CN101397401B - Water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antibiotic composite material, preparation method and use thereof - Google Patents
Water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antibiotic composite material, preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a WBPU base cluster-shaped zinc oxide nano-crystal whisker antibiosis composite material and a preparation method and application thereof. In terms of parts by weight, the composite material of the invention contains 100 parts by weight of WBPU substrate and 0.3-2 parts by weight of cluster-shaped zinc oxide nano-crystal whisker antibacterial agent which undergoes ultrasonic dispersion treatment for preparing the composite material by using the blending of an ultrasonic auxiliary solution. The invention has simple preparation method and small addition amount, overcomes the problem of the inferior antibiosis effect of pure zinc series antibacterial agent and has high-efficiency, broad-spectrum and lasting antibiosis effect, as well as safe application and easy processing; the prepared composite material can be used as either an antibiosis coating directly or the masterbatch of the inorganic nano-antibiosis material of a polymer base and is applicable to the fields of food packaging, construction material, textiles, sanitary articles, daily article, household appliances, communication material and the like.
Description
Technical field
The present invention relates to anti-biotic material and its production and application field, particularly a kind of water polyurethane base flower cluster-shaped zinc oxide nanometer whisker Antibacterial Composite Material and Preparation Method and application.
Background technology
Along with the raising of science and technology development and people's living standard, people's health perception constantly strengthens, and gives higher attention to the healthization and the cleaning of environment of articles for daily use especially food.Yet in the daily life environment, invasive organisms such as bacterium are ubiquitous, threatening human beings'health.Over past ten years, the global microorganism disaster event that is caused by pathogenic micro-organism and mutation thereof takes place again and again, from " the O139 vibrio cholerae " of the India, " O157:H of Japan
7Intestinal bacteria ", the incidents such as " crazy heifer disease virus " of Britain; to also allowing with reverence and awe " singapore hemorrhagic fever and the hemorrhagic fever " incident of people so far; arrive the outburst of epidemic situations such as " severe acute respiratory syndrome " and " bird flu " virus and popular again, caused serious loss of life and personal injury and enormous economic loss for respective country or area.
The development of anti-biotic material and application can reduce or avoid cross infection and the transmission of disease of bacterium effectively.Anti-biotic material is meant a class new function material that self has killing or suppress microbial function.Anti-biotic material generally is meant by adding certain antiseptic-germicide, thereby makes material have a class new function material that suppresses or kill the surface bacteria ability, as antibiotic plastic, antibacterial fiber and fabric, anti-bacteria ceramic and antibacterial metal material etc.
Antiseptic-germicide is meant that some microorganisms are extremely sensitive, adds the chemical substance that can give the material antimicrobial properties in the material on a small quantity to.At present the antiseptic-germicide of using mainly contains following several: 1. natural antibacterial agent.Mainly refining refinement forms from animals and plants, as chitosan and Hinokitiol etc.Natural antibacterial agent toxicity is little, safe, but poor heat resistance, work-ing life are short, are subject to processing the restriction of condition, can't realize mass marketization.2. organic antibacterial agent.Principal item has: quaternary ammonium salts, biguanides, alcohols, phenols, organo-metallic class, pyridines, imidazoles and thiophene-based etc.The organic antibacterial agent speed of action is fast, operability is good, stability is strong, restraining effect to microorganism has certain specificity, but easily produce the microorganism resistance, and have deficiencies such as easily migration, poor heat resistance, and many organic antibacterial agents are easy decomposition failure under high temperature, high pressure, high-shear processing conditions, and degradation production causes secondary pollution.3. inorganic antiseptic.Inorganic antiseptic is by methods such as physical adsorption-ion-exchanges, metals such as silver, copper, zinc or metal ion is carried on the surface of porous materials such as zeolite, silica gel, titanium dioxide or zirconium phosphate obtains.Wherein, the carrying silver antimicrobials antibacterial ability is the strongest, so mostly commercial antiseptic-germicide is silver-series antibacterial agent.The advantage of inorganic antiseptic be do not produce resistance, security is good, thermotolerance is high; Weak point is the antimicrobial late effect property, can not be as organic antibacterial agent killing bacteria rapidly.In addition, silver ions easily generates silver suboxide or becomes argent through photo catalytic reduction, so there is the shortcoming that makes the goods variable color.4. photocatalyst-type inorganic antiseptic.Be mainly n N-type semiconductorN material, as TiO
2, ZnO, CdS, WO
3, SnO
2, ZrO
2Deng.Nontoxic, the no special odor of photocatalyst-type anti-biotic agent, nonirritant, colour stability is good, nondiscoloration under the high temperature, do not decompose, aboundresources, cheap.But shortcoming is just to show bigger anti-microbial activity under UV-light.
