CN104525939B - A kind of preparation method of the amphiphilic nano silver based on stabilized polyurethane agent - Google Patents
A kind of preparation method of the amphiphilic nano silver based on stabilized polyurethane agent Download PDFInfo
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- CN104525939B CN104525939B CN201410837676.6A CN201410837676A CN104525939B CN 104525939 B CN104525939 B CN 104525939B CN 201410837676 A CN201410837676 A CN 201410837676A CN 104525939 B CN104525939 B CN 104525939B
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Abstract
The present invention relates to the preparation of inorganic metal nano material, more particularly to prepares amphiphilic nano silver based on the reverse miniemulsion techniques of stabilized polyurethane agent.New amphiphilic nano silver granuel footpath prepared by the present invention can be regulated and controled by simple control reaction condition (reactant concentration and ultrasonic emulsification power etc.) between 5 100 nanometers；The composition of regulation and control stabilized polyurethane agent can prepare amphiphilic nano silver, and which all has good dispersibility and dispersion stabilization in non-polar solven system (such as toluene) and polar solvent (such as water).Stabilized polyurethane agent synthetic method is simple, technique is controllable and synthesis material is easy to get, nonhazardouss, it is easy to industrialized production.Prepared amphiphilic nano silver can be applied to various polymeric systems as function nano auxiliary agent, can give the functions such as polymeric material antibiotic property, electric conductivity, photocatalytic.
Description
Technical field
The present invention relates to the preparation of inorganic metal nano material, the more particularly to reverse miniemulsion based on stabilized polyurethane agent
Technology prepares amphiphilic nano silver.
Background technology
Nanometer silver has excellent electric conductivity, conductivity of heat, surface activity, catalytic and antibiotic property etc., optics, catalysis,
The fields such as microelectronics, bio-sensing, antibacterial have a wide range of applications.In recent years, nano silver preparation technology is developed rapidly, preparation side
Method is varied, can be divided into chemical reduction method, microemulsion method, reverse micelle method, thermal decomposition method, template etc. by reaction condition.
But as nano-Ag particles specific surface area is big, specific surface energy is high, easily occur in preparation and application process particle oxidation and
Reunite, therefore how to stablize nano silver particles and solve its agglomeration traits and which is had in different media and polymeric system
There is the focus that good dispersibility and the compatibility are current nanometer silver area researches.With polymer as stabilizer fabricated in situ surface
Polymer-modified nanometer silver is to solve nanometer silver dispersion and the effective ways with the polymeric system compatibility.It is existing at present many
The report of nanometer silver is prepared using block polymer, graft polymers, dendritic, dissaving polymer etc. as stabilizer
Road.But above polymer design, synthesis condition are harsher.Present invention design synthesizing organo-silicon modified polyurethane molecule, its
Synthetic method is simple, the ripe controllable, raw material of synthesis technique is cheap and easy to get, it is easy to industrialized production, and organic-silicon-modified poly- with this
Urethane molecule is stabilizer, by the amphiphilic nano silver of anti-phase miniemulsion method synthesis of polyurethane surface modification, regulates and controls polyurethane
The composition of stabilizer can prepare amphiphilic nano silver, its in non-polar solven system (such as toluene) and polar solvent (such as water) all
With good dispersibility and dispersion stabilization.
The content of the invention
The present invention seeks to synthesize a kind of amphiphilic nano silver based on stabilized polyurethane agent, which can be in organic faciess and water phase
Middle stable dispersion.
