CN102391527B - Preparation method of uniform-dimension polymer nano microspheres - Google Patents
Preparation method of uniform-dimension polymer nano microspheres Download PDFInfo
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- CN102391527B CN102391527B CN201110192571A CN201110192571A CN102391527B CN 102391527 B CN102391527 B CN 102391527B CN 201110192571 A CN201110192571 A CN 201110192571A CN 201110192571 A CN201110192571 A CN 201110192571A CN 102391527 B CN102391527 B CN 102391527B
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Abstract
The invention relates to a preparation method of uniform-dimension polymer nano microspheres, which comprises the following steps: mixing copolymer and solvent in a certain proportion, and putting the mixture in a container; and heating the container containing the polymer and solvent to a certain temperature, and keeping for some time, thereby obtaining the polymer microspheres dispersed in solvent, wherein the copolymer is composed of a chain segment A and a chain segment B; the chain segment A is polystyrene, polymethylstyrene or polyacrylonitrile; and the chain segment B is polymethyl methacrylate, poly(N,N-dimethylaminoethyl methacrylate), dimethylamino methyl polymethacrylate, poly(2-vinyl pyridine), poly(4-vinyl pyridine) or polyoxyethylene. The polymer microspheres obtained by the method provided by the invention have highly uniform dimension, and the particle size can be regulated within the range of 20-200nm. The method provided by the invention is simple, is not related to chemical reaction, has the advantages of short technical process, low cost and high yield, and is especially applicable to large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of size homogeneous polymer nano-microspheres; Prepared polymer nano-microspheres can be used as standard metering material, pharmaceutical carrier, support of the catalyst, filler, coating, pigment, sorbent material etc., is widely used in fields such as precision instrument, precision sizing, clinical detection, chemical separating, inspection and quarantine, environment measuring, material be synthetic.
Background technology
Polymer microballoon is widely used in fields such as chemistry, chemical industry, material, biomedical engineering such as dimension standard material, pharmaceutical carrier, support of the catalyst, filler, coating, pigment, sorbent material.The size of polymer microballoon and distribution, surface properties directly determine performance and the result of use in application process.Especially in high precision such as photovaltaic material and reference material, value added applications occasion, the control of the particle diameter of polymer microballoon is more crucial.
Existing preparation has the method for polymer microballoon, mainly can be divided into two big types.The one, being set out by monomer obtains the chemical process of microballoon through polyreaction, like letex polymerization, precipitation polymerization etc.; The 2nd, being set out by polymkeric substance obtains the physical method of microballoon through processes such as volatilization, depositions, like film emulsification, micro-fluidic etc.But existing method all will be used plurality of raw materials or specific installation, and operation is many, and is restive, complex operation, and productive rate is low; And be difficult to prepare the microballoon of particle diameter below 100 nanometers.As disclosing a kind of method for preparing polymer microballoon through precipitation polymerization in the patent 200410072867.4.In the method; Need to use multiple organic reagents such as monomer, linking agent, initiator, washing composition; Relate to that reagent is refining, heated and stirred, solvent steam remove, a plurality of steps such as filtration under diminished pressure, washing; The microballoon size that obtains is not suitable for dimensional requirement smaller applications field more than 1 micron.Patent 200710064716.8 discloses a kind of method of utilizing film emulsification to prepare polymer microballoon.In the method; Need to use special-purpose film emulsifier unit and expensive SPG film; And use reagent and starting material such as polymkeric substance, organic solvent, water, emulsifying agent; Preparation process comprises a plurality of steps such as the solution preparation, ultrasonic emulsification, membrane filtration, solvent removal of pre-treatment, oil phase and the water of SPG film, and the microballoon size that obtains is also at micron order.Therefore, press for the method that the development advantages of simplicity and high efficiency prepares the nano grade polymer microballoon.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of size homogeneous polymer nano-microspheres for the deficiency of improving prior art.