The development of nano science makes that the photocatalyst-type inorganic antiseptic is further developed.But general zero-dimension nano material is because particle diameter is little, and surface-area is very big, and very difficult fully dispersion in use all will be carried out the surface to it before general the use and coat processing.The result who coats greatly reduces the performance of nano effect and anti-microbial effect on the one hand, and treatment process is loaded down with trivial details on the other hand, has increased extra cost.Institute is so that many investigators turn to the unidimensional nano material to sight.(spy opens flat 5-912 to Japanese Patent, Te Kaiping 8-133918) report is compound with four acicular type zinc oxide crystal whisker and silver salt, prepared inorganic antiseptic and obtained in differing materials and environment to use that (spy opens flat 5-78498 with excellent antibacterial effect, Te Kaiping 78218, Te Kaiping 6-140731 etc.), the technology of these Japanese Patent reports is utilized the needles active centre and the point effect of ZnOw, activates airborne water and oxygen, produces hydroxyl radical free radical (OH) and active oxygen ion (O
-2), destroy bacteria live and multiplication capacity and make bacterium dead and reach antibacterial effect.But owing to use common ZnOw, its whisker base diameter slightly reaches 0.1～10 μ m, and length reaches 30～100 μ m, and its needles active centre is few, and point effect is poor; In order to improve antibacterial effect, add silver ions as one of main anti-microbial activity composition, and wherein silver ions still faces discoloration problem.Chinese patent 03117502.3 has been reported a kind of ZnOw complex antimicrobials composition, and higher anti-microbial activity is arranged, but has mixed other metal ion in the lattice of described four acicular type zinc oxide crystal whisker, and added nano zine oxide, nano-titanium oxide, water glass carrier etc., complicated component.
Summary of the invention
It is strong to the purpose of this invention is to provide a kind of anti-microbial activity, and antibiotic process and effect can repeat to continue to carry out, and effect is stable, also need not the water polyurethane base flower cluster-shaped zinc oxide nanometer whisker Antibacterial Composite Material and Preparation Method and the application of ultraviolet light photocatalysis.The characteristics of maximum of the present invention are the advantages of nontoxic raw materials that is adopted, and preparation method's technology is simple.
The technical scheme that the present invention solves its technical problem employing is: a kind of water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material, it contains matrix aqueous polyurethane A and antiseptic-germicide B, by weight, the ratio of each component is in the matrix material: A:100 part; B:0.3 part～2 part;
Wherein A is the aqueous polyurethane that contains the micro phase separation structure of the hard section of nonpolar soft section and polarity, and B is base diameter 100～800nm, and length reaches the flower cluster-shaped zinc oxide nanometer whisker of being made up of nanometer rod or nano wire of 2～17 μ m.
The antiseptic-germicide component flower cluster-shaped zinc oxide nanometer whisker of above-mentioned antimicrobial composite material is prepared by following steps:
1. in NaOH solution, add excessive Zinc oxide powder and make the solution supersaturation;
2. get supernatant liquid behind the supersaturated solution standing demix and under agitation add in the quantitative distilled water, wherein the volume ratio of clear liquid and water is 4～10: 100, forms diluting soln;
3. diluting soln is packed in the airtight container 70～150 ℃ of following reacting by heating 5～15 hours;
4. the product that reaction obtained filters, and puts into baking oven with deionized water wash to the neutrality and dries.