A kind of preparation method of the amphiphilic nano silver based on stabilized polyurethane agent of the present invention, concrete preparation method are as follows：
(1). the anti-of silver salt inverted emulsion and reducing agent is prepared respectively using reverse miniemulsion method by stabilizer of polyurethane
To emulsion；(2). the ultrasonic fine crankshaft of difference, then mix the nanometer silver that fine crankshaft again generates polyurethane surface modification；(3). rotation
Turn evaporation toluene solvant, vacuum drying, washing centrifugation purification；(4). it is scattered in oil phase again, condensing reflux, removes body
In system, residual moisture obtains oiliness nano silver dispersion, in addition by purification ultrasonic disperse in water phase, obtains water nano silver
Dispersion liquid.Above reactant composition mainly includes stabilized polyurethane agent, toluene, silver salt, reducing agent, deionized water, dominant response
Thing proportioning is as follows：
Composition percentage by weight (wt%)
Reactant constitutes (1)
Reactant constitutes (2)
What is synthesized concretely comprises the following steps：Two parts of polyurethane toluene solutions are prepared by above proportioning first, A groups are respectively designated as
Point, B component；Equally silver salt solution is prepared by proportioning, be named as component C；Reducing agent aqueous solution is prepared by proportioning, D is named as
Component；Then component C is added drop-wise in component A, forms inverted emulsion component E；D components are added drop-wise in B component, form reverse
Emulsion F component；E, F component is moved in two beakers respectively, ultrasonic fine crankshaft 3-5 minutes；Emulsifying is anti-in two beakers after terminating
Re-mix in a beaker to emulsion, then carry out 3-5 minutes ultrasound fine crankshaft；Reduced pressure at 60 DEG C steaming with Rotary Evaporators
Send out, products therefrom under the conditions of 45 DEG C, is dried 24 hours in vacuum drying oven, deionized water is added in desciccate, is surpassed
Sound makes which be scattered in deionized water, centrifugation, removes impurity, is subsequently scattered in again in toluene, condensing reflux 24 hours,
Residual moisture is removed, that is, the nanometer silver being dispersed among in toluene based on stabilized polyurethane agent is obtained；After centrifugation being washed
Product ultrasonic disperse is obtained the nanometer silver for being dispersed among water based on stabilized polyurethane agent in water, that is, again.
Described stabilized polyurethane agent synthesis mainly with diisocyanate cpd, polyether polyol, organo-silicon compound,
Double methylol acid compounds, hydroxy acryl acid ester monomer be primary raw material, synthesis of polyurethane stabilizer, wherein diisocyanate
Compound is 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, isophorone diisocyanate, diphenyl methane two
Isocyanates, hexa-methylene -1,6- diisocyanate；Polyether polyol from the Polyethylene Glycol of different molecular weight, polypropylene glycol,
Polytetrahydrofuran diol, polycaprolactone glycol, PCDL, polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-
PEO) polyether polyol, its molecular weight ranges are 400-12000；Organo-silicon compound select ɑ, alpha, omega-dihydroxy polydimethyl silicon
Oxygen alkane, dihydroxy polydiphenylsiloxane, dihydroxy trifluompropyl methyl polysiloxane, dihydroxy polycaprolactone-poly dimethyl
One of siloxanes-polycaprolactone co-polymer is planted, and its molecular weight ranges is 400-24000；Double methylol acid compounds select two
Hydroxymethyl propionic acid, dimethylolpropionic acid；Hydroxy acryl acid ester monomer from 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate,
Hydroxypropyl acrylate, Hydroxypropyl methacrylate；Stabilized polyurethane agent is characterised by that its composition mainly includes：30-50wt%'s
Polyether polyol, the diisocyanate cpd of 10-25wt%, the organo-silicon compound of 5-15wt%, double hydroxyl first of 3-8wt%
Base acid compound, the hydroxy acryl acid ester compounds of 5-10wt%；The molecular weight ranges of synthesized stabilized polyurethane agent are
3000-30000, and require that the stabilized polyurethane agent has preferable dissolubility in toluene, by selecting different hydrophilic hydrophobic
Property, the polyether polyol of different molecular weight and adjust prepolymer in hydrophilic groups content method so that prepolymer is in toluene
In have preferable dissolubility.
Described silver salt is silver nitrate, silver nitrite, silver acetate.
Described reducing agent is ammonia, sodium borohydride, hydrazine hydrate.
