure, in order to further increase the performance of the antimicrobial composite material, under preferable case, above-mentioned composition
It can also include at least one of compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid.
Above-mentioned compatilizer, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid specific type can be with
The conventional kind being well known to those skilled in the art, for example, compatilizer can be for selected from Research of Grafting Malaic Anhydride Onto Polyethylene, benzene second
At least one of alkene grafted maleic anhydride, polypropylene grafted maleic anhydride and ABS grafted maleic anhydride；Antioxidant can be choosing
From β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 2- (1,1- dimethyl ethyl) -6- methyl-phenol,
At least one of double octadecyls of thio-2 acid；Heat stabilizer can be for selected from maleic acid tin octylate or carboxylic acid tin, methyl
At least one of tin mercaptides and sulfydryl ester group tin；Dispersing agent can be for selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, ten
Sodium dialkyl sulfate or at least one of fatty acid and macrogol ester；Ultraviolet absorber can be for selected from 2,4- dihydroxy two
Benzophenone, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ', 5 '-two
Tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel, (1,2,
2,6,6- pempidine base) phosphite ester, at least one of 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Processing helps
Agent can be at least one in calcium stearate, modified ethylene bis stearamide, polyethylene wax, ethylene bis stearic acid amide
Kind.
As a kind of preferred embodiment of the disclosure, the composition further include compatilizer, antioxidant, heat stabilizer,
Dispersing agent, ultraviolet absorber and processing aid；Preferably, the content of above-mentioned auxiliary agent can be with are as follows: relative to 100 parts by weight propylene
The content of nitrile-butadiene-styrene copolymer, compatilizer can be 0.5-5 parts by weight, and the content of antioxidant can be 0.2-2
Parts by weight, the content of heat stabilizer can be 0.2-2 parts by weight, and the content of dispersing agent can be 0.1-2 parts by weight, UV absorption
The content of agent can be 0.2-2 parts by weight, and the content of processing aid can be 0.2-4 parts by weight.Above-mentioned preferred auxiliary agent and contain
The comprehensive performances such as the inoxidizability, weatherability and thermal stability of the antimicrobial composite material can be improved in amount range.
The disclosure is further illustrated by the following examples, but therefore the disclosure is not any way limited.At this
In disclosed following embodiments, acrylonitrile-butadiene-styrene copolymer is the ABS resin purchased from BASF Aktiengesellschaft
Terluran KR2883, bamboo fibre are purchased from Ningbo Qi Zhu company；Other chemical reagent are general commercial products；Melting is squeezed
It is prepared in upper tableland connection company's T L-55-55-500 type double screw extruder out.
Embodiment 1
The present embodiment is used to illustrate the composition for being used to prepare antimicrobial composite material of the disclosure.
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 15 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the grain of nano particle to 0.01 parts by weight nano silver material
Diameter is 20nm), 0.1 parts by weight Silane coupling agent KH550,15 parts by weight chemical modifier Aluminates.
Embodiment 2
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 60 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:20, the partial size of nano particle to 2 parts by weight nano silver materials
For 80nm), 10 parts by weight coupling agent isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, 0.1 parts by weight chemical modifier
Ethylene bis-fatty acid amides.
Embodiment 3
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 5 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:1, the grain of nano particle to 0.02 parts by weight nano silver material
Diameter is 30nm), 0.1 parts by weight Silane coupling agent KH550,0.2 parts by weight chemical modifier chromium picolinate.
Embodiment 4
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 15 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the grain of nano particle to 0.05 parts by weight nano silver material
Diameter is 20nm), 0.5 parts by weight Silane coupling agent KH550,10 parts by weight chemical modifier Aluminates.
Embodiment 5
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 35 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the partial size of nano particle to 0.4 parts by weight nano silver material
For 20nm), 5 parts by weight Silane coupling agent KH550s, 0.5 parts by weight chemical modifier Aluminate.
Embodiment 6
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 15 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the grain of nano particle to 0.01 parts by weight nano silver material
Diameter is 20nm), 0.1 parts by weight Silane coupling agent KH550,0.1 parts by weight chemical modifier Aluminate.
