CN106280218A - A kind of preparation method of the compositions and antimicrobial composite material for preparing antimicrobial composite material - Google Patents
A kind of preparation method of the compositions and antimicrobial composite material for preparing antimicrobial composite material Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
Present disclose provides a kind of method preparing antimicrobial composite material and for preparing the compositions of antimicrobial composite material, the method comprises the steps: that (1) uses the solution containing nano silver material that bamboo filament is padded process, obtains nanometer silver bamboo fibre composite fibre；(2) make described nanometer silver bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process, obtain the nanometer silver chopped bamboo fibre composite fibre of surface modification；(3) make acrylonitrile butadient styrene, chemical modifier and described nanometer silver chopped bamboo fibre composite fibre carry out melt extruding pelletize, obtain described antimicrobial composite material.The preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and the antimicrobial composite material prepared has significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, bamboo fibre surface and resin matrix are modified simultaneously, improve the mechanical property of antimicrobial composite material.
Description
Technical field
It relates to fibrous composite field, in particular it relates to a kind of combination for preparing antimicrobial composite material
Thing and the preparation method of antimicrobial composite material.
Background technology
In recent years, the development of auto industry has brought great convenience, and the appearance of new-energy automobile is further
Alleviating the predicament of Current resource shortage, the most also the requirement to automotive light weight technology grows with each passing day.For reply automotive light weight technology
Demand, fibre reinforced composites are as one of main solution, and in automotive material, proportion constantly increases.The most fine
Dimension strengthens composite and is mainly formed with plastic composition by glass fibre, carbon fiber etc., and the process of garbage is more difficult, produce ring
Border is severe, brings the biggest burden to environment.Along with people's environmental protection consciousness constantly strengthens, processing characteristics is excellent, by with
In the problem that the plastics pollution on the environment of various industrial products has become general concern.Therefore, natural fiber is as increasing
Strong material attracts attention for production environment friendly composite.
The research utilizing Plant fiber and synthetic resin to carry out being combined has longer history, and at present, bio-based materials exists
Application in terms of automobile has begun to, as natural fiber replaces glass fiber reinforcement；Toyota Company of Japan is in the car exhibition of Chicago
Illustrate the I/X plug-in hybrid concept car of flaxen fiber bio-based materials roof；Ford shows in model U
The backboard of soy resins support and seat foam；And use Plant fiber to strengthen PP material manufacture instrumental panel assembly shell and become
Main flow, a kind of abnormal smells from the patient is little, be difficult to aging, low-density and have the Plant fiber of more preferable environmental suitability to strengthen PP material,
Apply on car；The polypropylene automotive parts that 45% wood fiber occurred on German market strengthens, what the wood fiber strengthened subtracts
The products such as shake calendared sheet.The state such as India, Japan uses Corchorus olitorius L., Folium Agaves Sisalanae, flax fiber and hemp as reinforcing material and heat
Thermoplastic polymer is made natural plant fibre polymer composite product and is also had started to engineer applied.Natural fiber increases at home
Strong composite is at the early-stage, and the research in this field is still in the starting stage and really realizes the product of volume production and the most do not go out
Existing.
China's bamboo wood yield ranks first in the world, accounts for more than the 30% of the world, and cheap, and major part is distributed in
The mountain areas such as Hunan, Anhui, Zhejiang.Bamboo fiber has good biodegradable and recyclability simultaneously, utilizes this fibre
The dimension material developed compound with the thermoplastic resin such as low-melting point polyester and polypropylene, its intensity, specific modulus are of a relatively high, suitably
Make the reinforcement of the composite of automobile；Enhancing can be made to be separated with matrix by melt process simultaneously, effectively reach
The purpose recycled, thus embody the feature of environmental protection and the sustainable developability of materials application.Bamboo fiber reinforcement thermoplastic
Composite processing power consumption is few, and process equipment loss is little, is conducive to saving the energy.The maximum feature of bamboo fibre is the height of cross section
Degree natural hollow.Being covered with ellipse space on bamboo fibre cross section, space is quincunx arrangement, and this makes bamboo fibre and goods thereof
Moisture absorption, moisture releasing, wet transmitting performance are splendid, and expert is referred to as " fiber that can breathe ".Bamboo has natural antibacterial, fungi-proofing, protection merit
Can, free from insect pests in its growth course, nothing are rotted.In process of manufacture, these antibiotic substance will not be destroyed, its sky
So human body will not be caused any reaction by antibiotic property, and can also health-care and skin-care, the antibacterial that its effect adds after being much better than.Bamboo
Fiber reinforced thermoplastics composite has broad application prospects in fields such as automobile, electromechanics, interior decorations.
Nano silver particles particle diameter, typically at 25-50 ran, has high-specific surface area, unique physico-chemical property, efficiently
Antibacterial activity, the tens of kinds of pathogenic microorganism such as escherichia coli, gonococcus, chlamydia trachomatis are had strong suppression and kill
Effect.Finding according to the study, nanometer silver can kill 650 various bacteria in several minutes, and the cell wall of nano-Ag particles and pathogen/
After film combines, can be directly entered thalline, rapid and oxygen metabolism enzyme sulfydryl (-SH) combines, and makes enzyme inactivate, blocks respiratory metabolism and make
It is choked to death.Unique sterilization mechanism so that nano-Ag particles just can kill rapidly pathogenic bacterium at low concentration, and will not produce
Raw drug resistance, without any toxic reaction, does not finds any irritant reaction to skin yet.
Vehicle air conditioning outlet is for automotive interior heating, the exhaust apparatus of ventilating and air conditioning system, is car room
Outer air intercommunication, circulation must be through part, in addition to meeting in various mechanical properties and requiring, also need to ensure that air is in circulation
During keep cleaning, not by the pollution of mycete etc., protection rider respiratory health.And current most composite exists
In the case of air humidity is relatively big, all can generation mycete in various degree, thus contaminated air, bring hidden danger to health；
Meanwhile, in existing bamboo fiber composite material, bamboo fibre is bad with the compatibility of plastics, has had a strong impact on the performance of composite.
Summary of the invention
The purpose of the disclosure is to provide a kind of method preparing antimicrobial composite material, antimicrobial composite material prepared by the method
The composite that existing method can be overcome to prepare easily produces mycete, and fiber affects composite with resin compatible difference
The technical problem of energy.
Another object of the present disclosure is to provide a kind of compositions for preparing antimicrobial composite material, and said composition is permissible
Solve existing composite and easily produce mycete, and the fiber technology that affect composite property poor with resin compatible is asked
Topic.
