CN103333507A - Water-soluble nano/polymer brush composite material and preparation method thereof - Google Patents
Water-soluble nano/polymer brush composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a water-soluble nano/polymer brush composite material. According to the method for preparing the water-soluble nano/polymer brush composite material, a polyacrylate polymer brush is synthesized, multiple carboxyls are introduced to side chains of the polyacrylate polymer brush so as to enable the polyacrylate polymer brush to be capable of forming a stable aqueous solution, the polyacrylate polymer brush is compounded by using the strong coordination capacity between carboxyl and Ag particles so as to protect silver nanoparticles, a silver nanoparticle/polymer composite aqueous solution capable of being stably dispersed is obtained by using the spatial structural nature of the polymer brush, and nano particles with small particle diameter and uniform distribution can be obtained and can be stably stored for a longer time.
Description
Technical field
The invention belongs to the synthesis of polymer material field, relate in particular to a kind of water-soluble nano/polymer brush matrix material and preparation method thereof.
Background technology
Matrix material is because the designability of its excellent comprehensive performances, particularly its performance is widely used in fields such as aerospace, national defence, traffic, physical culture.Nano composite material particularly.Nano composite material is to be external phase with matrixes such as resin, rubber, pottery and metals, be modified as disperse phase with metal, semi-conductor, rigid particles and other inorganic particulates of nano-scale, fiber, CNT (carbon nano-tube) etc., by suitable preparation method properties-correcting agent homogeneity ground is scattered in the body material, formation one contains the compound system of nano-sized materials mutually, and this system material is referred to as nano composite material.
At present because the peculiar property of nanoparticle, its structure is compared with conventional material very big variation has been taken place, and makes the performances such as catalysis, photoelectricity, magnetic, heat, mechanics of material that very big improvement arranged, and has important use and is worth.Except promoting for the performance of material, nano silver particles can play very strong germicidal action, and it has good use value at aspects such as medical, coating.The compound aspect of present polymkeric substance and nano material much is to adopt blend technique, by mechanical force nanoparticle is distributed among the material, it is big usually at hundreds of even to the scope of thousands of nanometers that but this method prepares the nano particle diameter of nanometer/polymer composites, uniform particle diameter is poor, and the nanoparticle secondary agglomeration takes place in matrix material easily that obtain, instability, and make degradation.The present invention therefore.
Summary of the invention
At the deficiency of present technology, the present invention is compound by a kind of new type of polymer brush and nanoparticle are carried out, and it is less to obtain particle diameter, the distribution homogeneous, and also the energy stable existence is in the matrix material of the aqueous solution.
In order to solve these problems of the prior art, concrete technical scheme provided by the invention is as follows:
A kind of water-soluble nano/polymer brush matrix material is characterized in that described matrix material is prepared by the following method:
1) monomer solution that will contain tert-butyl acrylate at least under catalyst action under the starvation condition by atom transfer radical polymerization method synthetic polyacrylate main chain and the polyacrylate side chain of obtaining respectively, temperature of reaction is 60-80 ℃, and the reaction times is 4-6h;
2) with trifluoroacetic acid solution, chloride reagent, 2-propine-1 alcohol polyacrylate backbone is carried out modification successively and handle, make the alkynyl that is introduced as grafting site on the polyacrylate backbone; Adopt NaN
3Dimethyl formamide solution the polyacrylate side chain carried out azide handle;
3) will introduce polyacrylate side chain after polyacrylate main chain behind the grafting site and azide are handled and be mixed in and carry out graft reaction in the pyridine, temperature of reaction is 50-80 ℃, obtains the polyacrylate polymers brush; Then the polyacrylate polymers brush is hydrolyzed, obtains the water-soluble polyacrylate polymer brush;
4) the water-soluble polyacrylate polymer brush is dissolved in the water, control pH adds AgNO under the condition of 8-9
3Solution adopts the UV-light method of reducing at water-soluble polyacrylate polymer surfaces synthesis of nano Ag particle, obtains water-soluble nano/polymer brush matrix material.