The above-mentioned steps 1. mass concentration of middle NaOH solution is 4～6M; Step 2. in the pH value of diluting soln less than 13.5 o'clock, be more than or equal to 13.5 with NaOH solution adjusting pH value.
The matrix component of above-mentioned antimicrobial composite material is an anion-type water-thinned polyurethane, prepares gained by the performed polymer self-emulsification, can prepare with following technological process:
1. will join in the reactor through oligopolymer dibasic alcohol, vulcabond and the hydrophilic chain extender of drying treatment, be warmed up to 65～75 ℃, add the catalyzer dibutyl tin laurate, isothermal reaction 1.5～2.0 hours;
Wherein the molar ratio of vulcabond and oligopolymer dibasic alcohol is 1.5～3.0: 1, hydrophilic chain extender 2, the consumption of 2-dimethylol propionic acid be synthetic polymer heavy 3～6%, the dibutyl tin laurate consumption be synthetic polymer heavy 0.1%;
2. add the linking agent TriMethylolPropane(TMP), slowly be warming up to 80～85 ℃, isothermal reaction 4～5 hours;
Wherein the TriMethylolPropane(TMP) consumption be synthetic polymer heavy 2～6%;
3. cool to 40～45 ℃, add the neutralizing agent triethylamine, in stirring fast and 20～40 minutes;
Wherein the mol ratio of triethylamine and hydrophilic chain extender is 1: 1;
4. the performed polymer that neutralization is obtained slowly joins in a certain amount of deionized water, control solid content, high-speed stirring emulsification simultaneously;
The solid content of wherein controlling water-based emulsion is 35～40%.
5. add the chainextender quadrol and continue reaction 1～2 hour, obtain aqueous polyurethane emulsion.
The oligopolymer dibasic alcohol that relates in the above-mentioned steps is that polyester diol is as poly-hexanodioic acid-1,4-butanediol ester dibasic alcohol etc., polyether Glycols such as polyoxyethylene glycol etc., other oligopolymer dibasic alcohol or their mixture; Vulcabond that relates to such as isophorone diisocyanate, tolylene diisocyanate, other vulcabond or their mixture.
The present invention also provides the preparation method of above-mentioned any aqueous polyurethane matrix flower cluster-shaped zinc oxide nanometer whisker antibiotic composite material, specifically comprises being prepared as follows step:
0.3 the flower cluster-shaped zinc oxide nanometer whisker of～2 weight parts joins in the aqueous ethanolic solution, fully disperses the back to carry out ultrasonication 10～20 minutes in ultrasonic washing instrument with the homogeneous separating apparatus; Again resulting ultrasonic dispersing liquid is joined in the aqueous polyurethane of 100 weight parts,, thereby make composite emulsions by ultrasonic wave aid dispersion 20～40 minutes; Leave standstill natural levelling on the template that is poured on horizontal positioned behind the froth breaking, dry maintenance under the room temperature, treat film forming after, put into the baking oven heat drying to constant weight.
The volumetric concentration of above-mentioned aqueous ethanolic solution is 60～70%.
The matrix material that the present invention obtains can directly use as antimicrobial coating, also can be used as the master batch of polymer base inorganic nano anti-biotic material, be applicable to fields such as food product pack, material of construction, textiles, sanitary product, articles for daily use, household electrical appliance, communication material.
Principle of work of the present invention is: the flower cluster-shaped zinc oxide nanometer whisker of the antiseptic-germicide that the present invention adopts for forming by nanometer rod or nano wire, and whisker size homogeneous, base diameter 100～800nm, length reaches 2～17 μ m.The conductive network that its flowers shape is formed for antibiotic ion provides the high efficiency of transmission path, helps the transmission of zine ion in polymer matrix; The nano whisker active centre is many, and the point effect height just can obtain good antibacterial effect so needn't add other active ingredient in addition.