To achieve these goals, the disclosure provides the preparation method of a kind of antimicrobial composite material, and the method includes as follows
Step:
(1) use the solution containing described nano silver material that bamboo filament is padded process, obtain nanometer silver-bamboo
Fiber composite fiber；
(2) make described nanometer silver-bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process,
Obtain the nanometer silver-chopped bamboo fibre composite fibre of surface modification；
(3) acrylonitrile-butadiene-styrene copolymer, chemical modifier is made to be combined with described nanometer silver-chopped bamboo fibre
Fiber carries out melt extruding pelletize, obtains described antimicrobial composite material.
By technique scheme, the preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, prepares
Antimicrobial composite material there is significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, simultaneously to bamboo fibre table
Face and resin matrix are modified, and improve the mechanical property of antimicrobial composite material.
The disclosure also provides for a kind of compositions for preparing antimicrobial composite material, and said composition includes acrylic nitrile-butadiene two
Alkene-styrol copolymer, chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein, relative to 100 weight portions
Acrylonitrile-butadiene-styrene copolymer, the content of described chopped bamboo fibre is 5-60 weight portion, described nano silver material
Content is 0.01-2 weight portion, and the content of described coupling agent is 0.1-10 weight portion, and the content of described chemical modifier is 0.1-
20 weight portions；Described coupling agent is silane coupling agent and/or titante coupling agent；Described chemical modifier is selected from aluminic acid
At least one in ester, ethylene bis-fatty acid amides and chromium picolinate.
By technique scheme, containing bamboo fibre and nanometer silver material in the compositions of the disclosure and antimicrobial composite material
Material, has significant antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, simultaneously 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 be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Detailed description of the invention the most of this disclosure is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the disclosure, is not limited to the disclosure.
The disclosure provides the preparation method of a kind of antimicrobial composite material, and the method comprises the steps:
(1) use the solution containing described nano silver material that bamboo filament is padded process, obtain nanometer silver-bamboo
Fiber composite fiber；
(2) make described nanometer silver-bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process,
Obtain the nanometer silver-chopped bamboo fibre composite fibre of surface modification；
(3) acrylonitrile-butadiene-styrene copolymer, chemical modifier is made to be combined with described nanometer silver-chopped bamboo fibre
Fiber carries out melt extruding pelletize, obtains described antimicrobial composite material.
The preparation method of the disclosure uses bamboo fibre and nano silver material simultaneously, and the antimicrobial composite material prepared has
Significantly antibiotic and sterilizing effect；Coupling agent and chemical modifier are combined, bamboo fibre surface and resin matrix are changed simultaneously
Property, improve the mechanical property of antimicrobial composite material.
Wherein, described in pad the method for process and be well known to those skilled in the art, be referred to sizing fabric operation
Method for sizing, utilizes the cooperation of compregnate roller and sizing roller to carry out.Specifically processing method can be two leachings two roll, double leaching three press or
Double leaching four pressures etc., method is rolled in preferably two leachings two.
According to the disclosure, the consumption of each raw material components can in very large range change, and can be field of compound material skill
The consumption that art personnel are commonly used, such as, relative to 100 parts by weight of acrylonitrile-BS, chopped bamboo fibre
Consumption can be 5-60 weight portion, the consumption of nano silver material can be 0.01-2 weight portion, and the consumption of coupling agent can be
0.1-10 weight portion, the consumption of chemical modifier can be 0.1-20 weight portion；Coupling agent can be silane coupling agent and/or
Titante coupling agent；Chemical modifier can be in Aluminate, ethylene bis-fatty acid amides and chromium picolinate extremely
Few one.
In order to improve antibacterial effect and the mechanical property of the antimicrobial composite material prepared by said method, preferably feelings further
Under condition, relative to 100 parts by weight of acrylonitrile-BS, the consumption of chopped bamboo fibre can be 15-35 weight
Amount part, the consumption of nano silver material can be 0.01-0.5 weight portion, and the consumption of coupling agent can be 0.5-5 weight portion, chemistry
The consumption of modifying agent can be 0.5-10 weight portion.
According to the disclosure, described acrylonitrile-butadiene-styrene copolymer (ABS resin) is those skilled in the art institutes
Knowing, the relative amount of acrylonitrile unit therein unit, butadiene structural units and styrol structural unit is not important to
Ask, can be the conventional selection of field of compound material, such as, 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).Aforesaid propylene nitrile-
BS can be commercial products, can be such as purchased from NEC chemistry ABS resin GR-4000,
ABS Magnum800 purchased from Si Tailong company of the U.S., the ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft,
KR2885,828P or 846L etc..
According in the preparation method of the disclosure, coupling agent may be used for chopped bamboo fibre is carried out surface modification, described
Chemical modifier may be used for being modified resin matrix, and the two is with the use of being used for improving acrylonitrile-butadiene-styrene (ABS)
Copolymer and the interface compatibility of chopped bamboo fibre, thus improve the interface bond strength of the two.Each group of above-mentioned preparation method
In demultiplexing weight range, in order to improve acrylonitrile-butadiene-styrene copolymer and the interface cohesion of chopped bamboo fibre further
The amount ratio of power, coupling agent and chemical modifier can be preferably 1:(0.5-2.5).
Coupling agent is used nanometer silver-bamboo fibre composite fibre to carry out the method for surface-coated process also for art technology
Known to personnel, for example, it is possible to be scattered in by nanometer silver-bamboo fibre composite fibre containing 0.2-10% (wt) coupling agent is anhydrous
In ethanol, addition HCl regulation pH value is to 4-5, and at 50 DEG C, ultrasonic disperse reacts 1-2 hour.After reaction terminates, taking-up nanometer silver-
Bamboo fibre composite fibre, cleans to neutral with distilled water, dries 2-5 hour, obtain the nanometer of surface modification at 100-120 DEG C
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, VTES, ethylene
Base trimethoxy silane, double-(the silica-based propyl group of γ-triethoxy) tetrasulfide, γ-methacryloxypropyl trimethoxy
One or more in silane, triphenyl silicol, wherein, in order to make fiberglass surfacing that silane coupler processed with
Active force between cyclic olefin polymer interface is higher, under preferable case, selects the coupling agent containing olefin group, such as ethylene
Ethyl triethoxy silicane alkane, vinyltrimethoxy silane or γ-methacryloxypropyl trimethoxy silane；Titanate ester
Coupling agent can be selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy)
Titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters
The chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine and double (two octyloxy pyrophosphoric acid ester groups) second
At least one in support titanate esters.
Aluminate can be selected from aluminic acid three isopropyl ester, aluminic acid three benzyl ester；Ethylene bis-fatty acid amides can be that ethylene is double
At least one in the double oleamide of stearic amide, ethylene, the double palmitamide of ethylene and ethylene dilaurate amide.
