CN102731698A - Method for preparing monodisperse polymer microspheres - Google Patents
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- CN102731698A CN102731698A CN2012102366297A CN201210236629A CN102731698A CN 102731698 A CN102731698 A CN 102731698A CN 2012102366297 A CN2012102366297 A CN 2012102366297A CN 201210236629 A CN201210236629 A CN 201210236629A CN 102731698 A CN102731698 A CN 102731698A
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Abstract
The invention relates to a method for preparing monodisperse polymer microspheres. The method comprises the following process steps: adding a dispersion medium with a stabilizing agent dissolved inside to an impinging stream reactor, heating the dispersion medium, adding a monomer with an initiating agent dissolved inside in one step, carrying out constant-temperature polymerization reaction, obtaining polymer microsphere emulsion after stopping cooling, then using an ultracentrifuge to carry out centrifugal sedimentation, adding absolute ethyl alcohol after removing supernatant, carrying out ultrasonic washing multiple times and drying the washed microspheres to constant weight, thus obtaining the monodisperse polymer microspheres. Compared with the prior art, the method has the following advantages: the prepared polymer microspheres have good apparent morphology, good smoothness and monodispersity and uniform grain sizes; the process is simple to operate; the grain sizes of the microspheres can be well controlled according to the formula; and the grain size range applicability is better.
Description
Technical field
The invention belongs to field of polymer microsphere materials, be specifically related to a kind of Preparation of monodisperse polymer microsphere method.
Background technology
Polymeric microball material has a wide range of applications in fields such as chromatograph packing material, analytical chemistry, medical immunology, biotechnology, coating, microelectronics, and the preparation of therefore single dispersion, polymer micro balls with uniform grain diameter is the focus in micro-sphere material field.
Aspect microsphere preparation technology, preparation method and preparation system progressively improve, and have basically set up the preparation method of the polymer microballoon of single-size.Traditional preparation method has letex polymerization and suspension polymerization, but the former can only prepare the particle of particle diameter less than 1 μ m, and the polyalcohol microspherulite diameter of latter's preparation is between 100-1000 μ m, and polymolecularity.Since the seventies; Chinese scholars has worked out the new technology of many synthetic polymer microballoons; Wherein most important have a seed swelling method, can prepare the polymer microballoon with monodispersity of particle diameter at 1-100 μ m as required, but seed swelling method complex steps; The control difficulty, the cycle is long.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Preparation of monodisperse polymer microsphere method, adopts impact flow reactor, utilizes dispersion copolymerization method successfully to prepare particle size dispersion homogeneous, the good polymer microballoon of even, the apparent pattern of particle diameter.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of Preparation of monodisperse polymer microsphere method is characterized in that including following process step: in impact flow reactor, add the dispersion medium that is dissolved with stablizer, heat up; Disposable adding is dissolved with the monomer of initiator, and wherein, the monomer consumption is the 15-30 wt % of the total material of reaction (promptly being dissolved with the dispersion medium and the monomeric total amount that is dissolved with initiator of stablizer); Initiator amount is the 1-4 wt % of monomer consumption, and stabilizing agent dosage is 2-5 wt % of monomer consumption, at 65-75 ℃ of following constant temperature polyreaction 24h; Cooling stops; Obtain the polymer microballoon emulsion, carry out centrifugal settling with ultracentrifuge 5000r/min-7000r/min then, add absolute ethyl alcohol behind the supernatant liquid that inclines; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 ℃, promptly obtain Powdered monodisperse polymer micro-sphere.
Press such scheme, described monomer is any one or the multiple mixing in vinylbenzene, methyl acrylic ester and the esters of acrylic acid.
Press such scheme, described methyl acrylic ester is TEB 3K or NSC 20956, and described esters of acrylic acid is methyl acrylate or Bing Xisuandingzhi.
Press such scheme, described initiator is Diisopropyl azodicarboxylate (AIBN), ABVN (ADVN) or Lucidol (BPO).
Press such scheme, described stablizer is Vinylpyrrolidone polymer (PVP), hydroxypropylcellulose (HPC), ROHM (PAA), Z 150PH (PVA) or polyoxyethylene glycol (PEG).
Press such scheme, described dispersion medium is pure water class, and wherein pure quality proportional range is 100:0-70:30.
Press such scheme, described monodisperse polymer micro-sphere particle diameter is 1.0 μ m-5.5 μ m.
The present invention adopts impact flow reactor to replace conventional reactors to prepare monodisperse polymer micro-sphere, at impact flow reactor camber turbulent impingement region, can strengthen secondary flowing; Reduce circulation; Help the raising of chemical reaction rate, impact flow reactor intensive microcosmic mixed characteristic effectively raises the frequency of molecular impact, its intensive pressure surge simultaneously; Changed the mode of motion of molecule with stream group; Promoted the conversion of energy, thereby promoted the dynamic process of reaction, final chemical reaction rate and monomer conversion improve.