Embodiment 7
Contain in the composition of the present embodiment: 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, 30 parts by weight are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3, the partial size of nano particle to 0.2 parts by weight nano silver material
It is connect for 20nm), 1 parts by weight Silane coupling agent KH550,1 parts by weight chemical modifier Aluminate, 1 parts by weight of compatible agent styrene
Branch maleic anhydride, 0.5 parts by weight antioxidant β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 0.5 weight
Part heat stabilizer maleic acid tin octylate, 0.5 parts per weight dispersing agent macrogol ester, 0.5 parts by weight ultraviolet absorber 2,4- dihydroxy
Base benzophenone and 0.5 parts by weight processing aid calcium stearate.
Comparative example 1
This comparative example is for illustrating the composition that is used to prepare antimicrobial composite material different from the disclosure.
The ingredient of object is closed in the composition containing example 1 group, the difference is that nano silver material such as is replaced at the weight
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 2
This comparative example is for illustrating the composition that is used to prepare antimicrobial composite material different from the disclosure.
The ingredient of object is closed in the composition containing example 1 group, the difference is that chopped bamboo fibre such as is replaced at the weight
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 3
This comparative example is for illustrating the composition that is used to prepare antimicrobial composite material different from the disclosure.
The ingredient of object is closed in the composition containing example 1 group, the difference is that coupling agent KH550 such as is replaced at the weight
The chemical modifier Aluminate of amount.
Comparative example 4
This comparative example is for illustrating the composition that is used to prepare antimicrobial composite material different from the disclosure.
The ingredient for closing object in the composition containing example 1 group, the difference is that chemical modifier Aluminate is replaced with
Etc. weight coupling agent KH550.
Prepare embodiment 1
The present embodiment is used to illustrate the preparation method of the antimicrobial composite material of the disclosure, the antimicrobial composite material of the present embodiment
In each raw material dosage it is identical as the composition of embodiment 1, include the following steps:
(1) kayexalate is added in silver nitrate solution and is mixed evenly, in micro-wave oven, 500w heating
30min, centrifuge separation, obtains the aqueous solution containing nano silver material, bamboo fibre is immersed in concentration 1g/L's after drying process
It is compound to obtain nano silver-bamboo fibre for aqueous solution containing nano silver material, second dipping and rolling, heated by microwave fast dewatering, drying
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre obtained (1) is carried out after being chopped with Silane coupling agent KH550
The chopped bamboo fibre composite fibre (length 2-5mm) of the modified nano silver-in surface is obtained after the coating of surface；
(3) by ABS resin and chemical modifier put into heated at high speed mixing machine (2000 turns/min of speed of agitator) into
It is added twin-screw extrude (230 DEG C of temperature) after row mixing dispersion, then will the chopped compound fibre of bamboo fibre of nano silver-in (2)
Dimension is added from the side spout of extruder, carries out melt pelletization, by obtaining this reality after outlet mold sizing, water cooling, air-dried, pelletizing
Apply the antimicrobial composite material of example.
Prepare embodiment 2
Using preparation embodiment 1 method, the difference is that in the antimicrobial composite material of the present embodiment each raw material dosage
It is identical as the composition of embodiment 2.
Prepare embodiment 3
Using preparation embodiment 1 method, the difference is that in the antimicrobial composite material of the present embodiment each raw material dosage
It is identical as the composition of embodiment 3.
Prepare embodiment 4
Using preparation embodiment 1 method, the difference is that in the antimicrobial composite material of the present embodiment each raw material dosage
It is identical as the composition of embodiment 4.
Prepare embodiment 5
Using preparation embodiment 1 method, the difference is that in the antimicrobial composite material of the present embodiment each raw material dosage
It is identical as the composition of embodiment 5.
Prepare embodiment 6
Using preparation embodiment 1 method, the difference is that in the antimicrobial composite material of the present embodiment each raw material dosage
It is identical as the composition of embodiment 6.
