CN110093004A - A kind of nano-antibacterial ABS plastic and preparation method thereof - Google Patents
A kind of nano-antibacterial ABS plastic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nano-antibacterial ABS plastic, are made of following raw material: 25-30 parts of modified ABS resins, 10-15 parts of complex antimicrobials, 10-20 parts of pentaerythrites, 5-10 parts of crosslinking agents, 15-20 parts of plasticizer, 25-30 parts of methylene chloride, 50-70 parts of dehydrated alcohols；The invention also discloses a kind of preparation methods of nano-antibacterial ABS plastic；Agglomeration is carried out by polyacrylate dispersion and polybutadiene latex first in modified ABS resin preparation process, form bulky grain, the poor problem of polybutadiene latex tackness can be improved, styrene and acrylonitrile grafting can be improved again in the probability on polybutadiene glue surface, modified ABS resin can assign the plastics good anti-microbial property, the complex antimicrobials of addition itself can either increase its anti-microbial property, synergy can occur with modified ABS resin again, the stability for increasing antibacterial process, further ensures antibacterial effect.
Description
Technical field
The present invention relates to a kind of plastics, specially a kind of nano-antibacterial ABS plastic and preparation method thereof.
Background technique
ABS resin is one of five big synthetic resin, impact resistance, heat resistance, lower temperature resistance, chemical resistance and electricity
Gas function admirable also has the characteristics that easy processing, product size are stable, lustrous surface is good, is easy coating, coloring, can be with
Carry out the secondary operation such as surface metallization, plating, welding, hot pressing and bonding, be widely used in machinery, automobile, electronic apparatus,
The industrial circles such as instrument and meter, weaving and building are a kind of thermoplastic engineering plastics that purposes is extremely wide.Acrylonitrile-butadiene-benzene
Ethylene copolymer is by acrylonitrile, and the terpolymer ABS that butadiene and styrene form is usually light yellow or milky
Pellet non-crystalline resin.ABS is using one of most extensive non-universal plastics.
Chinese invention patent CN106496924A discloses a kind of Antibacterial ABS plastic and preparation method thereof, by following weight
The raw material of score forms: 130-150 parts of ABS plastic master batch, 3-7 parts of algin, 2-5 parts of diisopropyl trithioether, perlite
0.5-2 parts, 0.1-0.5 parts of zinc picolinate, 0.2-1 parts of kaolin, 0.05-0.2 parts of antioxidant, the antioxidant is anti-
Oxygen agent 264, TBHQ or antioxidant 1076.The Antibacterial ABS plastic has stronger antibacterial action and excellent intensity, is a kind of peace
Complete effective Antibacterial ABS plastic；And Antibacterial ABS plastic preparation method of the invention is simple, and cost of material is low, has preferable
Promotional value.But the Antibacterial ABS plastic antibacterial effect and means of invention preparation are more single, and antibacterial process stability
It can not ensure, furthermore the toughness and impact strength of the antibiotic plastic are inadequate.
Summary of the invention
In order to overcome above-mentioned technical problem, the present invention provides a kind of nano-antibacterial ABS plastic and preparation method thereof.
Technical problem solved by the invention:
1, existing Antibacterial ABS plastic antibacterial effect and means are more single, and antibacterial process stability can not ensure,
Furthermore the toughness and impact strength of the antibiotic plastic are inadequate；
2, polybutadiene latex performance of technical process and stick together that performance is poor, by the ABS resin stability of its preparation compared with
Difference, the ABS stability and weatherability finally prepared are poor.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of nano-antibacterial ABS plastic, is made of following raw material: 25-30 parts of modified ABS resins, and 10-15 parts multiple
Close antibacterial agent, 10-20 parts of pentaerythrites, 5-10 parts of crosslinking agents, 15-20 parts of plasticizer, 25-30 parts of methylene chloride, 50-70 parts of nothings
Water-ethanol；
The nano-antibacterial ABS plastic is made by the following method:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, and complex antimicrobials and anhydrous are added
Ethyl alcohol crosslinking agent and plasticizer is added after magnetic agitation 1h, after being warming up to 75 DEG C, magnetic agitation 50min, ultrasonic vibration 15min
It is transferred in reaction kettle, reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, reacts 4h at this temperature, is mixed
Colloid；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, the nano-antibacterial ABS plastic is made.