The present invention adopts anion-type water-thinned polyurethane as matrix, and the diblock structure copolymer that anion-type water-thinned polyurethane is made up of hydrophilic, hydrophobic two kinds of segments, urethane after the ionization can spontaneously form the macromole micella in water, can be regarded as a kind of tensio-active agent, so be equivalent to the flower cluster-shaped zinc oxide nanometer whisker that adds be carried out surface modification, increased the consistency between antibiotic filler and matrix with a kind of tensio-active agent.Add the method that adopts ultrasonic aid dispersion, reduced the reunion of nano whisker, improved the homogeneity that it distributes in matrix, thereby improved the interaction between antibiotic filler and macromolecule matrix, reach the purpose that improves matrix material stability.
The present invention has following beneficial effect:
(1) the present invention adopts the matrix of the aqueous polyurethane of environment-friendly type as matrix material, do not need to add other auxiliary agent in the whole synthetic and process for making, also do not need deleterious organic solvent, gained material and building-up process thereof are nonpoisonous and tasteless, belong to the environmental friendliness production technique.
(2) preparation method of the present invention is simple, has overcome the relatively poor problem of pure zinc series antibacterial agent antibacterial effect.
(3) matrix material anti-microbial activity of the present invention is strong, and antibiotic process and effect can repeat to continue to carry out, act on stable.
Description of drawings
Fig. 1 is the sem photograph of flower cluster-shaped zinc oxide nanometer whisker.
Embodiment
Below in conjunction with embodiment, the present invention is done detailed description further, but implementation of the present invention is not limited thereto.
Embodiment 1
Set of dispense is than as shown in table 1.
(1) preparation of flower cluster-shaped zinc oxide nanometer whisker
Used flower cluster-shaped zinc oxide nanometer whisker (base diameter 200～500nm, length is 2～3 μ m) preparation process of being made up of nanometer rod of embodiment 1 is as follows:
1. in the NaOH of 5M solution, add excessive Zinc oxide powder and make the solution supersaturation.
2. get the 40mL supernatant liquid behind the supersaturated solution standing demix and under agitation add in the 500mL distilled water, form diluting soln.
3. diluting soln is packed in the airtight container at 90 ℃ of following reacting by heating 10h;
4. the product that reaction obtained filters, and puts into baking oven with deionized water wash to the neutrality and dries.
(2) Synthesis of Waterborne Polyurethane.
1. will be through the poly-hexanodioic acid-1 of drying treatment, 4-butanediol ester dibasic alcohol, isophorone diisocyanate (isophorone diisocyanate and poly-hexanodioic acid-1, the molar ratio of 4-butanediol ester dibasic alcohol is 2.5: 1) and 2, the 2-dimethylol propionic acid (consumption be synthetic polymer heavy 3.6%) join in the reactor, being warmed up to 75 ℃ makes it fuse fully, add again the catalyzer dibutyl tin laurate (consumption be synthetic polymer heavy 0.1%), 75 ℃ of isothermal reactions 1.5 hours.
2. add again the linking agent TriMethylolPropane(TMP) (consumption be synthetic polymer heavy 4%), slowly be warming up to 80 ℃, and remain on 80 ℃ of down reactions 4 hours.
3. cool to about 40 ℃, add neutralizing agent triethylamine (triethylamine and 2, the mol ratio of 2-dimethylol propionic acid are 1: 1), in stirring fast with about 20 minutes.
4. the performed polymer that will neutralize slowly joins (the control solid content is 38%) in a certain amount of deionized water, high-speed stirring emulsification simultaneously.
5. add quadrol again and continued chain extending reaction 1 hour, obtain aqueous polyurethane emulsion.
(3) preparation of antimicrobial composite material
To join the 8mL volumetric concentration be in 60% the aqueous ethanolic solution with obtaining the amount of flower cluster-shaped zinc oxide nanometer whisker by table 1 in (1), fully disperses the back to carry out ultrasonication 15 minutes in power is the ultrasonic washing instrument of 200W with the homogeneous separating apparatus.Again the nano whisker dispersion liquid is joined in the aqueous polyurethane,, thereby make composite emulsions by ultrasonic wave aid dispersion 30 minutes.Leave standstill natural levelling on the template that is poured on horizontal positioned behind the froth breaking, dry maintenance under the room temperature, treat film forming after, put into the baking oven heat drying to constant weight.