The present invention adopts diffuse-aggregate principle in impact flow reactor, to prepare monodisperse polymer micro-sphere; Dispersion polymerization is a kind of polymkeric substance that is insoluble to this solvent by the monomer that is dissolved in organic solvent (or water) through the polymerization generation; And form the polymerization technique of the stable dispersion system of colloidal state, and the maximum characteristics of dispersion polymerization are directly to prepare the monodispersed polymer microballoon of big particle diameter.Main ingredient is monomer, dispersion medium, stablizer and initiator in the dispersion polymerization system, and the polymer particle surface adsorption stablizer that generates in the system reaches the effect of stefic stabilization.In impact flow reactor, carry out dispersion polymerization, help promoting diffuse-aggregate mass transfer and heat transfer, make that equal phase time microcosmic mixed effect is better, particle disperses more even, has improved the rate of polymerization and the monomer conversion of reaction, and reaction efficiency is higher.
Compared with present technology the present invention has following advantage:
1) adopt impact flow reactor to replace traditional reactor among the present invention; Utilize impact flow reactor intensive microcosmic to mix and the pressure surge characteristic; Reach promotion reaction kinetics process through increasing the collision of molecules frequency with the raising effective collision, thereby help the raising of chemical reaction rate and monomer conversion;
2) the apparent pattern of polymer microballoon of the present invention's preparation is good, smooth, monodispersity is good, uniform particle diameter;
3) technological operation of the present invention is simple, can be according to prescription better controlled microspherulite diameter, and the particle size range suitability is better.
Description of drawings
The sem photograph of the polystyrene microsphere that Fig. 1 prepares for the embodiment of the invention 1 different monomers consumption; Wherein: (a) 15%, (b) 20%;
The sem photograph of the polystyrene microsphere of four-hole boiling flask preparation when Fig. 2 is the embodiment of the invention 6 monomer consumptions 20%;
The size distribution figure of the polystyrene microsphere that Fig. 3 prepares for the embodiment of the invention 1 different monomers consumption; Wherein the monomer consumption is 25%;
The sem photograph of the polystyrene microsphere that Fig. 4 prepares for the embodiment of the invention 2 different initiator amounts; Wherein initiator amount is 2%;
The sem photograph of the polystyrene microsphere that Fig. 5 prepares for the embodiment of the invention 3 different stabilizers consumptions; Wherein stabilizing agent dosage is 5%;
Fig. 6 is the sem photograph of the polystyrene microsphere for preparing under the embodiment of the invention 5 differing tempss; Wherein temperature is 70 degrees centigrade.
Embodiment
Understand the present invention for ease, further illustrate content of the present invention, but content of the present invention is not limited to following examples below in conjunction with specific embodiment.
Embodiment 1:
Take by weighing 10g stablizer PVP and be dissolved in the system (732.5g) of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 7.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; So repeatedly for several times, the microballoon after cleaning is dried to constant weight under 40-60 degree centigrade, can obtains the polystyrene microsphere powder under the percussion flow condition; In a series of experiments, keeping under the constant situation of other experiment conditions, the monomer consumption is increased to 300g from 150g, prepares the polystyrene microsphere under the different monomers consumption.From Fig. 1-(a), can find out at the monomer consumption to be that smooth surface, the exterior appearance of polystyrene microsphere of 15% time preparation is good, particle size dispersion is even; Fig. 1-(b) is to be the polystyrene microsphere sem photograph for preparing under 20% condition at the monomer consumption, its smooth surface, do not have damaged; Fig. 3 is the grain-size graph of the polystyrene microsphere of 25% monomer consumption preparation, and the median size that can access the polystyrene microsphere under this condition is about 2.4 microns.
Embodiment 2:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 2.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition; In a series of experiments, under the constant situation of other conditions of maintenance, initiator A IBN consumption is increased to 10g from 2.5g, prepares the polystyrene microsphere under the different initiator A IBN consumptions; As can beappreciated from fig. 4, at initiator amount be good, no damaged, the microspherulite diameter distribution homogeneous of smooth surface, exterior appearance of the polystyrene microsphere of preparation in 2% o'clock.
Embodiment 3:
Take by weighing 5.0g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 7.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition; In a series of experiments, keep under the constant situation of other conditions, stabilizing agent dosage is increased to 12.5g by 5.0g, prepares the polystyrene microsphere under the consumption of different stabilizers PVP; As can beappreciated from fig. 5, be 5% o'clock at stablizer PVP consumption, good, the smooth nothing of the surface condition of the polystyrene microsphere of preparation is damaged, the microballoon degree of scatter is good, the size distribution homogeneous.
Embodiment 4:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 100:0 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 7.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition; Under a series of experiment conditions, keep under the constant situation of other conditions, dispersion medium alcohol water changes to 70:30 than from 100:0, prepares the polystyrene microsphere under the different dispersion situation.
Embodiment 5:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 60 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 7.5g initiator A IBN, disposable joining in the impact flow reactor, 60 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition; Under a series of experiment conditions, keep under the constant situation of other conditions, polymeric reaction temperature is increased to 75 degrees centigrade by 60 degrees centigrade, prepares the polystyrene microsphere under the differing temps; As can beappreciated from fig. 6, the outward appearance of the polystyrene microspheres of preparation is good under temperature is 70 degrees centigrade, and smooth nothing is damaged.