Technical scheme of the present invention is: a kind of preparation method of size homogeneous polymer nano-microspheres, it is characterized in that with the multipolymer that is made up of segments A and segment B be starting material, and heating is dissolved multipolymer in solvent, obtain polymer microballoon; Its concrete steps are following:
The multipolymer and the solvent that 1) will constitute by segments A and segment B;
2) with the mixture heating up and the insulation of multipolymer and solvent, promptly obtain being scattered in the polymer microballoon in the solvent.
Preferred above-mentioned multipolymer is made up of segments A and segment B; Segments A is PS, polyvinyltoluene or polyacrylonitrile, and segment B is polymethylmethacrylate, polymethyl acrylic acid dimethylaminoethyl, polymethyl acrylic acid dimethylamino methyl esters, gathers (2-vinyl pyridine), gathers (4-vinylpridine) or T 46155.The weight ratio of preferred segments A and segment B is 1: 0.2-1: 1.The total molecular weight of preferred copolymer is 10,000-300,000 dalton.
Preferred above-mentioned solvent is ethanol, Virahol, terepthaloyl moietie, formic acid, acetate or propionic acid.The weight ratio of preferred copolymer and solvent is 1: 4-1: 10000.
As improvement of the present invention, above-mentioned steps 1) can use heat resistant plastice container or heavy wall Glass Containers or stainless steel autoclave in.As further improvement of the present invention, above-mentioned steps 2) in heating and insulation time, can use stir or concussion to accelerate the formation of polymer microballoon.
The temperature of the heating described in the preferred above-mentioned steps 2 is controlled at 30 ℃-200 ℃; The time of insulation was controlled at 0.1-100 hour.
Beneficial effect:
The present invention is based on the technology of solvent to a certain segmental selectivity swelling system monodisperse polymer Nano microsphere in the multipolymer.When multipolymer and selective solvent mixing and heating; Solvophilic segment in the multipolymer is because intensive solvation and swelling, and another kind of repeating unit is because temperature raises, and the segmental mobility is reinforced; Two segments are because incompatible on the thermodynamics; Be separated, forming with solvophilic segment is shell, and solvophobic segment is the spherical nanostructure of nuclear.The particle diameter of microballoon can be regulated through the conditions such as chemical constitution, solvent types and treatment temp that change employed multipolymer within the specific limits.The polyalcohol microspherulite diameter homogeneous that this method obtains, big I is regulated in the scope of 20-200 nanometer.If what use is polar solvent, the polarity segment in the multipolymer can form the shell of microballoon, is beneficial to the dispersion of microballoon in water medium and uses and follow-up chemical modification functionalization.The inventive method does not relate to chemical reaction, need not to use the special preparation device, only uses polymkeric substance and solvent; Only comprise mixing, two simple steps of heating for dissolving, preparation process height is controlled, with low cost; Productive rate is high, has good scale operation prospect.
Description of drawings
Fig. 1 is sem (SEM) figure of the prepared polymer microballoon of embodiment 1;
Fig. 2 is sem (SEM) figure of the prepared polymer microballoon of embodiment 3.
Embodiment
Embodiment 1
1) is that 1: 0.3 PS and the multipolymer of polymethylmethacrylate (molecular weight is 70,000) place 50 milliliters the glass flask of being furnished with reflux with 1 gram weight ratio, in flask, adds 30 gram propionic acid again;
2) with oil bath with liquid heat to 110 in the flask ℃, and kept 10 hours;
3) stop heating, cool to room temperature promptly obtains being scattered in the polymer microballoon in the propionic acid.
Figure is as shown in Figure 1 for the sem of the polymer microballoon of gained (SEM); The microsphere diameter that records from SEM figure is 55 nanometers; And size homogeneous.
Embodiment 2
Embodiment 2 has increased polymer loading with the raising productive rate with respect to embodiment 1 step 1), and has improved solvent temperature to reduce the dissolving required time.
1) be that 1: 0.3 the PS and the molecular weight of copolymer of polymethylmethacrylate are 70,000 dalton with 5 gram weight ratio) place 50 milliliters the glass flask of being furnished with reflux, in flask, add 30 gram propionic acid again;
2) with oil bath with liquid heat to 150 in the flask ℃, and kept 2 hours;
3) stop heating, cool to room temperature promptly obtains being scattered in the polymer microballoon in the propionic acid.