(4) test of antimicrobial composite material anti-microbial activity
Antiseptic-germicide activity according to standard QB/T 2591-2003 working sample.The check bacterial classification is colon bacillus (intestinal bacteria) ATCC 25922 and streptococcus aureus ATCC 6538.On sample to be checked, make bacterium uniform contact sample 24 hours by quantitative inoculated bacteria,, record the viable count in the sample, and calculate the antibacterium rate of sample through after the cultivation of certain hour with the method for pad pasting.The anti-bacterial result sees Table 2～3.
Embodiment 2
(1) preparation of flower cluster-shaped zinc oxide nanometer whisker
The preparation process of the flower cluster-shaped zinc oxide nanometer whisker that present embodiment is used is as follows:
1. in the NaOH of 4M solution, add excessive Zinc oxide powder and make the solution supersaturation.
2. get the 50mL supernatant liquid behind the supersaturated solution standing demix and under agitation add in the 500mL distilled water, form diluting soln.
3. diluting soln is packed in the airtight container at 70 ℃ of following reacting by heating 15h;
4. the product that reaction obtained filters, and puts into baking oven with deionized water wash to the neutrality and dries.
(2) Synthesis of Waterborne Polyurethane
1. will be through polyoxyethylene glycol, the tolylene diisocyanate (molar ratio of tolylene diisocyanate and polyoxyethylene glycol is 1.5: 1) and 2 of drying treatment, the 2-dimethylol propionic acid (consumption be synthetic polymer heavy 3%) join in the reactor, being warmed up to 65 ℃ makes it fuse fully, add again the catalyzer dibutyl tin laurate (consumption be synthetic polymer heavy 0.1%), 65 ℃ of isothermal reactions 1.5 hours.
2. add again the linking agent TriMethylolPropane(TMP) (consumption be synthetic polymer heavy 6%), slowly be warming up to 85 ℃, and remain on 85 ℃ of down reactions 4 hours.
3. cool to about 45 ℃, add neutralizing agent triethylamine (triethylamine and 2, the mol ratio of 2-dimethylol propionic acid are 1: 1), in stirring fast with about 40 minutes.
4. the performed polymer that will neutralize slowly joins (the control solid content is 35%) in a certain amount of deionized water, high-speed stirring emulsification simultaneously.
5. add quadrol again and continued chain extending reaction 2 hours, obtain aqueous polyurethane emulsion.
(3) preparation of antimicrobial composite material
To join the 10mL volumetric concentration be in 70% the aqueous ethanolic solution with obtaining the amount of flower cluster-shaped zinc oxide nanometer whisker by table 1 in (1), fully disperses the back to carry out ultrasonication 10 minutes in power is the ultrasonic washing instrument of 200W with the homogeneous separating apparatus.Again the nano whisker dispersion liquid is joined in the aqueous polyurethane,, thereby make composite emulsions by ultrasonic wave aid dispersion 20 minutes.Leave standstill natural levelling on the template that is poured on horizontal positioned behind the froth breaking, dry maintenance under the room temperature, treat film forming after, put into the baking oven heat drying to constant weight.
(4) test of antimicrobial composite material anti-microbial activity
Method and embodiment 1 are same, and The anti-bacterial result sees Table 2～3.
Embodiment 3
(1) preparation of flower cluster-shaped zinc oxide nanometer whisker
The preparation process of the used flower cluster-shaped zinc oxide nanometer whisker of present embodiment is as follows:
1. in the NaOH of 6M solution, add excessive Zinc oxide powder and make the solution supersaturation.
2. get the 33mL supernatant liquid behind the supersaturated solution standing demix and under agitation add in the 500mL distilled water, form diluting soln.
3. diluting soln is packed in the airtight container at 150 ℃ of following reacting by heating 5h;
4. the product that reaction obtained filters, and puts into baking oven with deionized water wash to the neutrality and dries.