According to the disclosure, nano silver material can be any form containing nano silver particles, and such as, nano silver material can
Think and comprise only nano silver particles, it is also possible on the carrier particles, kind and the content present invention of carrier granular are not spy in dispersion
Other requirement, if meet nano silver particles be evenly distributed in nano silver material and content suitably.In order to improve nanometer
Silver particles and the compatibility of resin matrix, under preferable case, can select the knot with acrylonitrile-butadiene-styrene copolymer
The polymer that structure unit is identical or structure is close is as the carrier granular of nano silver particles, and such as, nano silver material can contain
Nano silver particles and polystyrene.
In nano silver material, polystyrene can in very large range change, preferably with the relative amount of nano silver particles
In the case of, the weight ratio of described nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, by these public affairs
Nano silver particles content in the antimicrobial composite material that the preparation method opened prepares is suitable, and nano silver particles and propylene
The compatibility of nitrile-BS resin matrix is good, is conducive to improving the antibacterial effect of composite.
In nano silver material, the carrier granular such as nano silver particles and polystyrene may be constructed nano-particle, this nanometer
The size of grain can in very large range change, wherein, in order to improve antibacterial effect and the compatibility of nano silver particles, preferably
Ground, in nano silver material, the particle diameter of nano-particle can be 10-80nm.
According to the disclosure, nano silver material can be disperseed to obtain by the material containing nano silver particles, it is also possible to by chemistry
Reaction obtains.In preferably a kind of embodiment of the disclosure, nano silver material can contain polystyrene and nanometer silver granuel
Son, can be carried out redox reaction by kayexalate and silver nitrate solution and obtain described molten containing nano silver material
Liquid, shown in its chemical equation such as following formula (1),
Reaction condition can in very large range change, and such as, reaction temperature can be 20-100 DEG C, and the response time is permissible
For 5-60min, it is preferable that reaction temperature can be 50-90 DEG C, the response time can be 10-40min.Above-mentioned containing nanometer silver
The solution of material can be aqueous solution or the solution of other suitable solvent formation.In this one preferred embodiment, oxidation
The nano silver particles that reduction reaction obtains with uniform adsorption on granules of polystyrene, thus can improve dividing of nano silver particles
Dissipate uniformity, simultaneously by with granules of polystyrene absorption can improve further nano silver particles and copolymer resin matrix and
The compatibility of bamboo fibre.
According to the disclosure, the length of chopped bamboo fibre can also in very large range change, as long as meeting chopped bamboo fibre
Play potentiation, and can be uniformly dispersed in described composite.Under preferable case, the length of chopped bamboo fibre can
Think 2-5mm.In above-mentioned preferred length range, chopped bamboo fibre and acrylonitrile-butadiene-styrene copolymer resin base
The compatibility of body is good, and obvious to the potentiation of composite.
According to the disclosure, in order to improve the chemical modifier modification to acrylonitrile-butadiene-styrene copolymer further
Effect, improves the compatibility of copolymer resin matrix and chopped bamboo fibre, and under preferable case, the method includes: make acrylic nitrile-butadiene
Carry out with described nanometer silver-chopped bamboo fibre composite fibre again after diene-styrene copolymer and chemical modifier mix homogeneously
Melt extrude pelletize, obtain described antimicrobial composite material.
It is highly preferred that in order to improve the comprehensive of the composite prepared by antimicrobial composite material preparation method further
Can, antimicrobial composite material preparation method may include that and makes in heat stabilizer, processing aid, ultraviolet absorber and antioxidant extremely
Few a kind of and described acrylonitrile-butadiene-styrene copolymer and chemical modifier mix after again with described nanometer silver-chopped bamboo
Fiber composite fiber carries out melt extruding pelletize, obtains described antimicrobial composite material；
Wherein, the concrete kind of antioxidant, heat stabilizer, ultraviolet absorber and processing aid can be people in the art
Conventional kind known to Yuan, such as, antioxidant can be selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive 18
At least one in the double octadecyl of carbon alcohol ester, 2-(1,1-dimethyl ethyl)-6-methyl-phenol, thio-2 acid；Thermally-stabilised
Agent can be at least one in maleic acid tin octylate or carboxylic acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Uv absorption
Agent can be selected from 2,4 dihydroxyl benzophenone, ESCALOL 567,2-hydroxyl-4-n-octyloxy hexichol
Ketone, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis
(4-t-octyl phenol epoxide) nickel, (1,2,2,6,6-pempidine base) phosphite ester, 4-benzoyloxy-2,2,6,6-tetramethyl
At least one in piperidines；Processing aid can be selected from calcium stearate, modified ethylene bis stearamide, Tissuemat E, ethylene
At least one in double stearic amides.
In the another embodiment of the disclosure, in order to improve the compatibility of bamboo fibre and copolymer resin matrix, anti-
Bacterium composite material and preparation method thereof may include that and makes described nanometer silver-bamboo fibre composite fibre after chopped and the painting of coupling agent surface
After covering process, with compatilizer and/or dispersant, obtain the nanometer silver-bamboo fibre composite fibre of surface modification；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 in branch maleic anhydride；Dispersant can be selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, dodecyl sulfur
At least one in acid sodium or fatty acid and macrogol ester.
As preferably a kind of embodiment of the disclosure, antimicrobial composite material preparation method includes: make described nanometer silver-bamboo
Fiber composite fiber, after chopped and after the process of coupling agent surface-coated, with compatilizer and dispersant, obtains surface modification
Nanometer silver-bamboo fibre composite fibre；
Further, heat stabilizer, processing aid, ultraviolet absorber and antioxidant and described acrylonitrile-butadiene-styrene (ABS) are made
Carry out melt extruding pelletize with described nanometer silver-chopped bamboo fibre composite fibre again after copolymer and chemical modifier mixing,
To described antimicrobial composite material；
The concrete kind of above-mentioned compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid is permissible
As hereinbefore；The amount ranges of compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid can be
Change in very wide range, it is preferable that relative to 100 parts by weight of acrylonitrile-BS, the consumption of compatilizer
Can be 0.5-5 weight portion, the consumption of antioxidant can be 0.2-2 weight portion, and the consumption of heat stabilizer can be 0.2-2 weight
Part, the consumption of dispersant can be 0.1-2 weight portion, and the consumption of ultraviolet absorber can be 0.2-2 weight portion, processing aid
Consumption can be 0.2-4 weight portion.In this one preferred embodiment, the method the antioxygen of the antimicrobial composite material prepared
The combination properties such as the property changed, weatherability and heat stability are all obviously improved.
According to the disclosure, in above-mentioned preparation process, the method melt extruding pelletize is well known to those skilled in the art, institute
Stating and melt extrude pelletize and can carry out on such as screw extruder at extrusion equipment, described screw extruder can be single screw rod
Extruder or double screw extruder, the present invention does not do special requirement.