Embodiment 6:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the four-hole boiling flask after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 7.5g initiator A IBN, disposable joining in the four-hole boiling flask, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition; As can beappreciated from fig. 2, the polystyrene microsphere surface and the outward appearance situation of its preparation are undesirable, and with Fig. 1-(b) contrast, the polystyrene microsphere effect of the present invention's preparation is better than the microballoon of four-hole boiling flask preparation.
Embodiment 7:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g TEB 3K solution (total amount is in 1000g) that is dissolved with 2.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the poly (methyl methacrylate) micro-sphere powder under the percussion flow condition.
Embodiment 8:
Take by weighing 10g stablizer PVA and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 2.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition.
Embodiment 9:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g TEB 3K solution (total amount is in 1000g) that is dissolved with 2.5g initiator B PO, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the poly (methyl methacrylate) micro-sphere powder under the percussion flow condition.
Embodiment 10:
Take by weighing 10g stablizer HPC and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein methyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 2.5g initiator A IBN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition.
Embodiment 11:
Take by weighing 10g stablizer PVA and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein methyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g TEB 3K solution (total amount is in 1000g) that is dissolved with 2.5g initiator A DVN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the poly (methyl methacrylate) micro-sphere powder under the percussion flow condition.
Embodiment 12:
Take by weighing 10g stablizer PVA and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g styrene solution (total amount is in 1000g) that is dissolved with 2.5g initiator A DVN, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the polystyrene microsphere powder under the percussion flow condition.
Embodiment 13:
Take by weighing 10g stablizer PVP and be dissolved in the system of absolute ethyl alcohol and deionized water, wherein absolute ethyl alcohol is 95:5 with deionized water quality ratio, joins in the impact flow reactor after stirring, and is warmed up to 70 degrees centigrade; With the 250g NSC 20956 solution (total amount is in 1000g) that is dissolved with 2.5g initiator B PO, disposable joining in the impact flow reactor, 70 degrees centigrade of reaction 24h postcooling terminations down; Then the emulsion that obtains is carried out centrifugal settling through ultracentrifuge 5000r/min-7000r/min; Incline and add absolute ethyl alcohol behind the supernatant liquid; Through ultrasonic cleaning; Repeatable operation is dried to constant weight with the microballoon after cleaning for several times under 40-60 degree centigrade, can obtain the poly-n-butyl methacrylate microballoon powder under the percussion flow condition.
Claims (7)
1. a Preparation of monodisperse polymer microsphere method is characterized in that including following process step: in impact flow reactor, add the dispersion medium that is dissolved with stablizer, heat up; Disposable adding is dissolved with the monomer of initiator, and wherein, the monomer consumption is the 15-30 wt % of the total material of reaction; Initiator amount is the 1-4 wt % of monomer consumption, and stabilizing agent dosage is 2-5 wt % of monomer consumption, at 65-75 ℃ of following constant temperature polyreaction 24h; Cooling stops, and obtains the polymer microballoon emulsion, carries out centrifugal settling with ultracentrifuge 5000r/min-7000r/min then; Inclining adds absolute ethyl alcohol behind the supernatant liquid, and through ultrasonic cleaning, repeatable operation for several times; Microballoon after cleaning is dried to constant weight under 40-60 ℃, promptly obtains Powdered monodisperse polymer micro-sphere.
2. by the described Preparation of monodisperse polymer microsphere method of claim 1, it is characterized in that described monomer is any one or the multiple mixing in vinylbenzene, methyl acrylic ester and the esters of acrylic acid.
3. by the described Preparation of monodisperse polymer microsphere method of claim 2, it is characterized in that described methyl acrylic ester is TEB 3K or NSC 20956, described esters of acrylic acid is methyl acrylate or Bing Xisuandingzhi.
4. by claim 1 or 3 described Preparation of monodisperse polymer microsphere methods, it is characterized in that described initiator is Diisopropyl azodicarboxylate, ABVN or Lucidol.
5. by claim 1 or 3 described Preparation of monodisperse polymer microsphere methods, it is characterized in that described stablizer is a Vinylpyrrolidone polymer, hydroxypropylcellulose, ROHM, Z 150PH or polyoxyethylene glycol.
6. by claim 1 or 3 described Preparation of monodisperse polymer microsphere methods, it is characterized in that described dispersion medium is pure water class, wherein pure quality proportional range is 100:0-70:30.
7. Preparation of monodisperse polymer microsphere method according to claim 1 is characterized in that: described monodisperse polymer micro-sphere particle diameter is 1.0 μ m-5.5 μ m.
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| CN106243268B (en) * | 2016-08-03 | 2017-12-29 | 台州艾斐建材有限公司 | A kind of tap of antimicrobial form resin composite materials cladding |
| CN107486132A (en) * | 2017-09-01 | 2017-12-19 | 湖南明裕环保科技有限公司 | A kind of preparation method of the porous heavy-metal adsorption material of nano ferriferrous oxide |
| CN108913140A (en) * | 2018-07-27 | 2018-11-30 | 武汉工程大学 | A kind of micron order up-conversion luminescent material and preparation method thereof |
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Application publication date: 20121017 |