Further, the modified ABS resin is made of following raw material: 10-15 parts of polybutadiene latexs, 5-10
Part polyacrylate dispersion, 20-28 parts of styrene-acrylonitrile copolymer, 50-75 parts of desalted waters, 1-3 parts of ammonium sulfate, 3-5 parts months
Cinnamic acid monoglyceride, 5-8 parts of carboxymethyl chitosans.
Further, the modified ABS resin is made by the following method:
(1) polybutadiene latex is added in beaker with polyacrylate dispersion and is mixed, with the revolving speed of 120r/min
Magnetic agitation 30min, is transferred in holding vessel, and 45 DEG C of heating water baths simultaneously stir 4h with the revolving speed of 150r/min, after agglomeration is made
Polybutadiene latex；
(2) polybutadiene latex after agglomeration is stood into 5h, added later with styrene-acrylonitrile copolymer and desalted water
Enter in three-necked flask, 60 DEG C of heating water baths, react 1h, ammonium sulfate is added, ultrasonic 15min is warming up to 75 DEG C, and lauric acid list is added
Glyceride is dispersed 5min with the revolving speed of 2000r/min, carboxymethyl chitosan is added with the revolving speed magnetic agitation 45min of 180r/min
Sugar, reacts 2h, and dehydration, drying are squeezed out, pelletizing by double screw extruder, modified ABS resin are made, control extruder barrel
Temperature is 220 DEG C.
Polybutadiene latex used in step (1) is that the component of toughness is provided for ABS resin, but its technique processability
It is poor and to stick together performance, it is unstable to will lead to system when mixing with styrene-acrylonitrile copolymer, passes through polyacrylate
Lotion carries out agglomeration with it, and polybutadiene latex particle collides under 120r/min magnetic agitation with polyacrylate particle
Flocculate is formed, the collision between particle is accelerated by 45 DEG C of heating water baths, raising mixing speed, later in the work of surface tension
Bulky grain is formed with lower generation connection, completes agglomeration, the bulky grain after agglomeration has the high resiliency and polyacrylic acid of polybutadiene
The excellent weather resistance of ester, and polyacrylate also assigns its good adhesive strength, improves polybutadiene latex and sticks together
The poor problem of performance；Polybutadiene latex after agglomeration is stood 5h by step (2), is to make polybutadiene latex further
Polymerization and crosslinking occurs, increases its gel content, polybutadiene glue after agglomeration is mixed with styrene-acrylonitrile copolymer
Styrene and acrylonitrile grafting be can be improved afterwards in the probability on polybutadiene glue surface, and the bulky grain formed after agglomeration is opposite
In polybutadiene latex, partial size increases, and styrene and acrylonitrile are effectively grafted area increase, point of the polybutadiene glue in system
Divergence improves, and then improves the impact strength of modified ABS resin finally prepared, be added carboxymethyl chitosan to ABS resin into
Row be modified, carboxymethyl chitosan surface contain great amount of hydroxy group, amino etc. can modification group, the group can be coupled after polybutadiene
Graft copolymerization occurs for alkene glue and styrene-acrylonitrile copolymer, and the modified ABS resin of micro- crosslinking, the carboxylic after grafting is made
Methyl chitosan can assign its good anti-microbial property.
Further, the complex antimicrobials are made of following raw material: 5-15 parts of silver nitrates, 0.5-1.0 parts of lemons
Lemon acid trisodium, 35-50 parts of deionized waters, 10% ammonium hydroxide of 0.3-0.5 part, 15-20 parts of nano titanic oxide sols, 25-40 parts of nothings
Water-ethanol, 10-20 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, 20-30 parts of methyl methacrylates.