Wherein, the reaction condition melt extruding pelletize can also be well known to those skilled in the art, can be according to matrix
Kind and the character of resin adjust accordingly.Under preferable case, in order to improve the melting mixing effect of each raw material components, melt extrude
The temperature of pelletize can be 210-250 DEG C.
The disclosure also provides for a kind of compositions for preparing antimicrobial composite material, and said composition includes acrylic nitrile-butadiene two
Alkene-styrol copolymer, chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein, relative to 100 weight portions
Acrylonitrile-butadiene-styrene copolymer, the content of described chopped bamboo fibre is 5-60 weight portion, described nano silver material
Content is 0.01-2 weight portion, and the content of described coupling agent is 0.1-10 weight portion, and the content of described chemical modifier is 0.1-
20 weight portions；Described coupling agent is silane coupling agent and/or titante coupling agent；Described chemical modifier is selected from aluminic acid
At least one in ester, ethylene bis-fatty acid amides and chromium picolinate.
Containing bamboo fibre and nano silver material in the compositions of the disclosure and antimicrobial composite material, there is the most antibacterial killing
Bacterium effect；Coupling agent and chemical modifier are combined, bamboo fibre surface and resin matrix are modified simultaneously, improve antibacterial
The mechanical property of composite.
According to the disclosure, in order to improve antibacterial effect and the power of the antimicrobial composite material prepared by described compositions further
Learn performance, under preferable case, relative to 100 parts by weight of acrylonitrile-BS, the content of chopped bamboo fibre
Can be 15-35 weight portion, the content of nano silver material can be 0.01-0.5 weight portion, and the content of coupling agent can be 0.5-
5 weight portions, the content of chemical modifier can be 0.5-10 weight portion.
According to the disclosure, described acrylonitrile-butadiene-styrene copolymer (ABS resin) is those skilled in the art institutes
Knowing, the relative amount of acrylonitrile unit therein unit, butadiene structural units and styrol structural unit is not important to
Ask, can be the conventional selection of field of compound material, such as, 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).Aforesaid propylene nitrile-
BS can be commercial products, can be such as purchased from NEC chemistry ABS resin GR-4000,
ABS Magnum800 purchased from Si Tailong company of the U.S., the ABS resin Terluran KR2883 purchased from BASF Aktiengesellschaft,
KR2885,828P or 846L etc..
According in the described compositions of the disclosure, coupling agent may be used for carrying out chopped bamboo fibre surface modification, institute
Stating chemical modifier to may be used for being modified resin matrix, the two is with the use of being used for improving acrylonitrile-butadiene-benzene second
Alkene copolymer and the interface compatibility of chopped bamboo fibre, thus improve the interface bond strength of the two.Containing at above-mentioned composition
In weight range, in order to improve acrylonitrile-butadiene-styrene copolymer and the interface binding power of chopped bamboo fibre further, even
The amount ratio of connection 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, VTES, ethylene
Base trimethoxy silane, double-(the silica-based propyl group of γ-triethoxy) tetrasulfide, γ-methacryloxypropyl trimethoxy
One or more in silane, triphenyl silicol, wherein, in order to make fiberglass surfacing that silane coupler processed with
Active force between cyclic olefin polymer interface is higher, under preferable case, selects the coupling agent containing olefin group, such as ethylene
Ethyl triethoxy silicane alkane, vinyltrimethoxy silane or γ-methacryloxypropyl trimethoxy silane；Titanate ester
Coupling agent can be selected from isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy)
Titanate esters, isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters
The chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine and double (two octyloxy pyrophosphoric acid ester groups) second
At least one in support titanate esters.
Aluminate can be selected from aluminic acid three isopropyl ester, aluminic acid three benzyl ester；Ethylene bis-fatty acid amides can be that ethylene is double
At least one in the double oleamide of stearic amide, ethylene, the double palmitamide of ethylene and ethylene dilaurate amide.
According to the disclosure, nano silver material can be any form containing nano silver particles, and such as, nano silver material can
Think and comprise only nano silver particles, it is also possible on the carrier particles, kind and the content present invention of carrier granular are not spy in dispersion
Other requirement, if meet nano silver particles be evenly distributed in nano silver material and content suitably.In order to improve nanometer
Silver particles and the compatibility of resin matrix, under preferable case, can select the knot with acrylonitrile-butadiene-styrene copolymer
The polymer that structure unit is identical or structure is close is as the carrier granular of nano silver particles, such as, can contain in nano silver material
There are nano silver particles and polystyrene.
In nano silver material, polystyrene can in very large range change, preferably with the relative amount of nano silver particles
In the case of, the weight ratio of described nano silver particles and polystyrene can be 1:(1-20), in above-mentioned content range, by described
Nano silver particles content in antimicrobial composite material prepared by compositions is suitable, and nano silver particles and acrylonitrile-butadiene-benzene
The compatibility of ethylene copolymer resin matrix is good, is conducive to improving the antibacterial effect of composite.
In nano silver material, the carrier granular such as nano silver particles and polystyrene may be constructed nano-particle, this nanometer
The size of grain can in very large range change, wherein, in order to improve antibacterial effect and the compatibility of nano silver particles, preferably
Ground, in nano silver material, the particle diameter of nano-particle can be 10-80nm.
According to the disclosure, the length of nanometer silver-chopped bamboo fibre composite fibre can also in very large range change, as long as
Meet chopped bamboo fibre and play potentiation, and can be uniformly dispersed in described composite.Under preferable case, nanometer
The length of silver-chopped bamboo fibre composite fibre can be 2-5mm.In above-mentioned preferred length range, nanometer silver-chopped bamboo is fine
Dimension composite fibre is good with the compatibility of acrylonitrile-butadiene-styrene copolymer resin matrix, and the enhancing to composite is made
With substantially.
According to the disclosure, in order to improve the performance of described antimicrobial composite material, under preferable case, above-mentioned composition further
At least one in compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid can also be included.
The concrete kind of above-mentioned compatilizer, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid is permissible
The conventional kind being well known to those skilled in the art, such as, compatilizer can be selected from Research of Grafting Malaic Anhydride Onto Polyethylene, benzene second
At least one in 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) propanoic acid positive octadecanol ester, 2-(1,1-dimethyl ethyl)-6-methyl-phenol,
At least one in the double octadecyl of thio-2 acid；Heat stabilizer can be selected from maleic acid tin octylate or carboxylic acid stannum, methyl
At least one in tin mercaptides and sulfydryl ester group stannum；Dispersant can be selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, ten
At least one in sodium dialkyl sulfate or fatty acid and macrogol ester；Ultraviolet absorber can be selected from 2,4-dihydroxy two
Benzophenone, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl-3 ', 5 '-two
Tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel, (1,2,
2,6,6-pempidine base) phosphite ester, at least one in 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Processing helps
Agent can be at least in calcium stearate, modified ethylene bis stearamide, Tissuemat E, ethylene bis stearic acid amide
Kind.
