CN102796219B - Preparation method of composite microspheres - Google Patents
Preparation method of composite microspheres Download PDFInfo
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- CN102796219B CN102796219B CN201210307865.3A CN201210307865A CN102796219B CN 102796219 B CN102796219 B CN 102796219B CN 201210307865 A CN201210307865 A CN 201210307865A CN 102796219 B CN102796219 B CN 102796219B
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Abstract
The invention relates to a preparation method of composite microspheres, in particular to the preparation method of the composite microspheres which are obtained by using acrylamide as well as acrylic acids and derivatives thereof as monomers and carrying on multivariate copolymerization on the monomers by a distillation precipitation method. The preparation method of the composite microspheres, provided by the invention, can be widely used for the biological medical, medical immunology and cosmetic manufacturing fields, in particular the tertiary oil recovery field, and can be used for profile control and oil flooding of low-permeability reservoirs. Polymer microspheres are prepared by using the distillation precipitation method, an improvement is made on the basis of the precipitation method and stirring is replaced with distillation; and the preparation method comprises the following steps of: in a distilled state, copolymerizing a mixture of one or more of the acrylamide as well as the acrylic acids and the derivatives thereof in a reaction container in the presence of an oil-soluble initiator; after all solvents are distilled, dispersing and washing obtained solid polymer microspheres by ethanol; and centrifuging, drying and grinding the solid polymer microspheres so as to obtain dry microspheres. The preparation method of the composite microspheres, provided by the invention, has the advantages of simple process and convenience in implementation.
Description
Technical field
The invention belongs to the preparation method of complex microsphere, more specifically, relate to a kind ofly with acrylamide, and vinylformic acid and derivative thereof be monomer, by the distillation precipitator method, the preparation method of the complex microsphere that multi-component copolymer obtains.Can be widely used in biomedicine, immune medical science, makeup manufacture, especially tertiary oil recovery field, can be for to the profile control of low permeability pay and the displacement of reservoir oil.
Background technology
Traditional preparation method of monodispersed polyacrylamide and multipolymer complex microsphere thereof, mainly contains suspension polymerization, verse phase microemulsion polymer, dispersion copolymerization method, the precipitator method etc.It is too wide that yet microspherulite diameter prepared by suspension polymerization distributes; Conversed phase micro emulsion copolymerization method complex steps, introduce a large amount of oil phases and emulsifying agent, is unfavorable for recycling, and caused the larger wasting of resources, and particle diameter is less than normal, in 100nm left and right, is also unfavorable for suitability for industrialized production; The microballoon sphericity that dispersion copolymerization method obtains is not fine, and has introduced a large amount of dispersion agents at microsphere surface.The precipitator method refer to that the polymkeric substance of generation is insoluble to monomer and solvent, the polyreaction of the continuous Precipitation of polymkeric substance forming in polymerization process.And the precipitator method are compared with front several method, technique is simple, and the microballoon monodispersity obtaining is good, but that defect is monomer concentration is low, expend quantity of solvent large, and productive rate is lower.(patent No. 200510037918.4) that Southeast China University in 2005 turns round and look at loyal pool also once water or water-ol system as solvent, using hydrophobicity or oil-soluble material as monomer, with persulfuric acid salt as initiator, prepared hydrophobic microsphere polymer, but also do not prepare acrylamide by the precipitator method up to now, and the complex microsphere of one or more copolymerization of vinylformic acid and derivative thereof.
Summary of the invention
The present invention is in order to overcome the defect of above-mentioned prior art, simple in order to obtain a kind of manufacturing process, is convenient to the complex microsphere of enforcement, and the technical scheme adopting is as follows, comprises the steps:
(1) get acrylamide, one or more mixture with vinylformic acid and derivative thereof, wherein one or more the mol ratio of mixture of acrylamide and vinylformic acid and derivative thereof is 1:10-10:1, join in reaction vessel, in reaction vessel, add solvent, fully mix, then ultrasonic scattering, in reaction vessel, add linking agent and initiator, also ultrasonic scattering; (2) heater heats heats up, and in 10-18 minute, heats to boiling state, then oil bath temperature is remained on to 90 ℃ of left and right, keeps this state 15 minutes; (3) regulate heater temperature to 110-120 ℃, strengthen distillation intensity, the solvent in reaction vessel constantly flow in receiving vessel, and after 90-100 minute, the solvent in reaction vessel all distills; (4) stop heating, in reaction vessel, add ethanol, and ultrasonic dispersion, then centrifugation goes out the microballoon that reaction obtains; (5) purify: use again the ultrasonic dispersion of ethanol, centrifugal twice, to purify resulting microballoon; (6) then the described microballoon obtaining after purifying is put in to 10-14 hour in the baking oven of 40-60 ℃, dries and obtain the microballoon that needs.