Amphiphilic nano silver of the present invention synthesis based on stabilized polyurethane agent has advantages below：The amphiphilic nano of synthesis
Silver granuel footpath can adjust nanometer by the control to silver salt concentrations and ultrasonic fine crankshaft power between 5-100 nanometers
The particle diameter of silver, and resulting nanometer silver has good dispersibility and stably dispersing in the organic solvents such as toluene and water phase
Property；The self-control polyurethane synthetic method that used is simple, the ripe controllable, raw material of synthesis technique is cheap and easy to get and nonhazardouss, it is easy to
Industrialized production；Using anti-phase miniemulsion method synthesizing inorganic nano material, stable system is good, controllable, and at ambient temperature
Nanometer silver can be prepared；Resulting amphiphilic nano silver can be as function nano applying filler in various polymeric systems, can
Give the functions such as polymeric material antibiotic property, electric conductivity, photocatalytic.
Description of the drawings
Fig. 1 nanometer silvers are dispersed in the digital photograph figure in toluene and water respectively
Fig. 2 nanometer silvers are dispersed in the transmission electron microscope picture in toluene
The transmission electron microscope picture that Fig. 3 nanometer silvers are dispersed in water
Specific embodiment
In order to preferably explain the present invention, the present invention is further explained in detail with reference to specific embodiment.
Case 1.
Two parts of each 1.12g of polycarbonate polyurethane, two parts of each 93.6g of toluene, by proportioning respectively by 1.12g are weighed first
Polyurethane, 93.6g toluene are mixed in small beaker, and which at 65 DEG C is heated and be stirred continuously, fully dissolving (A.B. groups
Point)；Silver nitrate 1.61g, deionized water 4.4g are equally weighed, silver nitrate, deionized water is mixed in small beaker by proportioning, it is right
Which is heated to fully dissolving at 65 DEG C, then ultrasonic 10 minutes (component C)；Weigh sodium borohydride 0.74g, deionized water
5.35g, is mixed in hydroboration sodium sodium, deionized water in small beaker by proportioning, is heated to fully dissolving to which at 65 DEG C,
Then ultrasonic 10 minutes (D components).Secondly component C is moved in component A (component E)；D components are moved in B component (F components) point
Quick stirring 1.5 hours not in there-necked flask, under room temperature condition, emulsifying (and before C, D are moved into, A, B component are stirred in there-necked flask
Mix).Then E, F component is moved in two beakers respectively, ultrasonic emulsification 3 minutes；Emulsifying terminates inverted emulsion in rear two beakers
Re-mix in a beaker, still provide for 3 minutes ultrasonic emulsifications.Then it is evaporated under reduced pressure at 60 DEG C with Rotary Evaporators, is obtained
Solid product it is drying for one day in vacuum drying oven.Then deionized water rinse 3 times, remove nitrate nonahydrate and other are miscellaneous
Matter.Then it is scattered in again in oil phase, condensing reflux one day.Nanometer silver based on stabilized polyurethane agent for surface modification is obtained
Toluene dispersion liquid (its outward appearance is as shown in Figure 1), transmission electron microscope (TEM) image can measure nanometer silver particle diameter in 12nm or so (such as Fig. 2
It is shown).Product after purification is directly dispersed in water, the nanometer silver moisture for surface modification based on stabilized polyurethane agent is obtained
(its outward appearance is as shown in figure 1, transmission electron microscope (TEM) image can measure particle diameter that nanometer silver is dispersed in water (such as Fig. 3 institutes to dispersion liquid
Show).
Case 2.