Another object of the present invention is to provide a kind of method for preparing water-soluble nano/polymer brush matrix material, it is characterized in that said method comprising the steps of:
1) monomer solution that will contain tert-butyl acrylate at least under catalyst action under the starvation condition by atom transfer radical polymerization method synthetic polyacrylate main chain and the polyacrylate side chain of obtaining respectively, temperature of reaction is 60-80 ℃, and the reaction times is 4-6h;
2) with trifluoroacetic acid solution, chloride reagent, 2-propine-1 alcohol polyacrylate backbone is carried out modification successively and handle, make the alkynyl that is introduced as grafting site on the polyacrylate backbone; Adopt NaN
3Dimethyl formamide solution the polyacrylate side chain carried out azide handle;
3) will introduce polyacrylate side chain after polyacrylate main chain behind the grafting site and azide are handled and be mixed in and carry out graft reaction in the pyridine, temperature of reaction is 50-80 ℃, obtains the polyacrylate polymers brush; Then the polyacrylate polymers brush is hydrolyzed, obtains the water-soluble polyacrylate polymer brush;
4) the water-soluble polyacrylate polymer brush is dissolved in the water, control pH adds AgNO under the condition of 8-9
3Solution adopts the UV-light method of reducing at water-soluble polyacrylate polymer surfaces synthesis of nano Ag particle, obtains water-soluble nano/polymer brush matrix material.
Preferably, described method steps 1) monomer solution is the mixing solutions of tert-butyl acrylate and other monomers in, and described other monomers are selected from one or more any mixing wherein of acrylamide, vinyl cyanide, methyl methacrylate.
Preferably, described method steps 1) molar content of tert-butyl acrylate is 60-100% in the middle monomer solution.
Preferably, described method steps 1) solvent of monomer solution is selected from N in, one or both any mixing wherein of dinethylformamide, acetone; Described catalyzer is made up of Organohalogen compounds/low-valent transition metals halogenide/part.
Preferably, described method steps 1) Organohalogen compounds are selected from trichloromethane, 1 in, wherein a kind of of 2-phenyl-chloride ethane, 2,2-dibromo-isobutyl acetoacetic ester, aryl sulfonyl chloride; Low-valent transition metals halogenide is one or more any mixing of cuprous chloride, cuprous bromide, iron protochloride; Described part is 2,2 ' Lian two pyridines, triphenylphosphine, N, N, N', N, `N', any mixing of one or more of a pentamethyl-diethylenetriamine (PMDETA), triethylamine; The ratio of three kinds of components is followed successively by (0.8-1) in the described catalyzer: (0.8-1): (0.8-1); The ratio that described catalyst system accounts for all monomers that feed intake is 2-30%.
Preferably, the polyacrylate backbone molecule amount described method steps 1) is 2000-7000; The molecular weight of described polyacrylic ester side chain is 2000-10000.
Preferably, described method steps 2) solvent of trifluoroacetic acid solution is chloroform or methylene dichloride in, and its concentration is 10-20mol/L; Chloride reagent is selected from: sulfur oxychloride, phosphorus oxychloride, wherein a kind of of oxalyl chloride.
Preferably, NaN described method steps 2)
3Dimethyl formamide solution concentration be 0.01-0.1mol/L, temperature of reaction is 40-70 ℃, the treatment time is 40-50h.
Preferably, the adding molar ratio of the polyacrylate side chain after the polyacrylate main chain described method steps 3) behind the introducing grafting site and azide are handled is: 1～8, the condition of described graft reaction is: catalyzer is cupric bromide/2,2 ' Lian two pyridine systems, its content is for dropping into 0.5% and 1.1% of reactant total mass, solvent is Virahol, and solvent load is 30-50 times of reactant quality, reaction times 60-80h.