Prepare embodiment 7
The composition of dosage with embodiment 7 of each raw material is identical in the antimicrobial composite material of the present embodiment, preparation method packet
Include following steps:
(1) kayexalate is added in silver nitrate solution and is mixed evenly, in micro-wave oven, 500w heating
30min, centrifuge separation, obtains the aqueous solution containing nano silver material, bamboo fibre is immersed in concentration 1g/L's after drying process
It is compound to obtain nano silver-bamboo fibre for aqueous solution containing nano silver material, second dipping and rolling, heated by microwave fast dewatering, drying
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre obtained (1) is carried out after being chopped with Silane coupling agent KH550
It is reacted with compatilizer, dispersing agent through heated at high speed mixing machine (2000 turns/min of speed of agitator) after the coating of surface, in compatilizer
Esterification occurs for the hydroxyl (- OH) in maleic anhydride and bamboo fibre, the carboxyl (- COOH) that reaction process generates again with natural fibre
Subsequent esterification occurs for the hydroxyl (- OH) in dimension, and it is (long to obtain the chopped bamboo fibre composite fibre of the modified nano silver-in surface
Degree is 2-5mm)；
(3) ABS resin, chemical modifier, heat stabilizer, processing aid, ultraviolet absorber and antioxidant are put into height
(temperature 230 is added twin-screw extrude after carrying out mixing dispersion (2000 turns/min of speed of agitator) in speed heating mixing machine
DEG C), then the nano silver-in (2) is chopped bamboo fibre composite fibre from the addition of the side spout of extruder, melt pelletization is carried out,
Again by obtaining the antimicrobial composite material of the present embodiment after outlet mold sizing, water cooling, air-dried, pelletizing.
Prepare comparative example 1-4
Using preparation embodiment 1 method, the difference is that in antimicrobial composite material the dosage of each raw material respectively with comparison
The composition of example 1-4 is identical.
Prepare comparative example 5
The composition of dosage with embodiment 1 of each raw material is identical in the antimicrobial composite material of the present embodiment, including walks as follows
It is rapid:
Composition in embodiment 1 is put into heated at high speed mixing machine carry out mixing dispersion (2000 turns of speed of agitator/
Min add twin-screw extrude (230 DEG C of temperature) after) and carry out melt pelletization, then by outlet mold sizing, water cooling, air-dry, cut
The antimicrobial composite material of the present embodiment is obtained after grain.
Testing example 1
Batten is made in antimicrobial composite material obtained in preparation embodiment 1-7 and preparation comparative example 1-5 on injection molding machine,
Then it performs the following performance tests respectively:
Tensile strength is tested according to ASTM D638 standard, and batten is having a size of 170*13*3.22mm, tensile speed
50mm/min, bending strength and bending modulus are tested according to ASTM D790 standard, and batten is having a size of 127*12.7*
3.22mm, span 56mm, rate of bending 2mm/min, notch impact strength are tested according to ASTMD256 standard, batten ruler
Very little is 63.5*12.7*3.22mm, and notch depth is the one third of sample thickness, and test result is listed in table 1
According to light industry of China professional standard QB/T 2591-2003, " antibiotic plastic-anti-microbial property is commented for the test of antibiotic rate
Valence and its test method " standard tests it.Test the strain used: staphylococcus aureus, Escherichia coli, black song
Mould, Aspergillus terreus, test result are listed in table 2.
Table 1
| Tensile strength (MPa) | Bending strength (MPa) | Notch impact strength (J/m) | |
| Prepare embodiment 1 | 40.8 | 62.7 | 113.8 |
| Prepare embodiment 2 | 31.8 | 53.3 | 68.0 |
| Prepare embodiment 3 | 39.6 | 61.4 | 109.7 |
| Prepare embodiment 4 | 42.3 | 63.8 | 103.6 |
| Prepare embodiment 5 | 47.2 | 68.4 | 105.3 |
| Prepare embodiment 6 | 48.5 | 69.7 | 87.4 |
| Prepare embodiment 7 | 47.8 | 70.8 | 95.5 |
| Prepare comparative example 1 | 40.5 | 62.8 | 112.8 |
| Prepare comparative example 2 | 35.8 | 52.3 | 120.9 |
| Prepare comparative example 3 | 38.3 | 60.9 | 108.7 |
| Prepare comparative example 4 | 37.9 | 59.6 | 106.7 |
| Prepare comparative example 5 | 29.4 | 45.9 | 86.4 |
Table 2
According to Tables 1 and 2 data, can be seen that relatively from preparation embodiment 1 and the data comparison for preparing comparative example 1-2
In the composite material for containing only nano silver material or bamboo fibre, the antimicrobial composite material of the disclosure contain simultaneously nano silver material and
Bamboo fibre has more significant antibiotic and sterilizing effect；It can with the data comparison for preparing comparative example 3-4 from preparation embodiment 1
Out, relative to the composite material for containing only chemical modifier or coupling agent, the antimicrobial composite material and preparation method of the disclosure will
Coupling agent and chemical modifier combination, while bamboo fibre surface and resin matrix are modified, improve antimicrobial composite material
Mechanical property；Preparation embodiment 1 can be seen that with the data comparison for preparing comparative example 5 and be obtained using the preparation method of the disclosure
To antimicrobial composite material keep mechanical property be basically unchanged while, improve antibacterial effect and mechanical property.