Further, the complex antimicrobials are made by the following method:
(1) silver nitrate is added in deionized water, 40 DEG C of heating water baths, magnetic agitation 45min, trisodium citrate is added,
60 DEG C are warming up to, 30min is stirred, elargol is made；
(2) sodium sulfate of polyethenoxy ether of fatty alcohol is poured into the beaker equipped with dehydrated alcohol, metering system is then added
Sour methyl esters, magnetic agitation 10min, is added deionized water after mixing, and microemulsion is made, nanometer titanium dioxide is added in microemulsion
In titanium colloidal sol, modified nano-titanium dioxide colloidal sol is made in 60 DEG C of heating water bath 5h；
(3) elargol prepared in step (1) is added in modified nano-titanium dioxide colloidal sol, 10% ammonia of mass fraction is added
Water, 50 DEG C of heating water baths simultaneously stir 4h, are centrifuged 1min with the revolving speed of 12000r/min, filtering, with dehydrated alcohol by washing of precipitate
Three times, the complex antimicrobials are made.
Nano-titanium dioxide surface is in hydrophily, is not easy to disperse in organic system, passes through fatty alcohol polyoxy in step (2)
Ethylene ether sodium sulfate and methyl methacrylate prepare a kind of microemulsion, are carried out by microemulsion to nano titanic oxide sol
Modified, the hydroxyl of part carboxyl and nano-titanium dioxide surface in organic microemulsion reacts, and esterification condensation forms strength
Chemical bond so that nano-titanium dioxide is not easy to reunite, and then nano-titanium dioxide surface is no longer in hydrophily, in organic system
In easily disperse, improve its dispersibility, modified nanometer titanium dioxide-coated is in silver surface, Neng Goufang after mixing with elargol
Only there is the phenomenon reunited and stability is inadequate in silver particles, can enhance the stability of system, improve anti-microbial property.
Further, one or more of the crosslinking agent tetraisocyanate, methacrylic acid and trimethoxy silane.
Further, the plasticizer is dioctyl phthalate, dibutyl phthalate and phthalic acid two
One or more of different nonyl ester.
A kind of preparation method of nano-antibacterial ABS plastic, includes the following steps:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, and complex antimicrobials and anhydrous are added
Ethyl alcohol crosslinking agent and plasticizer is added after magnetic agitation 1h, after being warming up to 75 DEG C, magnetic agitation 50min, ultrasonic vibration 15min
It is transferred in reaction kettle, reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, reacts 4h at this temperature, is mixed
Colloid；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, the nano-antibacterial ABS plastic is made.
Beneficial effects of the present invention:
(1) during preparing a kind of nano-antibacterial ABS plastic, modified ABS resin resists the present invention with compound in step S1
Microbial inoculum is mixed under the action of crosslinking agent, and modified ABS resin is carboxymethyl chitosan grafted branch to by polyacrylate
The bulky grain ABS resin formed after agglomeration, complex antimicrobials are modified nanometer titanium dioxide-coateds in silver particles surface shape
At core-shell structure, after modified ABS resin is mixed with complex antimicrobials, the carboxymethyl chitosan meeting of grafting and complex antimicrobials
Synergistic effect is generated, complex antimicrobials can form albumen silver precipitating with sulfydryl, the carboxyl etc. in mycoprotein during antibacterial,
Albumen silver releases micro silver ion and generates fungistatic effect later, and the amino in carboxymethyl chitosan glycan molecule after grafting can
In conjunction with silver ion, it is stablized, ensures the stability of antibacterial, the carboxyl energy that complex antimicrobials generate during the preparation process
Esterification occurs for the hydroxyl on enough and carboxymethyl chitosan glycan molecule, and the carboxymethyl chitosan after capable of ensureing grafting resists with compound
The fastness that microbial inoculum combines further ensures the stability of Synergistic antimicrobial；
(2) present invention has prepared a kind of nano-antibacterial ABS plastic, by the way that one is modified and prepared to ABS resin
Kind of complex antimicrobials enhance its anti-microbial property, prepare during modified ABS resin first through polyacrylate dispersion and poly-