As preferably a kind of embodiment of the disclosure, described compositions also include compatilizer, antioxidant, heat stabilizer,
Dispersant, ultraviolet absorber and processing aid；Preferably, the content of above-mentioned auxiliary agent can be: relative to 100 parts by weight propylene
Nitrile-BS, the content of compatilizer can be 0.5-5 weight portion, and the content of antioxidant can be 0.2-2
Weight portion, the content of heat stabilizer can be 0.2-2 weight portion, and the content of dispersant can be 0.1-2 weight portion, uv absorption
The content of agent can be 0.2-2 weight portion, and the content of processing aid can be 0.2-4 weight portion.Above-mentioned preferred auxiliary agent and containing
Weight range can improve the combination properties such as the non-oxidizability of described antimicrobial composite material, weatherability and heat stability.
Further illustrate the disclosure by the following examples, but the disclosure is the most any way limited.At this
In disclosed following embodiment, acrylonitrile-butadiene-styrene copolymer is the ABS resin purchased from BASF Aktiengesellschaft
Terluran KR2883, bamboo fibre is purchased from Ningbo Qi Zhu company；Other chemical reagent are general commercial products；Melted crowded
Go out in the connection company's T L-55-55-500 type double screw extruder of upper tableland and prepare.
Embodiment 1
The present embodiment is for illustrating the compositions for preparing antimicrobial composite material of the disclosure.
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 15 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.01 weight portion nano silver material, the grain of nano-particle
Footpath is 20nm), 0.1 weight portion Silane coupling agent KH550,15 weight portion chemical modifier Aluminates.
Embodiment 2
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 60 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:20 to 2 weight portion nano silver materials, the particle diameter of nano-particle
For 80nm), 10 weight portion coupling agent isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, 0.1 weight portion chemical modifier
Ethylene bis-fatty acid amides.
Embodiment 3
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 5 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:1 to 0.02 weight portion nano silver material, the grain of nano-particle
Footpath is 30nm), 0.1 weight portion Silane coupling agent KH550,0.2 weight portion chemical modifier chromium picolinate.
Embodiment 4
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 15 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.05 weight portion nano silver material, the grain of nano-particle
Footpath is 20nm), 0.5 weight portion Silane coupling agent KH550,10 weight portion chemical modifier Aluminates.
Embodiment 5
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 35 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.4 weight portion nano silver material, the particle diameter of nano-particle
For 20nm), 5 weight portion Silane coupling agent KH550s, 0.5 weight portion chemical modifier Aluminate.
Embodiment 6
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 15 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.01 weight portion nano silver material, the grain of nano-particle
Footpath is 20nm), 0.1 weight portion Silane coupling agent KH550,0.1 weight portion chemical modifier Aluminate.
Embodiment 7
The compositions of the present embodiment contains: 100 parts by weight of acrylonitrile-BS, 30 weight portions are short
Cut bamboo fibre, (weight ratio of nano silver particles and polystyrene is 1:3 to 0.2 weight portion nano silver material, the particle diameter of nano-particle
For 20nm), 1 weight portion Silane coupling agent KH550,1 weight portion chemical modifier Aluminate, 1 parts by weight of compatible agent styrene connects
Branch maleic anhydride, 0.5 weight portion antioxidant β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 0.5 weight
Part heat stabilizer maleic acid tin octylate, 0.5 parts per weight dispersing agent macrogol ester, 0.5 weight portion ultraviolet absorber 2,4-dihydroxy
Base benzophenone and 0.5 weight portion processing aid calcium stearate.
Comparative example 1
This comparative example is for illustrating the compositions for prepare antimicrobial composite material different from the disclosure.
Said composition contains the composition of embodiment 1 compositions, except that, by weight such as nano silver material replace with
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 2
This comparative example is for illustrating the compositions for prepare antimicrobial composite material different from the disclosure.
Said composition contains the composition of embodiment 1 compositions, except that, by weight such as chopped bamboo fibre replace with
Acrylonitrile-butadiene-styrene copolymer.
Comparative example 3
This comparative example is for illustrating the compositions for prepare antimicrobial composite material different from the disclosure.
Containing the composition of embodiment 1 compositions in said composition, except that, coupling agent KH550 is replaced with and waits heavily
The chemical modifier Aluminate of amount.
Comparative example 4
This comparative example is for illustrating the compositions for prepare antimicrobial composite material different from the disclosure.
Said composition contains the composition of embodiment 1 compositions, except that, chemical modifier Aluminate is replaced with
Coupling agent KH550 etc. weight.
Preparation embodiment 1
The present embodiment is for illustrating the preparation method of the antimicrobial composite material of the disclosure, the antimicrobial composite material of the present embodiment
In the consumption of each raw material identical with the compositions of embodiment 1, comprise the steps:
(1) kayexalate joining mixing and stirring in silver nitrate solution, in microwave oven, 500w heats
30min, centrifugation, obtain the aqueous solution containing nano silver material after dried, bamboo fibre is immersed in concentration 1g/L
Containing the aqueous solution of nano silver material, two leachings two are rolled, and heated by microwave fast dewatering, are dried, and obtain nanometer silver-bamboo fibre and are combined
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre (1) obtained is carried out with Silane coupling agent KH550 after chopped
Nanometer silver-chopped bamboo fibre the composite fibre (a length of 2-5mm) of surface modification is obtained after surface-coated；
(3) put into ABS resin and chemical modifier in heated at high speed mixer (2000 turns/min of speed of agitator)
Add in double screw extruder (temperature 230 DEG C) after row mixing dispersion, then by compound for the nanometer silver in (2)-chopped bamboo fibre fibre
Tie up and add from the side spout of extruder, carry out melt pelletization, by obtaining this reality after outlet mold sizing, water-cooled, air-dried, pelletizing
Execute the antimicrobial composite material of example.
Preparation embodiment 2
The method using preparation embodiment 1, except that, the consumption of each raw material in the antimicrobial composite material of the present embodiment
Identical with the compositions of embodiment 2.
Preparation embodiment 3
The method using preparation embodiment 1, except that, the consumption of each raw material in the antimicrobial composite material of the present embodiment
Identical with the compositions of embodiment 3.
Preparation embodiment 4
The method using preparation embodiment 1, except that, the consumption of each raw material in the antimicrobial composite material of the present embodiment
Identical with the compositions of embodiment 4.
Preparation embodiment 5
The method using preparation embodiment 1, except that, the consumption of each raw material in the antimicrobial composite material of the present embodiment
Identical with the compositions of embodiment 5.