From preparation embodiment 1-3 and prepare embodiment 4-5 data comparison can be seen that the disclosure preferably relative to
100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of the chopped bamboo fibre is 15-35 parts by weight, described to receive
The dosage of rice ag material is 0.01-0.5 parts by weight, and the dosage of the coupling agent is 0.5-5 parts by weight, the chemical modifier
In the case that dosage is 0.5-10 parts by weight, the antibacterial effect and mechanics of the antimicrobial composite material that the preparation method of the disclosure obtains
Performance is more preferable；From preparation embodiment 1 and prepare embodiment 6 data comparison can be seen that in the preferred coupling agent of the disclosure and
The amount ratio of chemical modifier is 1:(0.5-2.5) in the case where, the mechanical property of the antimicrobial composite material of the disclosure is more preferable；From
Preparation embodiment 1 and the data comparison of preparation embodiment 7 can be seen that preferably the composition further includes compatible in the disclosure
Agent, antioxidant, heat stabilizer, dispersing agent, ultraviolet absorber and processing aid, relative to 100 parts by weight of acrylonitrile-butadiene-
Styrol copolymer, the content of the compatilizer are 0.5-5 parts by weight, and the content of the antioxidant is 0.2-2 parts by weight, described
The content of heat stabilizer is 0.2-2 parts by weight, and the content of the dispersing agent is 0.1-2 parts by weight, and the ultraviolet absorber contains
Amount is 0.2-2 parts by weight, in the case that the content of the processing aid is 0.2-4 parts by weight, the antimicrobial composite material of the disclosure
Mechanical property it is more preferable
The preferred embodiment of the disclosure is described in detail above, still, during the disclosure is not limited to the above embodiment
Detail a variety of simple variants can be carried out to the technical solution of the disclosure in the range of the technology design of the disclosure, this
A little simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as content provided by the disclosure.
Claims (19)
1. a kind of method for preparing antimicrobial composite material, which is characterized in that this method comprises the following steps:
(1) bamboo filament is carried out to pad processing using the solution containing nano silver material, it is compound obtains nano silver-bamboo fibre
Fiber；
(2) make the nano silver-bamboo fibre composite fibre after being chopped, contacted with coupling agent and carry out surface coating processing, obtained
The chopped bamboo fibre composite fibre of the modified nano silver-in surface；
(3) make the chopped bamboo fibre composite fibre of acrylonitrile-butadiene-styrene copolymer, chemical modifier and the nano silver-
Melting extrusion granulation is carried out, the antimicrobial composite material is obtained；
Relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of the chopped bamboo fibre is 5-60 weight
Part, the dosage of the nano silver material is 0.01-2 parts by weight, and the dosage of the coupling agent is 0.1-10 parts by weight, the chemistry
The dosage of modifying agent is 0.1-20 parts by weight；The nano silver material contains nano silver particles and polystyrene, the nano silver
The weight ratio of particle and polystyrene is 1:(1-20).
2. the method according to claim 1, wherein the coupling agent is silane coupling agent and/or titanate esters
Class coupling agent；The chemical modifier is selected from least one of Aluminate, ethylene bis-fatty acid amides and chromium picolinate.
3. the method according to claim 1, wherein relative to 100 parts by weight of acrylonitrile-butadiene-styrene
Copolymer, the dosage of the chopped bamboo fibre are 15-35 parts by weight, and the dosage of the nano silver material is 0.01-0.5 weight
Part, the dosage of the coupling agent is 0.5-5 parts by weight, and the dosage of the chemical modifier is 0.5-10 parts by weight.
4. the method according to claim 1, wherein the amount ratio of the coupling agent and the chemical modifier is
1:(0.5-2.5).