Butadiene latex carries out agglomeration, forms bulky grain, on the one hand improves the poor problem of polybutadiene latex tackness, on the other hand
Styrene and acrylonitrile grafting are improved in the probability on polybutadiene glue surface, be added later carboxymethyl chitosan to ABS resin into
Row be modified, by carboxymethyl chitosan surface contain great amount of hydroxy group, amino etc. can modification group and its graft copolymerization occurs,
And then assign its good anti-microbial property；Complex antimicrobials are that one is modified nanometer titanium dioxide-coateds in silver granuel sublist
The core-shell structure that face is formed, not easy to reunite and no longer hydrophilic modified nano-titanium dioxide are coated on silver surface, can prevent
There is the phenomenon reunited and stability is inadequate in silver particles, can enhance the stability of system, improve anti-microbial property；Modified ABS
Resin can assign the plastics good anti-microbial property, and be capable of providing stronger toughness and higher impact strength, addition
Complex antimicrobials itself can either increase its anti-microbial property, and synergy can occur with modified ABS resin, increase antibacterial mistake
The stability of journey further ensures the effect of antibacterial process.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, all other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
A kind of nano-antibacterial ABS plastic, is made of following raw material: 25 parts of modified ABS resins, 10 parts of composite antibacterial
Agent, 10 parts of pentaerythrites, 5 parts of tetraisocyanates, 15 parts of dioctyl phthalates, 25 parts of methylene chloride, 50 parts of dehydrated alcohols；
The nano-antibacterial ABS plastic is made by the following method:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, and complex antimicrobials and anhydrous are added
Tetraisocyanate and dioctyl phthalate are added after magnetic agitation 1h, is warming up to 75 DEG C, magnetic agitation 50min for ethyl alcohol, surpass
Acoustic shock is transferred in reaction kettle after swinging 15min, and reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, at this temperature instead
4h is answered, complex colloid is obtained；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, the nano-antibacterial ABS plastic is made.
The modified ABS resin is made by the following method:
(1) polybutadiene latex is added in beaker with polyacrylate dispersion and is mixed, with the revolving speed of 120r/min
Magnetic agitation 30min, is transferred in holding vessel, and 45 DEG C of heating water baths simultaneously stir 4h with the revolving speed of 150r/min, after agglomeration is made
Polybutadiene latex；
(2) polybutadiene latex after agglomeration is stood into 5h, added later with styrene-acrylonitrile copolymer and desalted water
Enter in three-necked flask, 60 DEG C of heating water baths, react 1h, ammonium sulfate is added, ultrasonic 15min is warming up to 75 DEG C, and lauric acid list is added
Glyceride is dispersed 5min with the revolving speed of 2000r/min, carboxymethyl chitosan is added with the revolving speed magnetic agitation 45min of 180r/min
Sugar, reacts 2h, and dehydration, drying are squeezed out, pelletizing by double screw extruder, modified ABS resin are made, control extruder barrel
Temperature is 220 DEG C.
The complex antimicrobials are made by the following method:
(1) silver nitrate is added in deionized water, 40 DEG C of heating water baths, magnetic agitation 45min, trisodium citrate is added,
60 DEG C are warming up to, 30min is stirred, elargol is made；
(2) sodium sulfate of polyethenoxy ether of fatty alcohol is poured into the beaker equipped with dehydrated alcohol, metering system is then added
Sour methyl esters, magnetic agitation 10min, is added deionized water after mixing, and microemulsion is made, nanometer titanium dioxide is added in microemulsion
In titanium colloidal sol, modified nano-titanium dioxide colloidal sol is made in 60 DEG C of heating water bath 5h；
(3) elargol prepared in step (1) is added in modified nano-titanium dioxide colloidal sol, 10% ammonium hydroxide of addition, 50 DEG C
Heating water bath simultaneously stirs 4h, is centrifuged 1min with the revolving speed of 12000r/min, filtering, with dehydrated alcohol by washing of precipitate three times, system
Obtain the complex antimicrobials.