In the 250mL four-neck flasks equipped with agitator, thermometer and reflux condensing tube, add 17.4g isophorones two different
Cyanate (IPDI), stirs the PCDL that water is weeded out with Dropping funnel Deca 51.3g Jing molecules under room temperature
With the mixed solution of 0.05g catalyst dibutyltin dilaurates (DBTDL), rate of addition control is in 1.5h.Deca is tied
1-2h are reacted at 45 ± 5 DEG C after beam, to reach theoretical value (anti-by di-n-butylamine until determining NCO group to then heat to 60 DEG C
Obtained by titration measuring), the base polyurethane prepolymer for use as of NCO end-blockings is obtained, the polydimethylsiloxane (PDMS) of 6.83g is added,
2h is reacted at 50 DEG C, is equally determined system-NCO group content, theoretical value is close in-NCO content, 3.76g is pre-dried
Dihydromethyl propionic acid (DMPA) powder be added in base polyurethane prepolymer for use as I in three batches, reacted at 65 ± 5 DEG C, reacted
Add proper amount of acetone regulation system viscosity in journey.The extent of reaction is determined by di-n-butylamine back titration method, will after reaching theoretical value
0.01g hydroquinone of polymerization retarder and 2.83g hydroxyethyl methylacrylates (HEMA) are added drop-wise in performed polymer II, are warming up to 75 ± 5
DEG C reaction, until can't detect NCO in 2265cm with infrared spectrum-1The absworption peak at place, obtains organic-silicon-modified polyurethane steady
Determine agent.
Claims (4)
1. a kind of preparation method of the amphiphilic nano silver based on stabilized polyurethane agent, concrete preparation method are as follows：
(1). the reverse breast of silver salt inverted emulsion and reducing agent is prepared respectively with polyurethane as stabilizer using reverse miniemulsion method
Liquid；(2). the ultrasonic fine crankshaft of difference, then mix the nanometer silver that fine crankshaft again generates polyurethane surface modification；(3). rotation is steamed
Send out toluene solvant, vacuum drying, washing centrifugation purification；(4). it is scattered in oil phase again, condensing reflux, in removing system
Residual moisture obtains oiliness nano silver dispersion, in addition by purification ultrasonic disperse in water phase, obtains water nano silver dispersion
Liquid；Above reactant composition mainly includes stabilized polyurethane agent, toluene, silver salt, reducing agent, deionized water, and main reactant is matched somebody with somebody
Than as follows：
What is synthesized concretely comprises the following steps：Two parts of polyurethane toluene solutions are prepared by above proportioning first, component A, B groups is respectively designated as
Point；Equally silver salt solution is prepared by proportioning, be named as component C；Reducing agent aqueous solution is prepared by proportioning, D components are named as；So
Afterwards component C is added drop-wise in component A, inverted emulsion component E is formed；D components are added drop-wise in B component, inverted emulsion F groups are formed
Point；E, F component is moved in two beakers respectively, ultrasonic fine crankshaft 3-5 minutes；Emulsifying terminates inverted emulsion weight in rear two beakers
Newly it is mixed in a beaker, then carries out 3-5 minutes ultrasound fine crankshaft；It is evaporated under reduced pressure at 60 DEG C with Rotary Evaporators, by gained
Product under the conditions of 45 DEG C, is dried 24 hours in vacuum drying oven, and deionized water is added in desciccate, and ultrasound disperses which
In deionized water, centrifugation removes impurity, is subsequently scattered in again in toluene, condensing reflux 24 hours, removes residual water
Point, that is, the nanometer silver for being dispersed among toluene based on stabilized polyurethane agent is obtained；Product after washing centrifugation is surpassed again
Sound is dispersed in water, that is, the nanometer silver for being dispersed among water based on stabilized polyurethane agent is obtained.