Preferably, described method steps 4) its concentration of the aqueous solution of water-soluble polymer brush is 0.01-0.1g/mL in, regulates its pH with NaOH solution, the AgNO of adding
3Strength of solution is 0.01-0.1mol/L, and adding volume is the 0.01-0.1% of the aqueous solution volume of water-soluble polymer brush.
Preferably, described method steps 4) the medium ultraviolet rayed reduction reaction time is 1～5h; The particle size range of the nano silver particles that obtains is 1-30nm.
Technical scheme steps 2 of the present invention) polyacrylate backbone that obtains in is handled with trifluoroacetic acid solution, the tert-butyl ester is hydrolyzed to carboxyl, the recycling chloride reagent with the effect of 2-propine-1 alcohol, is introduced the alkynyl that can be used for grafting again with the carboxyl chloride at main chain.The polyacrylic ester side chain that acrylate monomer is synthetic is put into NaN
3Dimethyl formamide solution in handle, its azide is handled;
It is similar with the hydrolytic process of polyacrylate backbone in the step 3) polyacrylate polymers brush to be hydrolyzed, and adopts trifluoroacetic acid solution to handle, and the tert-butyl ester is hydrolyzed to carboxyl, the method unanimity.
Polymer brush (polymer brush) refers to that the end by the very high polymer molecular chain of density is connected on chain, surface or the interface and a kind of special macromolecular structure that forms.The size of the molecular chain that connects of surface is more neat, to such an extent as to and its density must can make greatly enough that polymer molecular chain is accurate to be arranged, and be forced to the outside stretching, extension in Surface Vertical ground to form the structure of similar brush to avoid the overlapping of molecular chain.Because the characteristic of the many novelties of the special initiation of its structure can be applied to many fields.
The present invention relates to a kind of water miscible nanometer/polymer brush (polymer brushes; Polymer brush) matrix material particularly is the matrix material of a kind of water miscible nano silver particles/polyacrylate polymers brush, belongs to nanometer and polymer composite field.The present invention is compound by a kind of new type of polymer brush and nanoparticle are carried out, and it is less to obtain particle diameter, the distribution homogeneous, and also the energy stable existence is in the matrix material of the aqueous solution.
Present method is by synthetic polyacrylate polymers brush; and at a lot of carboxyls of its side chain introducing; enable to form the stable aqueous solution, utilize simultaneously carboxyl can and the Ag particle between strong coordination ability, it is compound; protect for nano silver particles; also utilize simultaneously the space structure character of polymer brush, obtain can stable dispersion nano silver particles/polymkeric substance compound aqueous solution, and it is very little to obtain particle diameter; the nano particle of distribution homogeneous, the stable preservation of energy long period simultaneously.
Because the peculiar property of the polyacrylate polymers that the present invention obtains brush, make it that excellent stability arranged aspect the aqueous solution, the coating, resulting coating has by a relatively large margin lifting in properties such as sticking power, wear resistance and uniform surface, sterilization effects.