Embodiment 2
A kind of nano-antibacterial ABS plastic, is made of following raw material: 26 parts of modified ABS resins, 12 parts of composite antibacterial
Agent, 14 parts of pentaerythrites, 6 parts of tetraisocyanates, 14 parts of dioctyl phthalates, 25 parts of methylene chloride, 55 parts of dehydrated alcohols；
The nano-antibacterial ABS plastic is made by the following method:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, and complex antimicrobials and anhydrous are added
Tetraisocyanate and dioctyl phthalate are added after magnetic agitation 1h, is warming up to 75 DEG C, magnetic agitation 50min for ethyl alcohol, surpass
Acoustic shock is transferred in reaction kettle after swinging 15min, and reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, at this temperature instead
4h is answered, complex colloid is obtained；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, the nano-antibacterial ABS plastic is made.
Embodiment 3
A kind of nano-antibacterial ABS plastic, is made of following raw material: 28 parts of modified ABS resins, 14 parts of composite antibacterial
Agent, 18 parts of pentaerythrites, 8 parts of tetraisocyanates, 18 parts of dioctyl phthalates, 27 parts of methylene chloride, 65 parts of dehydrated alcohols；
The nano-antibacterial ABS plastic is made by the following method:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, and complex antimicrobials and anhydrous are added
Tetraisocyanate and dioctyl phthalate are added after magnetic agitation 1h, is warming up to 75 DEG C, magnetic agitation 50min for ethyl alcohol, surpass
Acoustic shock is transferred in reaction kettle after swinging 15min, and reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, at this temperature instead
4h is answered, complex colloid is obtained；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, the nano-antibacterial ABS plastic is made.
Embodiment 4
A kind of nano-antibacterial ABS plastic, is made of following raw material: 30 parts of modified ABS resins, 15 parts of composite antibacterial
Agent, 20 parts of pentaerythrites, 10 parts of tetraisocyanates, 20 parts of dioctyl phthalates, 30 parts of methylene chloride, 70 parts of anhydrous second
Alcohol；
The nano-antibacterial ABS plastic is made by the following method:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, and complex antimicrobials and anhydrous are added
Tetraisocyanate and dioctyl phthalate are added after magnetic agitation 1h, is warming up to 75 DEG C, magnetic agitation 50min for ethyl alcohol, surpass
Acoustic shock is transferred in reaction kettle after swinging 15min, and reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, at this temperature instead
4h is answered, complex colloid is obtained；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, the nano-antibacterial ABS plastic is made.
Comparative example 1
This comparative example is to be modified to ABS resin compared with Example 1, and preparation process is as follows:
Step S1, ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths, at the uniform velocity stirring 30min,
Pentaerythrite is added later, pours into agitating device, stands 1h after stirring 30min, complex antimicrobials and dehydrated alcohol, magnetic is added
Tetraisocyanate and dioctyl phthalate is added after stirring 1h in power, is warming up to 75 DEG C, magnetic agitation 50min, ultrasonic vibration
It is transferred in reaction kettle after 15min, reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, reacts 4h at this temperature, obtains
To complex colloid；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, nano-antibacterial ABS plastic is made.
Comparative example 2
This comparative example compared with Example 1, complex antimicrobials is not added, and preparation process is as follows:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths at the uniform velocity stir
Pentaerythrite is added in 30min later, pours into agitating device, stands 1h after stirring 30min, dehydrated alcohol, magnetic agitation is added
Tetraisocyanate and dioctyl phthalate are added after 1h, after being warming up to 75 DEG C, magnetic agitation 50min, ultrasonic vibration 15min
It is transferred in reaction kettle, reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, reacts 4h at this temperature, is mixed
Colloid；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtain grain in vacuum oven
The solid powder that diameter is 7-80 μm；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, heat
1h is stood after pressure 20min, nano-antibacterial ABS plastic is made.