2. the preparation method of the amphiphilic nano silver based on stabilized polyurethane agent according to claim 1, it is characterised in that
The synthesis of the stabilized polyurethane agent for being used is mainly with diisocyanate cpd, polyether polyol, organo-silicon compound, double hydroxyls
Methyl acid compound, hydroxy acryl acid ester monomer be primary raw material, synthesis of polyurethane stabilizer, wherein diisocyanate chemical combination
Thing is 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, isophorone diisocyanate, two isocyanide of diphenyl methane
Acid esters, hexa-methylene -1,6- diisocyanate；Polyether polyol from the Polyethylene Glycol of different molecular weight, polypropylene glycol, poly- four
Hydrogen furan glycol, polycaprolactone glycol, PCDL, polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO)
Polyether polyol, its molecular weight ranges are 400-12000；Organo-silicon compound select ɑ, alpha, omega-dihydroxy polydimethyl siloxane,
Dihydroxy polydiphenylsiloxane, dihydroxy trifluompropyl methyl polysiloxane, dihydroxy polycaprolactone-polydimethylsiloxanes
One of alkane-polycaprolactone co-polymer is planted, and its molecular weight ranges is 400-24000；Double methylol acid compounds select dihydroxy first
Base propanoic acid, dimethylolpropionic acid；Described hydroxy acryl acid ester monomer selects 2-(Acryloyloxy)ethanol, hydroxyethyl methacrylate second
Ester, Hydroxypropyl acrylate, Hydroxypropyl methacrylate；Stabilized polyurethane agent is characterised by that its composition mainly includes：30-50wt%
Polyether polyol, the diisocyanate cpd of 10-25wt%, the organo-silicon compound of 5-15wt%, double hydroxyls of 3-8wt%
Methyl acid compound, the hydroxy acryl acid ester compounds of 5-10wt%；The molecular weight ranges of synthesized stabilized polyurethane agent
For 3000-30000, and require that the stabilized polyurethane agent has preferable dissolubility in toluene, dredged by selecting different hydrophilic
In aqueouss, the polyether polyol of different molecular weight and regulation prepolymer, the content method of hydrophilic groups is so that prepolymer is in first
There is preferable dissolubility in benzene.
3. the preparation method of the amphiphilic nano silver based on stabilized polyurethane agent according to claim 1, it is characterised in that
Described silver salt is silver nitrate, silver nitrite and silver acetate.
4. the preparation method of the amphiphilic nano silver based on stabilized polyurethane agent according to claim 1, it is characterised in that
Described reducing agent is ammonia, sodium borohydride and hydrazine hydrate.
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| CN111116859B (en) * | 2019-12-31 | 2021-08-03 | 杭州吉华高分子材料股份有限公司 | Preparation method of antibacterial modified waterborne polyurethane |
| CN114346252B (en) * | 2021-12-30 | 2023-12-01 | 南通大学 | Nano silver colloid solution, preparation method thereof and washing-resistant antibacterial antiviral fabric |
| CN114163913B (en) * | 2022-01-18 | 2023-08-04 | 苏州邦得纳米涂层科技有限公司 | Preparation method of polyurethane cured silver-hybrid fluorine-containing antibacterial anticorrosive paint and coating |
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| KR20040026281A (en) * | 2002-09-23 | 2004-03-31 | 김주영 | Synthesis of Polyurethane Nanocomposite Film Containing Silver Nanoparticles |
| KR20030038585A (en) * | 2003-03-28 | 2003-05-16 | 인교진 | Synthesis of Silver/Polyurethane Nanocomposite Using Amphiphilic Urethane Acrylate |
| DE102008029858A1 (en) * | 2008-04-23 | 2009-10-29 | Byk-Chemie Gmbh | Stable dispersions of inorganic nanoparticles |
| CN102344697B (en) * | 2011-06-23 | 2013-06-12 | 江南大学 | Preparation method for photosensitive and amphiphilic polyurethane-stabilized nano-zinc oxide |
| CN102875736B (en) * | 2011-07-12 | 2015-05-13 | 比亚迪股份有限公司 | Waterborne polyurethane resin emulsion and preparation method thereof, two-component waterborne silver powder coating composition and preparation method thereof |
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Effective date of registration: 20191129 Address after: 225300 No. 17 Cultural West Road, Taixing Economic Development Zone, Taizhou City, Jiangsu Province Patentee after: Ruentex chemical (Taixing) Co. Ltd. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University |