(2) Synthesis of Waterborne Polyurethane
1. will be through the poly-hexanodioic acid-1 of drying treatment, 4-butanediol ester dibasic alcohol, isophorone diisocyanate (isophorone diisocyanate and poly-hexanodioic acid-1, the molar ratio of 4-butanediol ester dibasic alcohol is 3: 1) and 2, the 2-dimethylol propionic acid (consumption be synthetic polymer heavy 6%) join in the reactor, being warmed up to 70 ℃ makes it fuse fully, add again the catalyzer dibutyl tin laurate (consumption be synthetic polymer heavy 0.1%), 70 ℃ of isothermal reactions 1.5 hours.
2. add again the linking agent TriMethylolPropane(TMP) (consumption be synthetic polymer heavy 2%), slowly be warming up to 80 ℃, and remain on 80 ℃ of down reactions 5 hours.
3. cool to about 42 ℃, add neutralizing agent triethylamine (triethylamine and 2, the mol ratio of 2-dimethylol propionic acid are 1: 1), in stirring fast with about 30 minutes.
4. the performed polymer that will neutralize slowly joins (the control solid content is 40%) in a certain amount of deionized water, high-speed stirring emulsification simultaneously.
5. add quadrol again and continued chain extending reaction 1 hour, obtain aqueous polyurethane emulsion.
(3) preparation of antimicrobial composite material
To join the 15mL volumetric concentration be in 65% the aqueous ethanolic solution with obtaining the amount of flower cluster-shaped zinc oxide nanometer whisker by table 1 in (1), fully disperses the back to carry out ultrasonication 20 minutes in power is the ultrasonic washing instrument of 200W with the homogeneous separating apparatus.Again the nano whisker dispersion liquid is joined in the aqueous polyurethane,, thereby make composite emulsions by ultrasonic wave aid dispersion 40 minutes.Leave standstill natural levelling on the template that is poured on horizontal positioned behind the froth breaking, dry maintenance under the room temperature, treat film forming after, put into the baking oven heat drying to constant weight.
(4) test of antimicrobial composite material anti-microbial activity
Method and embodiment 1 are same, and The anti-bacterial result sees Table 2～3.
Embodiment 5～6
(1) preparation of flower cluster-shaped zinc oxide nanometer whisker
The preparation process of the used flower cluster-shaped zinc oxide nanometer whisker of being made up of nano wire (base diameter 100～800nm, length is 7～16 μ m) is as follows:
1. in the NaOH of 5M solution, add excessive Zinc oxide powder and make the solution supersaturation.
2. get the 20mL supernatant liquid behind the supersaturated solution standing demix and under agitation add in the 500mL distilled water, form diluting soln, the pH value that adds the NaOH solution regulator solution of an amount of 5M again is 13.5.
3. diluting soln is packed in the airtight container at 90 ℃ of following reacting by heating 10h;
4. the product that reaction obtained filters, and puts into baking oven with deionized water wash to the neutrality and dries.
(2) Synthesis of Waterborne Polyurethane
Method and embodiment 1 are together
(3) preparation of antimicrobial composite material
Method and embodiment 1 are together
(4) test of antimicrobial composite material anti-microbial activity
Method and embodiment 1 are same, and The anti-bacterial result sees Table 2～3.
By table 2～3 as can be seen, when flower cluster-shaped zinc oxide nanometer whisker is more than 0.4 part the time with respect to the proportioning of matrix, matrix material has strong antibacterium effect to colon bacillus and streptococcus aureus.
Table 1 antimicrobial composite material compositing formula
The result of table 2 antimicrobial composite material print Chinese People's Anti-Japanese Military and Political College intestines Escherichia
The result of the anti-streptococcus aureus of table 3 antimicrobial composite material print
(annotate: table 2, "＜50 " are meant that the colony number result who measures by the method for GB/T 4789.2 is 0 in 3, multiply by the 50 actual recovered viable bacteria numerical value that obtain and represent with "＜50 "; Calculate by 50 colony numbers when calculating antibiotic rate.The antibiotic plastic of antibacterium rate 〉=90% can have been reported the antibacterium effect; The antibiotic plastic of antibacterium rate 〉=99% can have been reported strong antibacterium effect.)