The method that the present invention prepares water miscible nanometer polymer brush matrix material is:
1) solution that will contain the monomer of tert-butyl acrylate at least synthesizes under the starvation condition by atom transferred free radical earlier under catalyst action, and temperature of reaction is 60-80 ℃, and the reaction times is 4-6h, obtains the main chain of polyacrylate; All the other monomers can be acrylamide, vinyl cyanide, methyl methacrylate one or more mixtures wherein; Wherein the molar content of tert-butyl acrylate is 60-100%; The solvent of monomer solution is N, a kind of or mixing wherein of dinethylformamide, acetone; Described catalyst system is made up of machine halogenide/low-valent transition metals halogenide/part.Wherein Organohalogen compounds are selected from: wherein a kind of of trichloromethane, 1,2-phenyl-chloride ethane, 2,2-dibromo-isobutyl acetoacetic ester, aryl sulfonyl chloride; Low-valent transition metals halogenide is wherein one or more of cuprous chloride, cuprous bromide, iron protochloride; Part is: 2,2 '-Lian, two pyridines, triphenylphosphine, N, N, N', N, `N', a pentamethyl-diethylenetriamine (PMDETA), triethylamine wherein one or more; The ratio of three kinds of components is respectively (0.8-1): (0.8:1): (0.8-1); Catalyst system accounts for all monomer ratio that feed intake and is (2-30) %;
2) with 1) polyacrylate backbone that obtains handles with trifluoroacetic acid solution, and the tert-butyl ester is hydrolyzed to carboxyl, and the recycling chloride reagent with the effect of 2-propine-1 alcohol, is introduced the alkynyl that can be used for grafting again with the carboxyl chloride at main chain; The solvent of trifluoroacetic acid solution is chloroform or methylene dichloride, and its concentration is 10-20mol/L; Chloride reagent is selected from: sulfur oxychloride, phosphorus oxychloride, wherein a kind of of oxalyl chloride;
3) adopt the method identical with step 1), with the side chain of the synthetic polyacrylic ester of acrylate monomer; Side chain is put into NaN
3Dimethyl formamide solution in handle, its azide is handled; NaN
3Dimethyl formamide solution concentration be 0.01-0.1mol/L, temperature of reaction is 40-70 ℃, the treatment time is 40-50h;
4) with 2) with 3) obtaining main chain and side chain is blended in the pyridine, temperature of reaction is about 50-80 ℃, carries out graft reaction, again with its hydrolysis, obtains the water-soluble polyacrylate polymer brush;
5) with 4) polymer brush that obtains is dissolved in the water, and regulating pH is between the 8-9, adds AgNO
3Solution adopts UV-light method of reducing synthesis of nano Ag particle, and obtaining can the matrix material of stable dispersion in the aqueous solution.
The backbone molecule amount of described polyacrylate is 2000-7000, and this molecular weight is the molecular weight before the hydrolysis; Polyacrylic ester branched chain molecule amount is 2000-10000, and this molecular weight is the molecular weight before azide is handled.
With respect to scheme of the prior art, advantage of the present invention is:
The present invention is by synthetic polyacrylate polymers brush; and at a lot of carboxyls of its side chain introducing; enable to form the stable aqueous solution, utilize simultaneously carboxyl can and the Ag particle between strong coordination ability, it is compound; protect for nano silver particles; also utilize simultaneously the space structure character of polymer brush, obtain can stable dispersion nano silver particles/polymkeric substance compound aqueous solution, and it is very little to obtain particle diameter; the nano particle of distribution homogeneous, the stable preservation of energy long period simultaneously.By the synthetic nanometer silver of present method/polyacrylate polymers brush matrix material, can access the very little nano aqueous solution of particle diameter of stable existence, have good result of use, the energy stable dispersion is in the aqueous solution.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 is the nano silver particles Electronic Speculum figure of 2nm for embodiment 1 gained particle diameter;
Fig. 2 is the nano silver particles Electronic Speculum figure of 4nm for embodiment 2 gained particle diameters;
Fig. 3 is the nano silver particles Electronic Speculum figure of 20nm for embodiment 3 gained particle diameters;
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention, all equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment 1
(1) the polymer brush main chain is synthetic:
Elder generation is with the cuprous bromide of 0.361g, 0.384g triethylamine and 3mL acetone ultrasonic mixing in vial, add 0.487g dibromo-isobutyl acetoacetic ester again, 3.575g (mass ratio is Acrylic Acid Monomer: tert-butyl acrylate 80%, acrylamide 20%) stir after, inert gas replacement seals, 70 ℃ of reaction 4.5h.Stopped reaction is solvent with the tetrahydrofuran (THF), is that precipitation agent repeatedly cleans drying with the mixing solutions of methyl alcohol and water volume ratio 1:2; Obtain the polyacrylic ester long-chain.
(2) backbone modification adds grafting site:
The polyacrylic ester that 2.567g step (1) is obtained joins in the dichloromethane solution of trifluoroacetic acid that 6mL concentration is 15mol/L and stirs the reaction 16h that is hydrolyzed, and hydrolysate can be precipitated out, centrifugal, filtration, cleaning, drying.