Comparative example 3
This comparative example is a kind of Antibacterial ABS plastic in market.
The antibiotic property, impact strength and tensile strength of embodiment 1-4 and comparative example 1-3 are detected, test result is such as
Shown in the following table 1；
Tensile strength: referring to shown in ASTM-D638；
Impact strength: referring to shown in ASTM-D256；
Antibiotic property: referring to shown in QB/T2591-2003；
Table 1
It can be seen that embodiment 1-4 tensile strength is between 113-128MPa from upper table 1, the stretching of comparative example 1-3 is strong
Degree is between 75-110MPa；Embodiment 1-4 impact strength is in 13.5-15.1KJ/m2In range, the impact strength of comparative example 1-3
In 11.5-13.3KJ/m2In range；The antibiotic rate of embodiment 1-4 reaches 97.5-98.1%, and the antibiotic rate of comparative example 1-3 reaches
78.6-85.3%.So nano-antibacterial ABS plastic prepared by the present invention not only antibiotic rate with higher, but also have good
Tensile strength and impact strength.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched
The specific embodiment stated does various modifications or additions or is substituted in a similar manner, and without departing from invention or surpasses
More range defined in the claims, is within the scope of protection of the invention.
Claims (8)
1. a kind of nano-antibacterial ABS plastic, which is characterized in that be made of following raw material: 25-30 parts of modified ABS resins,
10-15 parts of complex antimicrobials, 10-20 parts of pentaerythrites, 5-10 parts of crosslinking agents, 15-20 parts of plasticizer, 25-30 parts of methylene chloride,
50-70 parts of dehydrated alcohols；
The nano-antibacterial ABS plastic is made by the following method:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths, at the uniform velocity stirring 30min,
Pentaerythrite is added later, pours into agitating device, stands 1h after stirring 30min, complex antimicrobials and dehydrated alcohol, magnetic is added
Crosslinking agent and plasticizer is added after stirring 1h in power, is transferred to after being warming up to 75 DEG C, magnetic agitation 50min, ultrasonic vibration 15min anti-
It answers in kettle, reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, reacts 4h at this temperature, obtains complex colloid；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, the vacuum that temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtaining partial size is in drying box
7-80 μm of solid powder；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, hot pressing
1h is stood after 20min, and the nano-antibacterial ABS plastic is made.
2. a kind of nano-antibacterial ABS plastic according to claim 1, which is characterized in that the modified ABS resin is by as follows
Raw material is made: 10-15 parts of polybutadiene latexs, 5-10 parts of polyacrylate dispersions, 20-28 parts of styrene-acrylonitriles
Copolymer, 50-75 parts of desalted waters, 1-3 parts of ammonium sulfate, 3-5 parts of lauric monoglycerides, 5-8 parts of carboxymethyl chitosans.
3. a kind of nano-antibacterial ABS plastic according to claim 1, which is characterized in that the modified ABS resin is by as follows
Method is made:
(1) polybutadiene latex is added in beaker with polyacrylate dispersion and is mixed, with the revolving speed magnetic force of 120r/min
30min is stirred, is transferred in holding vessel, 45 DEG C of heating water baths simultaneously stir 4h with the revolving speed of 150r/min, poly- after agglomeration is made
Butadiene latex；
(2) polybutadiene latex after agglomeration is stood into 5h, is added three with styrene-acrylonitrile copolymer and desalted water later
In mouth flask, 60 DEG C of heating water baths react 1h, and ammonium sulfate is added, and ultrasonic 15min is warming up to 75 DEG C, and lauric monoglyceride is added
Ester is dispersed 5min with the revolving speed of 2000r/min, carboxymethyl chitosan is added with the revolving speed magnetic agitation 45min of 180r/min,
2h is reacted, dehydration, drying are squeezed out, pelletizing by double screw extruder, modified ABS resin are made, control extruder barrel temperature
It is 220 DEG C.