5. the method according to claim 1, wherein the partial size of nano particle is 10- in the nano silver material
80nm。
6. preparation method according to claim 1, which is characterized in that the chopped bamboo fibre composite fibre of the nano silver-
Length is 2-5mm.
7. preparation method according to claim 1, which is characterized in that this method comprises: making acrylonitrile-butadiene-benzene second
Alkene copolymer and chemical modifier carry out melting extrusion with the chopped bamboo fibre composite fibre of the nano silver-again after mixing and make
Grain, obtains the antimicrobial composite material.
8. preparation method according to claim 7, which is characterized in that this method comprises: make heat stabilizer, processing aid,
At least one of ultraviolet absorber and antioxidant and the acrylonitrile-butadiene-styrene copolymer and chemical modifier are mixed
The bamboo fibre composite fibre that is chopped again with the nano silver-after conjunction carries out melting extrusion granulation, obtains the antimicrobial composite material；
The antioxidant is selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 2- (1,1- dimethyl
Ethyl) -6- methyl-phenol, at least one of double octadecyls of thio-2 acid；The heat stabilizer is misery selected from Malaysia
At least one of base tin or carboxylic acid tin, Methyl stannum mercaptide and sulfydryl ester group tin；The ultraviolet absorber is selected from 2,4- dihydroxy
Base benzophenone, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ',
5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel,
At least one of (1,2,2,6,6- pempidine base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Institute
Processing aid is stated to be selected from calcium stearate, be modified in ethylene bis stearamide, polyethylene wax and ethylene bis stearic acid amide extremely
Few one kind.
9. preparation method according to claim 1, which is characterized in that this method comprises: keeping the nano silver-bamboo fibre multiple
Condensating fiber, with compatilizer and/or dispersant, obtains receiving for surface modification after being chopped and after the coating processing of coupling agent surface
Meter Yin-bamboo fibre composite fibre；
The compatilizer is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride
At least one of with ABS grafted maleic anhydride；The dispersing agent is selected from two polyphosphate sodiums, triethyl group hexyl phosphoric acid sodium, ten
Sodium dialkyl sulfate or at least one of fatty acid and macrogol ester.
10. preparation method according to claim 9, which is characterized in that this method comprises: making the nano silver-bamboo fibre
Composite fibre, with compatilizer and dispersant, obtains receiving for surface modification after being chopped and after the coating processing of coupling agent surface
Meter Yin-bamboo fibre composite fibre；
Make heat stabilizer, processing aid, ultraviolet absorber and antioxidant and the acrylonitrile-butadiene-styrene copolymer and
The bamboo fibre composite fibre that is chopped again with the nano silver-after chemical modifier mixing carries out melting extrusion granulation, obtains described anti-
Bacterium composite material；
The antioxidant is selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 2- (1,1- dimethyl
Ethyl) -6- methyl-phenol, at least one of double octadecyls of thio-2 acid；The heat stabilizer is misery selected from Malaysia
At least one of base tin or carboxylic acid tin, Methyl stannum mercaptide and sulfydryl ester group tin；The ultraviolet absorber is selected from 2,4- dihydroxy
Base benzophenone, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ',
5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygroup) nickel,
At least one of (1,2,2,6,6- pempidine base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Institute
Processing aid is stated to be selected from calcium stearate, be modified in ethylene bis stearamide, polyethylene wax and ethylene bis stearic acid amide extremely
Few one kind；
Wherein, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer, the dosage of the compatilizer is 0.5-5 weight
Part is measured, the dosage of the antioxidant is 0.2-2 parts by weight, and the dosage of the heat stabilizer is 0.2-2 parts by weight, the dispersing agent
Dosage be 0.1-2 parts by weight, the dosage of the ultraviolet absorber is 0.2-2 parts by weight, and the dosage of the processing aid is
0.2-4 parts by weight.
11. preparation method described in any one of -10 according to claim 1, which is characterized in that the melting extrusion was granulated
Temperature is 210-250 DEG C.
12. preparation method described in any one of -10 according to claim 1, which is characterized in that this method comprises: making polyphenyl
Vinyl sulfonic acid sodium and silver nitrate solution carry out redox reaction and obtain the solution containing nano silver material.