Hydrolysate is dissolved in the sulfur oxychloride, and temperature is 50 ℃, and reaction 24h revolves to steam and removes unnecessary solvent, drying.
Main chain product 0.650g with the processing of chloride; be dissolved in the N of 50mL, add 2-propine-1 alcohol of 0.453g in dinethylformamide (DMF) solution, under the triethylamine catalysis of 1.1mL; 70 ℃ of reaction 12h, process is carried out under the protection of inert gas condition.Revolving the steaming desolventizing, add methylene dichloride, use the dilute hydrochloric acid acidifying again, is precipitation agent processing methylene dichloride liquid layer with the mixing solutions of methyl alcohol and water volume ratio 1:2, obtains having the main chain of alkynyl, cleaning, drying.
(3) the polyacrylic acid ester side chain is synthetic:
Adopt the method for step (1) to synthesize side chain, acrylate monomer is tert-butyl acrylate; Synthetic polyacrylic acid ester side chain 1.264g is dissolved in the NaN that 30mL concentration is 0.03mol/L
3Dimethyl formamide solution, 60 ℃ the reaction 50h, remove by filter excessive N aN
3The salt that generates revolves to steam and removes unnecessary solvent, extracts several times drying respectively with ethyl acetate and water.
(4) polymer brush is synthetic:
To introduce main chain product (main chain that the has alkynyl) 0.5g of alkynyl, and the side chain that the 1.83g azide is handled is dissolved in the aqueous isopropanol of 60mL, at 2 of 0.01g cupric bromide and 0.02g; under 2 '-Lian, the two pyridine effects; under the protection of inert gas, 60 ℃ of reaction 75h revolve the steaming desolventizing; with ethyl acetate, water; extraction respectively, dry ethyl acetate liquid layer filters; revolve the steaming desolventizing, drying obtains polymer brush.
Again according to the method for hydrolysis of step (2) with the polymer brush processing that is hydrolyzed, obtain containing the polymer brush of a large amount of carboxyls.
(5) UV-light reduction preparation nanometer/polymer brush matrix material:
Polymer brush 0.23g after the hydrolysis that (4) are made is dissolved in the 8mL water, and regulating pH with the NaOH solution of 3mol/L again is 8-9, and adding 3mL solubility is the AgNO of 0.1mol/L
3Solution, mixing, UV-irradiation 2h, reduction obtains the stable, aqueous solution of nanometer silver/polymer brush.
Embodiment 2
(1) the polymer brush main chain is synthetic:
With the cuprous bromide of 0.361g, 0.384g triethylamine and 3mL acetone ultrasonic mixing in vial adds 0.487g dibromo-isobutyl acetoacetic ester more earlier, after 3.575g Acrylic Acid Monomer (all being tert-butyl acrylate) stirs, inert gas replacement seals, 70 ℃ of reaction 4.5h.Stopped reaction is solvent with the tetrahydrofuran (THF), is that precipitation agent repeatedly cleans drying with the mixing solutions of methyl alcohol and water volume ratio 1:2; Obtain the polyacrylic ester long-chain.
(2) backbone modification adds grafting site:
With 2.567g(1) polyacrylic ester that obtains joins in the dichloromethane solution of trifluoroacetic acid that 6mL concentration is 15mol/L and stirs the reaction 16h that is hydrolyzed, and hydrolysate can be precipitated out, centrifugal, filtration, cleaning, drying.
Hydrolysate is dissolved in the sulfur oxychloride, and temperature is 50 ℃, and reaction 24h revolves to steam and removes unnecessary solvent, drying.
With the main chain product 0.650g that chloride is handled, be dissolved in the N of 50mL, add 2-propine-1 alcohol of 0.453g in the dinethylformamide solution, under the triethylamine catalysis of 1.1mL, 70 ℃ of reaction 12h, process is carried out under the protection of inert gas condition.Revolving the steaming desolventizing, add methylene dichloride, use the dilute hydrochloric acid acidifying again, is precipitation agent processing methylene dichloride liquid layer with the mixing solutions of methyl alcohol and water volume ratio 1:2, obtains the main chain that main chain has alkynyl, cleaning, drying.