4. a kind of nano-antibacterial ABS plastic according to claim 1, which is characterized in that the complex antimicrobials are by as follows
Raw material is made: 5-15 parts of silver nitrates, 0.5-1.0 parts of trisodium citrates, 35-50 parts of deionized waters, 0.3-0.5 part 10%
Ammonium hydroxide, 15-20 parts of nano titanic oxide sols, 25-40 parts of dehydrated alcohols, 10-20 parts of sodium sulfate of polyethenoxy ether of fatty alcohol,
20-30 parts of methyl methacrylates.
5. a kind of nano-antibacterial ABS plastic according to claim 1, which is characterized in that the complex antimicrobials are by as follows
Method is made:
(1) silver nitrate is added in deionized water, 40 DEG C of heating water baths, magnetic agitation 45min, trisodium citrate, heating is added
To 60 DEG C, 30min is stirred, elargol is made；
(2) sodium sulfate of polyethenoxy ether of fatty alcohol is poured into the beaker equipped with dehydrated alcohol, methyl methacrylate is then added
Ester, magnetic agitation 10min, is added deionized water after mixing, and microemulsion is made, and it is molten that nano-titanium dioxide is added in microemulsion
In glue, modified nano-titanium dioxide colloidal sol is made in 60 DEG C of heating water bath 5h；
(3) elargol prepared in step (1) is added in modified nano-titanium dioxide colloidal sol, 10% ammonium hydroxide, 50 DEG C of water-baths is added
Heat and stir 4h, 1min is centrifuged with the revolving speed of 12000r/min, filtering, with dehydrated alcohol by washing of precipitate three times, institute is made
State complex antimicrobials.
6. a kind of nano-antibacterial ABS plastic according to claim 1, which is characterized in that the crosslinking agent tetraisocyanate,
One or more of methacrylic acid and trimethoxy silane.
7. a kind of nano-antibacterial ABS plastic according to claim 1, which is characterized in that the plasticizer is O-phthalic
One or more of dioctyl phthalate, dibutyl phthalate and diisononyl phthalate.
8. a kind of preparation method of nano-antibacterial ABS plastic, which comprises the steps of:
Step S1, modified ABS resin is added in the beaker equipped with methylene chloride, 60 DEG C of heating water baths, at the uniform velocity stirring 30min,
Pentaerythrite is added later, pours into agitating device, stands 1h after stirring 30min, complex antimicrobials and dehydrated alcohol, magnetic is added
Crosslinking agent and plasticizer is added after stirring 1h in power, is transferred to after being warming up to 75 DEG C, magnetic agitation 50min, ultrasonic vibration 15min anti-
It answers in kettle, reactor pressure rises to 1.3-1.8MPa, is warming up to 85 DEG C, reacts 4h at this temperature, obtains complex colloid；
Step S2, the complex colloid of preparation is transferred in beaker, is placed in vacuum degree -0.09MPa, the vacuum that temperature is 100 DEG C
Dry 8h, obtains solid film, solid film is placed in the pulverizer of 10000r/min and is crushed, obtaining partial size is in drying box
7-80 μm of solid powder；
Step S3, solid powder is added in mold and carries out hot pressing, control pressure is 50-80MPa, and temperature is 120 DEG C, hot pressing
1h is stood after 20min, and the nano-antibacterial ABS plastic is made.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679872A (en) * | 2020-12-17 | 2021-04-20 | 安徽强旭塑业科技有限公司 | Antistatic plastic battery case and production method thereof |
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| CN104327281A (en) * | 2014-11-03 | 2015-02-04 | 天津大沽化工股份有限公司 | Preparation method of polybutadiene latex in unimodal distribution |
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| CN103044849A (en) * | 2013-01-06 | 2013-04-17 | 上海秋橙新材料科技有限公司 | Antibacterial abs plastic |
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