With the polymer microballoon of sem observation gained, the microsphere diameter that records from SEM figure also is 55 nanometers, and the size homogeneous.
Embodiment 3
Embodiment 2 has changed kind, molecular weight, the segmental weight ratio of the multipolymer that uses with respect to embodiment 1, and the weight ratio of multipolymer and solvent is to obtain the polymer microballoon of different chemical composition and size.
1) is that 1: 0.2 PS and the multipolymer that gathers (4-vinylpridine) (molecular weight 20,000 dalton) place 25 milliliters the glass flask of being furnished with reflux with 2 gram weight ratio, in flask, adds 10 gram propionic acid again;
2) with oil bath liquid agitation in the flask is heated to 30 ℃, and kept 10 minutes;
3) stop heating, cool to room temperature promptly obtains being scattered in the polymer microballoon in the propionic acid.
The scanning electron microscope image of the polymer microballoon of gained is as shown in Figure 2; The microsphere diameter that records from SEM figure is 30 nanometers; And size homogeneous.
Embodiment 4
Embodiment 4 has changed employed multipolymer and solvent types with respect to embodiment 1 step 1).
1) is that 1: 1 the polyvinyltoluene and the multipolymer of polymethyl acrylic acid dimethylaminoethyl (total molecular weight 300,000) place 250 milliliters the glass flask of being furnished with reflux with 0.01 gram weight ratio, in flask, adds 100 gram acetate again;
2) with oil bath with liquid heat to 110 in the flask ℃, and kept 1 hour;
3) stop heating, cool to room temperature promptly obtains being scattered in the polymer microballoon in the acetate.
The microsphere diameter that records from SEM figure is 200 nanometers, and the size homogeneous.
Embodiment 5
Embodiment 5 has changed the kind and the solvent of employed multipolymer with respect to embodiment 1 step 1).
1) is that 1: 0.5 the polyacrylonitrile and the multipolymer of T 46155 (total molecular weight 1.5 ten thousand dalton) place 50 milliliters stainless steel hydrothermal reaction kettle with 0.1 gram weight ratio, in reaction kettle, adds 10 gram Virahols again;
2) reaction kettle is placed 180 ℃ baking oven, and kept 100 hours;
3) stop heating, cool to room temperature promptly obtains being scattered in the polymer microballoon in the water.
The microsphere diameter that records from SEM figure is 60 nanometers, and the size homogeneous.
Claims (4)
1. the preparation method of a size homogeneous polymer nano-microspheres, its concrete steps are following:
The multipolymer and the solvent that 1) will constitute by segments A and segment B; The segments A of wherein said multipolymer is PS, polyvinyltoluene or polyacrylonitrile, and segment B is polymethylmethacrylate, polymethyl acrylic acid dimethylaminoethyl, polymethyl acrylic acid dimethylamino methyl esters, gathers (2-vinyl pyridine), gathers (4-vinylpridine) or T 46155; The weight ratio of segments A and segment B is 1:0.2-1:1; The total molecular weight of multipolymer is 10,000-300,000 dalton;
2) with the mixture heating up and the insulation of multipolymer and solvent, promptly obtain being scattered in the polymer microballoon in the solvent.
2. according to right 1 described method, it is characterized in that the weight ratio of multipolymer and solvent is 1:4-1:10000 in the step 1).
3. according to right 1 described method, it is characterized in that described solvent is ethanol, Virahol, terepthaloyl moietie, formic acid, acetate or propionic acid.
4. according to right 1 described method, it is characterized in that step 2) in the heating temperature be 30 ℃-200 ℃; The time of insulation is 0.1-100 hour.
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| CN102675568B (en) * | 2012-06-01 | 2013-08-14 | 同济大学 | Preparation method for organic-inorganic hybrid skin-friendly efficient sunscreen product |
| CN103147147B (en) * | 2013-03-04 | 2014-12-10 | 南京工业大学 | Preparation method of polymer nano-fiber with uniform diameter |
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