(3) the polyacrylic acid ester side chain is synthetic:
Adopt the method for step (1) to synthesize side chain, initiator dibromo-isobutyl acetoacetic ester content is 1/2 in the step (1), and acrylate monomer is tert-butyl acrylate; Synthetic polyacrylic acid ester side chain 1.264g is dissolved in the NaN that 30mL concentration is 0.03mol/L
3Dimethyl formamide solution, 60 ℃ the reaction 50h, remove by filter excessive N aN
3The salt that generates revolves the steaming solvent, extracts several times drying respectively with ethyl acetate and water.
(4) polymer brush is synthetic:
To introduce the main chain product 0.5g of alkynyl, and the side chain that the 1.83g azide is handled is dissolved in the aqueous isopropanol of 60mL, at 2 of 0.01g cupric bromide and 0.02g; 2 ' under the Lian two pyridine effects; under the protection of inert gas, 60 ℃ of reaction 75h revolve the steaming desolventizing; with ethyl acetate, water; extraction respectively, dry ethyl acetate liquid layer filters; revolve the steaming desolventizing, drying obtains polymer brush.
Again according to the method for hydrolysis of step (2) with the polymer brush processing that is hydrolyzed, obtain the polymer brush that side chain contains a large amount of carboxyls.
(5) UV-light reduction preparation nanometer/polymer brush matrix material:
Polymer brush 0.23g after the hydrolysis that (4) are made be dissolved in the 8mL water, regulating pH with the NaOH solution of 3mol/L again is 8-9, adding 4mL solubility is the AgNO of 0.1mol/L
3Solution, mixing, UV-irradiation 2h, reduction obtains the stable, aqueous solution of nanometer silver/polymer brush.
Embodiment 3
(1) the polymer brush main chain is synthetic:
Elder generation is with the cuprous bromide of 0.361g, 0.384g triethylamine and 3mL acetone ultrasonic mixing in vial, add 0.487g dibromo-isobutyl acetoacetic ester again, 3.575g (mass ratio is Acrylic Acid Monomer: tert-butyl acrylate 70%, methyl methacrylate 20%, vinyl cyanide 10%) stir after, inert gas replacement, seal 70 ℃ of reaction 4.5h.Stopped reaction is solvent with the tetrahydrofuran (THF), is that precipitation agent repeatedly cleans drying with the mixing solutions of methyl alcohol and water volume ratio 1:2; Obtain the polyacrylic ester long-chain.
(2) backbone modification adds grafting site:
With 2.567g(1) polyacrylic ester that obtains joins in the dichloromethane solution of trifluoroacetic acid that 6mL concentration is 15mol/L and stirs the reaction 16h that is hydrolyzed, and hydrolysate can be precipitated out, centrifugal, filtration, cleaning, drying.
Hydrolysate is dissolved in the sulfur oxychloride, and temperature is 50 ℃, and reaction 24h revolves to steam and removes unnecessary solvent, drying.
With the main chain product 0.650g that chloride is handled, be dissolved in the N of 50mL, add 2-propine-1 alcohol of 0.453g in the dinethylformamide solution, under the triethylamine catalysis of 1.1mL, 70 ℃ of reaction 12h, process is carried out under the protection of inert gas condition.Revolving the steaming desolventizing, add methylene dichloride, use the dilute hydrochloric acid acidifying again, is precipitation agent processing methylene dichloride liquid layer with the mixing solutions of methyl alcohol and water volume ratio 1:2, obtains the main chain that main chain has alkynyl, cleaning, drying.