Preparation embodiment 6
The method using preparation embodiment 1, except that, the consumption of each raw material in the antimicrobial composite material of the present embodiment
Identical with the compositions of embodiment 6.
Preparation embodiment 7
In the antimicrobial composite material of the present embodiment, the consumption of each raw material is identical with the compositions of embodiment 7, preparation method bag
Include following steps:
(1) kayexalate joining mixing and stirring in silver nitrate solution, in microwave oven, 500w heats
30min, centrifugation, obtain the aqueous solution containing nano silver material after dried, bamboo fibre is immersed in concentration 1g/L
Containing the aqueous solution of nano silver material, two leachings two are rolled, and heated by microwave fast dewatering, are dried, and obtain nanometer silver-bamboo fibre and are combined
Fiber；
(2) the drying nano silver-bamboo fibre composite fibre (1) obtained is carried out with Silane coupling agent KH550 after chopped
React through heated at high speed mixer (2000 turns/min of speed of agitator), in compatilizer with compatilizer, dispersant after surface-coated
There is esterification in the hydroxyl (-OH) in maleic anhydride and bamboo fibre, the carboxyl (-COOH) that course of reaction generates again with natural fibre
There is follow-up esterification in the hydroxyl (-OH) in dimension, the nanometer silver-chopped bamboo fibre composite fibre obtaining surface modification is (long
Degree is 2-5mm)；
(3) ABS resin, chemical modifier, heat stabilizer, processing aid, ultraviolet absorber and antioxidant are put into height
Speed adds to carry out in Hot mixer mixing disperses (2000 turns/min of speed of agitator) to add (temperature 230 in double screw extruder afterwards
DEG C), then the nanometer silver in (2)-chopped bamboo fibre composite fibre is added from the side spout of extruder, carry out melt pelletization,
Again by obtaining the antimicrobial composite material of the present embodiment after outlet mold sizing, water-cooled, air-dried, pelletizing.
Preparation comparative example 1-4
Use preparation embodiment 1 method, except that, in antimicrobial composite material the consumption of each raw material respectively with contrast
The compositions of example 1-4 is identical.
Preparation comparative example 5
In the antimicrobial composite material of the present embodiment, the consumption of each raw material is identical with the compositions of embodiment 1, including walking as follows
Rapid:
Compositions in embodiment 1 is put in heated at high speed mixer carry out mixing dispersion (speed of agitator 2000 turns/
Min) add (temperature 230 DEG C) in double screw extruder afterwards and carry out melt pelletization, then by outlet mold sizing, water-cooled, air-dry, cut
The antimicrobial composite material of the present embodiment is obtained after Li.
Testing example 1
The antimicrobial composite material obtained in preparation embodiment 1-7 and preparation comparative example 1-5 is made batten on injection machine,
Carry out following performance test the most respectively:
Hot strength is tested according to ASTM D638 standard, batten a size of 170*13*3.22mm, draw speed
50mm/min, bending strength and bending modulus are tested according to ASTM D790 standard, batten a size of 127*12.7*
3.22mm, span 56mm, rate of bending is 2mm/min, and notch impact strength is tested according to ASTMD256 standard, batten chi
Very little for 63.5*12.7*3.22mm, notch depth is 1/3rd of sample thickness, and test result is listed in table 1
According to light industry of China industry standard QB/T 2591-2003, " antibiotic plastic anti-microbial property is commented in the test of antibiotic rate
Valency and method of testing thereof " it is tested by standard.The strain that experiment uses: staphylococcus aureus, escherichia coli, black fermented preparation
Mould, aspergillus terreus, test result is listed in table 2.
Table 1
| Hot strength (MPa) | Bending strength (MPa) | Notch impact strength (J/m) | |
| Preparation embodiment 1 | 40.8 | 62.7 | 113.8 |
| Preparation embodiment 2 | 31.8 | 53.3 | 68.0 |
| Preparation embodiment 3 | 39.6 | 61.4 | 109.7 |
| Preparation embodiment 4 | 42.3 | 63.8 | 103.6 |
| Preparation embodiment 5 | 47.2 | 68.4 | 105.3 |
| Preparation embodiment 6 | 48.5 | 69.7 | 87.4 |
| Preparation embodiment 7 | 47.8 | 70.8 | 95.5 |
| Preparation comparative example 1 | 40.5 | 62.8 | 112.8 |
| Preparation comparative example 2 | 35.8 | 52.3 | 120.9 |
| Preparation comparative example 3 | 38.3 | 60.9 | 108.7 |
| Preparation comparative example 4 | 37.9 | 59.6 | 106.7 |
| Preparation comparative example 5 | 29.4 | 45.9 | 86.4 |
Table 2
According to Tables 1 and 2 data, from preparation embodiment 1 with the Data Comparison preparing comparative example 1-2 it can be seen that relative
In comprising only the composite of 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；Data Comparison from preparation embodiment 1 with preparation comparative example 3-4 can
Going out, relative to comprising only the composite of chemical modifier or coupling agent, the antimicrobial composite material of the disclosure and preparation method will
Coupling agent and chemical modifier combination, be modified bamboo fibre surface and resin matrix simultaneously, improve antimicrobial composite material
Mechanical property；Prepare the Data Comparison of embodiment 1 and preparation comparative example 5 it can be seen that use the preparation method of the disclosure to obtain
To antimicrobial composite material keeping while mechanical property is basically unchanged, improve antibacterial effect and mechanical property.
From preparation embodiment 1-3 with preparation embodiment 4-5 Data Comparison it can be seen that the disclosure preferably relative to
100 parts by weight of acrylonitrile-BS, the consumption of described chopped bamboo fibre is 15-35 weight portion, described in receive
The consumption of rice ag material is 0.01-0.5 weight portion, and the consumption of described coupling agent is 0.5-5 weight portion, described chemical modifier
In the case of consumption is 0.5-10 weight portion, the antibacterial effect of the antimicrobial composite material that the preparation method of the disclosure obtains and mechanics
Performance is more preferable；From the Data Comparison of preparation embodiment 1 and preparation embodiment 6 it can be seen that at the preferred coupling agent of the disclosure and
The amount ratio of chemical modifier is 1:(0.5-2.5) in the case of, the mechanical property of the antimicrobial composite material of the disclosure is more preferable；From
Prepare the embodiment 1 Data Comparison with preparation embodiment 7 it can be seen that also include compatible in the preferred described compositions of the disclosure
Agent, antioxidant, heat stabilizer, dispersant, ultraviolet absorber and processing aid, relative to 100 parts by weight of acrylonitrile-butadiene-
Styrol copolymer, the content of described compatilizer is 0.5-5 weight portion, and the content of described antioxidant is 0.2-2 weight portion, described
The content of heat stabilizer is 0.2-2 weight portion, and the content of described dispersant is 0.1-2 weight portion, containing of described ultraviolet absorber
Amount is 0.2-2 weight portion, in the case of the content of described processing aid is 0.2-4 weight portion, the antimicrobial composite material of the disclosure
Mechanical property more preferable
The preferred implementation of the disclosure described in detail above, but, the disclosure is not limited in above-mentioned embodiment
Detail, in the technology concept of the disclosure, multiple simple variant can be carried out with technical scheme of this disclosure, this
A little simple variant belong to the protection domain of the disclosure.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the disclosure to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the disclosure, as long as it is without prejudice to this
Disclosed thought, it should be considered as the content that the disclosure is provided equally.