Claims (8)
1. a water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material is characterized in that: contain matrix aqueous polyurethane A and antiseptic-germicide B, by weight, the ratio of each component is in the matrix material: A:100 part; B:0.3 part～2 part;
Wherein A is the aqueous polyurethane that contains the micro phase separation structure of the hard section of nonpolar soft section and polarity; B is base diameter 100～800nm, and length reaches the flower cluster-shaped zinc oxide nanometer whisker of being made up of nanometer rod or nano wire of 2～17 μ m.
2. water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material according to claim 1 is characterized in that: described aqueous polyurethane is an anion-type water-thinned polyurethane, is to prepare gained by the performed polymer self-emulsification.
3. water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material according to claim 1 is characterized in that: described flower cluster-shaped zinc oxide nanometer whisker is prepared by following steps:
1. in NaOH solution, add excessive Zinc oxide powder and make the solution supersaturation;
2. get supernatant liquid behind the supersaturated solution standing demix and under agitation add in the quantitative distilled water, wherein the volume ratio of clear liquid and water is 4～10: 100, forms diluting soln;
3. diluting soln is packed in the airtight container at 70～150 ℃ of following reacting by heating 5～15h;
4. the product that reaction obtained filters, and puts into baking oven with deionized water wash to the neutrality and dries.
4. water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material according to claim 3 is characterized in that: the described step 1. mass concentration of middle NaOH solution is 4～6M; It is more than or equal to 13.5 that the 2. middle diluting soln of described step is regulated the pH value with NaOH solution.
5. the preparation method of each described water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material of claim 1～4 is characterized in that comprising following concrete preparation process:
0.3 the flower cluster-shaped zinc oxide nanometer whisker of～2 weight parts joins in the aqueous ethanolic solution, fully disperses the back to carry out ultrasonication 10～20 minutes in ultrasonic washing instrument with the homogeneous separating apparatus; Again resulting ultrasonic dispersing liquid is joined in the aqueous polyurethane of 100 weight parts,, thereby make composite emulsions by ultrasonic wave aid dispersion 20～40 minutes; Leave standstill natural levelling on the template that is poured on horizontal positioned behind the froth breaking, dry maintenance under the room temperature, treat film forming after, put into the baking oven heat drying to constant weight.
6. the preparation method of water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material according to claim 5 is characterized in that: the volumetric concentration of described aqueous ethanolic solution is 60～70%.
7. the preparation method of water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material according to claim 5 is characterized in that: described aqueous polyurethane is an anion-type water-thinned polyurethane, is to prepare gained by the performed polymer self-emulsification.
In the claim 1～4 each described water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antimicrobial composite material in the application in food product pack, material of construction, textiles, sanitary product, articles for daily use, household electrical appliance or communication material field.
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| CN102321360B (en) * | 2011-07-27 | 2013-02-20 | 东南大学 | Preparation method of metal oxide whisker-polyurethane composite material with monodispersity |
| CN104494953A (en) * | 2014-12-02 | 2015-04-08 | 黄然 | Food-grade hygienic standard-based post-treatment process for textile product |
| CN107603190A (en) * | 2017-09-21 | 2018-01-19 | 河南驼人医疗器械集团有限公司 | A kind of medical antibacterial polyurethane material and preparation method thereof |
| CN110776818B (en) * | 2019-11-14 | 2021-07-20 | 深圳市冠为科技股份有限公司 | Adsorptive porous nano silver/aluminum oxide/polyester composite water-based coating agent and preparation method thereof |
| CN112226067A (en) * | 2020-10-23 | 2021-01-15 | 彭龙水 | Preparation process of nano antibacterial negative ion engineering plastic |
| CN112252030A (en) * | 2020-10-23 | 2021-01-22 | 彭龙水 | Preparation process of nano antibacterial and negative ion home textile product |
| CN113583287A (en) * | 2021-09-11 | 2021-11-02 | 福建鸿星尔克体育用品有限公司 | Preparation method of ultralight sole with hydrogen explosion structure, sole and sports shoe |
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| CN101397401A (en) | 2009-04-01 |
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