(3) the polyacrylic acid ester side chain is synthetic:
Adopt the method for step (1) to synthesize side chain, initiator dibromo-isobutyl acetoacetic ester content is 1/2 in the step (1), and acrylate monomer is tert-butyl acrylate; Synthetic polyacrylic acid ester side chain 1.264g is dissolved in the NaN that 30mL concentration is 0.03mol/L
3Dimethyl formamide solution, 60 ℃ the reaction 50h, remove by filter excessive N aN
3The salt that generates revolves the steaming desolventizing, extracts several times drying respectively with ethyl acetate and water.
(4) polymer brush is synthetic:
To introduce the main chain product 0.5g of alkynyl, and the side chain that the 1.83g azide is handled is dissolved in the aqueous isopropanol of 60mL, at 2 of 0.01g cupric bromide and 0.02g; 2 ' under the Lian two pyridine effects; under the protection of inert gas, 60 ℃ of reaction 75h revolve the steaming desolventizing; with ethyl acetate, water; extraction respectively, dry ethyl acetate liquid layer filters; revolve the steaming desolventizing, drying obtains polymer brush.
Again according to the method for hydrolysis of step (2) with the polymer brush processing that is hydrolyzed, obtain containing the polymer brush of a large amount of carboxyls.
(5) UV-light reduction preparation nanometer/polymer brush matrix material:
Polymer brush 0.23g after the hydrolysis that (4) are made be dissolved in the 8mL water, regulating pH with the NaOH solution of 3mol/L again is 8-9, adding 4mL solubility is the AgNO of 0.1mol/L
3Solution, mixing, UV-irradiation 2.5h, reduction obtains the stable, aqueous solution of nanometer silver/polymer brush.
Fig. 1 is the nano silver particles Electronic Speculum figure of 2nm for embodiment 1 gained particle diameter; Fig. 2 is the nano silver particles Electronic Speculum figure of 4nm for embodiment 2 gained particle diameters; Fig. 3 is the nano silver particles Electronic Speculum figure of 20nm for embodiment 3 gained particle diameters; Characterize by transmission electron microscope, the median size of embodiment 1,2,3 resulting nano silver particles is 2,4,20nm.It's 6 months has been past the resulting matrix material aqueous solution does not also have tangible clustering phenomena, stable existence.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (11)
1. water-soluble nano/polymer brush matrix material is characterized in that described matrix material is prepared by the following method:
1) monomer solution that will contain tert-butyl acrylate at least under catalyst action under the starvation condition by atom transfer radical polymerization method synthetic polyacrylate main chain and the polyacrylate side chain of obtaining respectively, temperature of reaction is 60-80 ℃, and the reaction times is 4-6h;
2) with trifluoroacetic acid solution, chloride reagent, 2-propine-1 alcohol polyacrylate backbone is carried out modification successively and handle, make the alkynyl that is introduced as grafting site on the polyacrylate backbone; Adopt NaN
3Dimethyl formamide solution the polyacrylate side chain carried out azide handle;
3) will introduce polyacrylate side chain after polyacrylate main chain behind the grafting site and azide are handled and be mixed in and carry out graft reaction in the pyridine, temperature of reaction is 50-80 ℃, obtains the polyacrylate polymers brush; Then the polyacrylate polymers brush is hydrolyzed, obtains the water-soluble polyacrylate polymer brush;
4) the water-soluble polyacrylate polymer brush is dissolved in the water, control pH adds AgNO under the condition of 8-9
3Solution adopts the UV-light method of reducing at water-soluble polyacrylate polymer surfaces synthesis of nano Ag particle, obtains water-soluble nano/polymer brush matrix material.