Claims (19)
1. the method preparing antimicrobial composite material, it is characterised in that the method comprises the steps:
(1) use the solution containing nano silver material that bamboo filament is padded process, obtain nanometer silver-bamboo fibre and be combined
Fiber；
(2) make described nanometer silver-bamboo fibre composite fibre after chopped, contact with coupling agent and carry out surface-coated process, obtain
The nanometer silver of surface modification-chopped bamboo fibre composite fibre；
(3) acrylonitrile-butadiene-styrene copolymer, chemical modifier and described nanometer silver-chopped bamboo fibre composite fibre are made
Carry out melt extruding pelletize, obtain described antimicrobial composite material.
Method the most according to claim 1, it is characterised in that relative to 100 parts by weight of acrylonitrile-butadiene-styrene
Copolymer, the consumption of described chopped bamboo fibre is 5-60 weight portion, and the consumption of described nano silver material is 0.01-2 weight portion, institute
The consumption stating coupling agent is 0.1-10 weight portion, and the consumption of described chemical modifier is 0.1-20 weight portion；Described coupling agent is
Silane coupling agent and/or titante coupling agent；Described chemical modifier be selected from Aluminate, ethylene bis-fatty acid amides and
At least one in chromium picolinate.
Method the most according to claim 2, it is characterised in that relative to 100 parts by weight of acrylonitrile-butadiene-styrene
Copolymer, the consumption of described chopped bamboo fibre is 15-35 weight portion, and the consumption of described nano silver material is 0.01-0.5 weight
Part, the consumption of described coupling agent is 0.5-5 weight portion, and the consumption of described chemical modifier is 0.5-10 weight portion.
Method the most according to claim 1, it is characterised in that the amount ratio of described coupling agent and described chemical modifier is
1:(0.5-2.5).
Method the most according to claim 1, it is characterised in that described nano silver material contains nano silver particles and polyphenyl second
Alkene, the weight ratio of described nano silver particles and polystyrene is 1:(1-20), the particle diameter of nano-particle in described nano silver material
For 10-80nm.
Preparation method the most according to claim 1, it is characterised in that described nanometer silver-chopped bamboo fibre composite fibre
A length of 2-5mm.
Preparation method the most according to claim 1, it is characterised in that the method includes: make acrylonitrile-butadiene-benzene second
Carry out melt extruding making with described nanometer silver-chopped bamboo fibre composite fibre again after alkene copolymer and chemical modifier mix homogeneously
Grain, obtains described antimicrobial composite material.
Preparation method the most according to claim 7, it is characterised in that the method includes: make heat stabilizer, processing aid,
At least one in ultraviolet absorber and antioxidant is mixed with described acrylonitrile-butadiene-styrene copolymer and chemical modifier
Carry out melt extruding pelletize with described nanometer silver-chopped bamboo fibre composite fibre again after conjunction, obtain described antimicrobial composite material；
Described antioxidant is selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2-(1,1-dimethyl
Ethyl)-6-methyl-phenol, at least one in the double octadecyl of thio-2 acid；Described heat stabilizer is misery selected from Malaysia
At least one in Ji Xi or carboxylic acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Described ultraviolet absorber is selected from 2,4-dihydroxy
Base benzophenone, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl-3 ',
5 '-two tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel,
At least one in (1,2,2,6,6-pempidine base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Institute
State processing aid be in calcium stearate, modified ethylene bis stearamide, Tissuemat E and ethylene bis stearic acid amide extremely
Few one.
Preparation method the most according to claim 1, it is characterised in that the method includes: make described nanometer silver-bamboo fibre multiple
Condensating fiber, after chopped and after the process of coupling agent surface-coated, with compatilizer and/or dispersant, obtains receiving of surface modification
Meter Yin-bamboo fibre composite fibre；
Described compatilizer is selected from Research of Grafting Malaic Anhydride Onto Polyethylene, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride
With at least one in ABS grafted maleic anhydride；Described dispersant be selected from two polyphosphate sodiums, triethyl group hexyl sodium phosphate, ten
At least one in sodium dialkyl sulfate or fatty acid and macrogol ester.
Preparation method the most according to claim 9, it is characterised in that the method includes: make described nanometer silver-bamboo fibre
Composite fibre, after chopped and after the process of coupling agent surface-coated, with compatilizer and dispersant, obtains receiving of surface modification
Meter Yin-bamboo fibre composite fibre；
Make heat stabilizer, processing aid, ultraviolet absorber and antioxidant and described acrylonitrile-butadiene-styrene copolymer and
Carry out melt extruding pelletize with described nanometer silver-chopped bamboo fibre composite fibre again after chemical modifier mixing, obtain described anti-
Bacterium composite；
Described antioxidant is selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2-(1,1-dimethyl
Ethyl)-6-methyl-phenol, at least one in the double octadecyl of thio-2 acid；Described heat stabilizer is misery selected from Malaysia
At least one in Ji Xi or carboxylic acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Described ultraviolet absorber is selected from 2,4-dihydroxy
Base benzophenone, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl-3 ',
5 '-two tertiary phenyl)-5-chlorination benzotriazole, single benzoic acid resorcinol, 2,2 '-thiobis (4-t-octyl phenol epoxide) nickel,
At least one in (1,2,2,6,6-pempidine base) phosphite ester, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine；Institute
State processing aid be in calcium stearate, modified ethylene bis stearamide, Tissuemat E and ethylene bis stearic acid amide extremely
Few one；
Wherein, relative to 100 parts by weight of acrylonitrile-BS, the consumption of described compatilizer is 0.5-5 weight
Amount part, the consumption of described antioxidant is 0.2-2 weight portion, and the consumption of described heat stabilizer is 0.2-2 weight portion, described dispersant
Consumption be 0.1-2 weight portion, the consumption of described ultraviolet absorber is 0.2-2 weight portion, and the consumption of described processing aid is
0.2-4 weight portion.
11. according to the preparation method described in any one in claim 1-10, it is characterised in that described in melt extrude pelletize
Temperature is 210-250 DEG C.