13. a kind of composition for being used to prepare antimicrobial composite material, which is characterized in that the composition includes acrylonitrile-butadiene-
Styrol copolymer, be chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein relative to 100 parts by weight third
The content of alkene nitrile-butadiene-styrene copolymer, the chopped bamboo fibre is 5-60 parts by weight, and the nano silver material contains
Amount is 0.01-2 parts by weight, and the content of the coupling agent is 0.1-10 parts by weight, and the content of the chemical modifier is 0.1-20
Parts by weight；The coupling agent is silane coupling agent and/or titante coupling agent；The chemical modifier is selected from aluminic acid
At least one of ester, ethylene bis-fatty acid amides and chromium picolinate；The nano silver material contains nano silver particles and gathers
The weight ratio of styrene, the nano silver particles and polystyrene is 1:(1-20).
14. composition according to claim 13, which is characterized in that relative to 100 parts by weight of acrylonitrile-butadiene-benzene
Ethylene copolymer, the content of the chopped bamboo fibre are 15-35 parts by weight, and the content of the nano silver material is 0.01-0.5 weight
Part is measured, the content of the coupling agent is 0.5-5 parts by weight, and the content of the chemical modifier is 0.5-10 parts by weight.
15. composition according to claim 13, which is characterized in that the content of the coupling agent and the chemical modifier
Than for 1:(0.5-2.5).
16. composition according to claim 13, which is characterized in that the partial size of nano particle is in the nano silver material
10-80nm。
17. composition according to claim 13, which is characterized in that the length of the chopped bamboo fibre is 2-5mm.
18. composition according to claim 13, which is characterized in that the composition further includes compatilizer, antioxidant, heat
At least one of stabilizer, dispersing agent, ultraviolet absorber and processing aid；The compatilizer is selected from polycthylene grafted Malaysia
At least one of acid anhydrides, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride and ABS grafted maleic anhydride；It is described
Antioxidant is selected from β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 2- (1,1- dimethyl ethyl) -6-
At least one of double octadecyls of methyl-phenol, thio-2 acid；The heat stabilizer is selected from maleic acid tin octylate or carboxylic
At least one of sour tin, Methyl stannum mercaptide and sulfydryl ester group tin；The dispersing agent is selected from two polyphosphate sodiums, triethyl group hexyl
Sodium phosphate, lauryl sodium sulfate or at least one of fatty acid and macrogol ester；The ultraviolet absorber be selected from 2,
4- dihydroxy benaophenonel, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls
Base -3 ', 5 '-two tertiary phenyl) -5- chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4- t-octyl phenol oxygen
Base) nickel, (1,2,2,6,6- pempidine base) phosphite ester, in 4 benzoyloxy 2,2,6,6 tetramethyl piperidine at least
It is a kind of；The processing aid is selected from calcium stearate, modified ethylene bis stearamide, polyethylene wax, ethylene bis stearic acid amide
At least one of.
19. composition according to claim 18, which is characterized in that the composition further includes compatilizer, antioxidant, heat
Stabilizer, dispersing agent, ultraviolet absorber and processing aid, relative to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer,
The content of the compatilizer is 0.5-5 parts by weight, and the content of the antioxidant is 0.2-2 parts by weight, and the heat stabilizer contains
Amount is 0.2-2 parts by weight, and the content of the dispersing agent is 0.1-2 parts by weight, and the content of the ultraviolet absorber is 0.2-2 weight
Part, the content of the processing aid is 0.2-4 parts by weight.
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| CN110669309A (en) * | 2019-10-29 | 2020-01-10 | 临沂大学 | High-strength and antibacterial material for bags and suitcases and preparation method thereof |
| CN114630862B (en) * | 2020-10-14 | 2024-04-23 | 株式会社Lg化学 | Thermoplastic resin composition, method of preparing the same, and molded article comprising the same |
| CN113293477A (en) * | 2021-05-26 | 2021-08-24 | 江西绣丽织带有限公司 | Elastic velvet ribbon with double-sided velvet and preparation method thereof |
| CN114015237B (en) * | 2021-10-29 | 2022-12-16 | 厦门赋源高科技有限公司 | Antibacterial composite material and preparation method thereof |
| CN114213804B (en) * | 2021-12-29 | 2024-03-08 | 重庆普利特新材料有限公司 | High-toughness antibacterial reinforced ABS composite material and preparation method thereof |
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