2. method for preparing water-soluble nano/polymer brush matrix material is characterized in that said method comprising the steps of:
1) monomer solution that will contain tert-butyl acrylate at least under catalyst action under the starvation condition by atom transfer radical polymerization method synthetic polyacrylate main chain and the polyacrylate side chain of obtaining respectively, temperature of reaction is 60-80 ℃, and the reaction times is 4-6h;
2) with trifluoroacetic acid solution, chloride reagent, 2-propine-1 alcohol polyacrylate backbone is carried out modification successively and handle, make the alkynyl that is introduced as grafting site on the polyacrylate backbone; Adopt NaN
3Dimethyl formamide solution the polyacrylate side chain carried out azide handle;
3) will introduce polyacrylate side chain after polyacrylate main chain behind the grafting site and azide are handled and be mixed in and carry out graft reaction in the pyridine, temperature of reaction is 50-80 ℃, obtains the polyacrylate polymers brush; Then the polyacrylate polymers brush is hydrolyzed, obtains the water-soluble polyacrylate polymer brush;
4) the water-soluble polyacrylate polymer brush is dissolved in the water, control pH adds AgNO under the condition of 8-9
3Solution adopts the UV-light method of reducing at water-soluble polyacrylate polymer surfaces synthesis of nano Ag particle, obtains water-soluble nano/polymer brush matrix material.
3. method according to claim 2, it is characterized in that described method steps 1) in monomer solution be the mixing solutions of tert-butyl acrylate and other monomers, described other monomers are selected from one or more any mixing wherein of acrylamide, vinyl cyanide, methyl methacrylate; The molar content of tert-butyl acrylate is 60-100% in the monomer solution.
4. method according to claim 2 is characterized in that described method steps 1) in the solvent of monomer solution be selected from N, one or both any mixing wherein of dinethylformamide, acetone; Described catalyzer is made up of Organohalogen compounds/low-valent transition metals halogenide/part.
5. method according to claim 4 is characterized in that described method steps 1) in Organohalogen compounds be selected from trichloromethane, 1, wherein a kind of of 2-phenyl-chloride ethane, 2,2-dibromo-isobutyl acetoacetic ester, aryl sulfonyl chloride; Low-valent transition metals halogenide is one or more any mixing of cuprous chloride, cuprous bromide, iron protochloride; Described part is 2,2 ' Lian two pyridines, triphenylphosphine, N, N, N', N, `N', any mixing of one or more of a pentamethyl-diethylenetriamine (PMDETA), triethylamine; The ratio of three kinds of components is followed successively by (0.8-1) in the described catalyzer: (0.8-1): (0.8-1); The ratio that described catalyst system accounts for all monomers that feed intake is 2-30%.
6. method according to claim 2 is characterized in that described method steps 1) described in polyacrylate backbone molecule amount be 2000-7000; The molecular weight of described polyacrylic ester side chain is 2000-10000.
7. method according to claim 2 is characterized in that described method steps 2) in the solvent of trifluoroacetic acid solution be chloroform or methylene dichloride, its concentration is 10-20mol/L; Chloride reagent is selected from: sulfur oxychloride, phosphorus oxychloride, wherein a kind of of oxalyl chloride.
8. method according to claim 2 is characterized in that described method steps 2) middle NaN
3Dimethyl formamide solution concentration be 0.01-0.1mol/L, temperature of reaction is 40-70 ℃, the treatment time is 40-50h.
9. method according to claim 2, it is characterized in that described method steps 3) in introduce the polyacrylate side chain after polyacrylate main chain and the azide processing behind the grafting site the adding molar ratio be: 1～8, the condition of described graft reaction is: catalyzer is cupric bromide/2,2 ' Lian two pyridine systems, its content is for dropping into 0.5% and 1.1% of reactant total mass, solvent is Virahol, and solvent load is 30-50 times of reactant quality, reaction times 60-80h.
10. method according to claim 2 is characterized in that described method steps 4) in its concentration of the aqueous solution of water-soluble polymer brush be 0.01-0.1g/mL, regulate its pH with NaOH solution, the AgNO of adding
3Strength of solution is 0.01-0.1mol/L, and adding volume is the 0.01-0.1% of the aqueous solution volume of water-soluble polymer brush.
11. method according to claim 2 is characterized in that described method steps 4) the medium ultraviolet rayed reduction reaction time is 1～5h; The particle size range of the nano silver particles that obtains is 1-30nm.
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