12. according to the preparation method described in any one in claim 1-10, it is characterised in that the method includes: make polyphenyl
Vinyl sulfonic acid sodium and silver nitrate solution carry out redox reaction and obtain the described solution containing nano silver material.
13. 1 kinds for preparing the compositionss of antimicrobial composite material, it is characterised in that said composition include acrylonitrile-butadiene-
Styrol copolymer, chopped bamboo fibre, nano silver material, coupling agent and chemical modifier, wherein, relative to 100 weight portions third
Alkene nitrile-BS, the content of described chopped bamboo fibre is 5-60 weight portion, containing of described nano silver material
Amount is 0.01-2 weight portion, and the content of described coupling agent is 0.1-10 weight portion, and the content of described chemical modifier is 0.1-20
Weight portion；Described coupling agent is silane coupling agent and/or titante coupling agent；Described chemical modifier is selected from aluminic acid
At least one in ester, ethylene bis-fatty acid amides and chromium picolinate.
14. compositionss according to claim 13, it is characterised in that relative to 100 parts by weight of acrylonitrile-butadiene-benzene
Ethylene copolymer, the content of described chopped bamboo fibre is 15-35 weight portion, and the content of described nano silver material is 0.01-0.5 weight
Amount part, the content of described coupling agent is 0.5-5 weight portion, and the content of described chemical modifier is 0.5-10 weight portion.
15. compositionss according to claim 13, it is characterised in that described coupling agent and the content of described chemical modifier
Ratio is 1:(0.5-2.5).
16. compositionss according to claim 13, it is characterised in that described nano silver material contains nano silver particles and gathers
Styrene, the weight ratio of described nano silver particles and polystyrene is 1:(1-20), nano-particle in described nano silver material
Particle diameter is 10-80nm.
17. compositionss according to claim 13, it is characterised in that a length of 2-5mm of described chopped bamboo fibre.
18. compositionss according to claim 13, it is characterised in that described compositions also includes compatilizer, antioxidant, heat
At least one in stabilizer, dispersant, ultraviolet absorber and processing aid；Described compatilizer is selected from polycthylene grafted Malaysia
At least one in anhydride, styrene-grafted maleic anhydride, polypropylene grafted maleic anhydride and ABS grafted maleic anhydride；Described
Antioxidant is selected from β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, 2-(1,1-dimethyl ethyl)-6-
At least one in the double octadecyl of methyl-phenol, thio-2 acid；Described heat stabilizer is selected from maleic acid tin octylate or carboxylic
At least one in acid stannum, Methyl stannum mercaptide and sulfydryl ester group stannum；Described dispersant is selected from two polyphosphate sodiums, triethyl group hexyl
At least one in sodium phosphate, sodium lauryl sulphate or fatty acid and macrogol ester；Described ultraviolet absorber is selected from 2,
4-dihydroxy benaophenonel, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl
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
A kind of；Described processing aid is selected from calcium stearate, modified ethylene bis stearamide, Tissuemat E, ethylene bis stearic acid amide
In at least one.
19. compositionss according to claim 18, it is characterised in that described compositions also includes compatilizer, antioxidant, heat
Stabilizer, dispersant, ultraviolet absorber and processing aid, relative to 100 parts by weight of acrylonitrile-BS,
The content of described compatilizer is 0.5-5 weight portion, and the content of described antioxidant is 0.2-2 weight portion, containing of described heat stabilizer
Amount is 0.2-2 weight portion, and the content of described dispersant is 0.1-2 weight portion, and the content of described ultraviolet absorber is 0.2-2 weight
Part, the content of described processing aid is 0.2-4 weight portion.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109778373A (en) * | 2018-12-13 | 2019-05-21 | 北京方诣生物医药有限公司 | A kind of bacteriostasis, and deodorization blend fibre and preparation method thereof and textile |
| 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 |
| CN113388945A (en) * | 2021-05-26 | 2021-09-14 | 江西绣丽织带有限公司 | Elastic velvet ribbon with double-sided velvet and preparation method thereof |
| CN114015237A (en) * | 2021-10-29 | 2022-02-08 | 厦门赋源高科技有限公司 | Antibacterial composite material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914298A (en) * | 2010-08-05 | 2010-12-15 | 宁波竹源新材料科技有限公司 | Method for preparing bamboo fiber composite plastic particles and application of product thereof |
| CN102219981A (en) * | 2011-06-13 | 2011-10-19 | 刘立文 | Modified acrylonitrile-butadiene-styrene copolymer and preparation method of modified acrylonitrile-butadiene-styrene copolymer |
| CN102952337A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Modified bamboo fiber reinforced polypropylene composite material and preparation method thereof |
| CN103992613A (en) * | 2014-05-22 | 2014-08-20 | 安徽嘉木橡塑工业有限公司 | Bamboo fiber reinforced ABS (acrylonitrile butadiene styrene) resin composite material |
-
2016
- 2016-08-11 CN CN201610656430.8A patent/CN106280218B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914298A (en) * | 2010-08-05 | 2010-12-15 | 宁波竹源新材料科技有限公司 | Method for preparing bamboo fiber composite plastic particles and application of product thereof |
| CN102219981A (en) * | 2011-06-13 | 2011-10-19 | 刘立文 | Modified acrylonitrile-butadiene-styrene copolymer and preparation method of modified acrylonitrile-butadiene-styrene copolymer |
| CN102952337A (en) * | 2012-11-15 | 2013-03-06 | 合肥会通新材料有限公司 | Modified bamboo fiber reinforced polypropylene composite material and preparation method thereof |
| CN103992613A (en) * | 2014-05-22 | 2014-08-20 | 安徽嘉木橡塑工业有限公司 | Bamboo fiber reinforced ABS (acrylonitrile butadiene styrene) resin composite material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109778373A (en) * | 2018-12-13 | 2019-05-21 | 北京方诣生物医药有限公司 | A kind of bacteriostasis, and deodorization blend fibre and preparation method thereof and textile |
| 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 |
| CN114630862A (en) * | 2020-10-14 | 2022-06-14 | 株式会社Lg化学 | Thermoplastic resin composition, method for preparing the same, and molded article comprising the same |
| 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 |
| CN113388945A (en) * | 2021-05-26 | 2021-09-14 | 江西绣丽织带有限公司 | Elastic velvet ribbon with double-sided velvet and preparation method thereof |
| CN114015237A (en) * | 2021-10-29 | 2022-02-08 | 厦门赋源高科技有限公司 | Antibacterial composite material 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 |
| CN114213804A (en) * | 2021-12-29 | 2022-03-22 | 重庆普利特新材料有限公司 | High-toughness antibacterial reinforced ABS 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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