Preferably, acrylic acid derivative is 2-acrylamido-methyl propane sulfonic acid (AMPS) or methyl methacrylate (MMA).
Preferably, the mol ratio of the mixture of vinylformic acid and methyl methacrylate is 1:3.
Preferably, it is characterized in that described solvent is acetonitrile, methyl alcohol, ethanol, one or more in ethyl acetate and tetrahydrofuran (THF), consumption is 17.3-36.5 times of acrylamide molar mass.
Preferably, described linking agent is N,N methylene bis acrylamide or Vinylstyrene, the 1-10%(mol per-cent that consumption is acrylamide).
Preferably, described initiator be Diisopropyl azodicarboxylate,
2,2'-Azobis(2,4-dimethylvaleronitrile)or azo-bis-iso-dimethyl, the 0.5-2%(mol per-cent that consumption is acrylamide).
Preferably, in step (3), keep being back to the solvent in reaction vessel and the velocity ratio of the solvent that distills in 2 left and right.
The microspherulite diameter distribution homogeneous wherein obtaining, microballoon is controlled between 200nm to 1 μ m, has solved that to receive in micron polymer microsphere building-up process microspherulite diameter chaotic, problem not of uniform size; And the microballoon preparing is all not easy to reunite in oil phase and aqueous phase solvent, is good monodisperse status; Whole reaction process is simple to operation, still-process is exactly the removal process of solvent, the solvent that recovery obtains can reuse, do not need the step of carrying out secondary purification or removing stopper yet, made up because monomer concentration is lower, expending the shortcoming that quantity of solvent is large, thereby contribute to suitability for industrialized production, is a kind of good method of preparing composition polymer microballoon.According to the microballoon of preparation, carried out corresponding aquation experiment, find that microballoon can expand in water, different microballoons has different hydratabilities, obtained from the microballoon of four size gradings between 200nm to 12 μ m, can optionally be injected in stratum, thereby reach water plugging and profile controlling, improve the object of recovery ratio.
First solvent will meet solvent polymerization reaction monomers, and can be settled out the character of the corresponding polymkeric substance obtaining.Like this, in reaction system, along with temperature rises, decomposition of initiator produces free radical, this free radical can react to obtain free radical newly with polymerization single polymerization monomer wherein, then attack again new monomer, free radical chain constantly increases like this, cause that self polarity changes, by the similar principle that mixes, molecular weight with polymer chain increases, solubleness in reaction medium reduces gradually, reach after critical chain length, from medium, precipitating out, many segments mutually tangle and form stable core and be suspended in medium, monomer and free radical in the elementary growth core absorption reaction medium forming, in core, proceed polyreaction, form polymer microballoon.But free radical runs into the molecule that some activity are higher in solution, such as Sauerstoffatom, just can react with it and stop the growth of free radical chain, thereby in solvent, existing oxygen can hinder polyreaction.According to gas Henry's law, the solubleness of oxygen in the solvent of boiling is almost nil.Thereby the polymerization in the solvent of boiling does not need nitrogen protection device and step.
In addition, because acetonitrile solvent can be good at dissolving monomer and the initiator adding, the system starting stage is a homogeneous phase solution, carrying out along with reaction, system reaches boiling state, and now heat transfer and mass transfer all reach maximum, there is no need to add whipping appts in system, once add stirring, can cause on the contrary the polymer microballoon sphericity obtaining good not or reunite.
Beneficial effect: according to the present invention, more common 65 ° of left and right of polymerization temperature are compared, improves polymerization temperature and can increase the initiation rate of decomposition of initiator and the rate of rise of free radical chain, thereby greatly improve polymerization velocity, Reaction time shorten.In addition, because body is in boiling state, under strong convection state, heat transfer coefficient is very big, can effectively alleviate the local superheating causing because of polymerization exotherm, thereby the diameter Distribution of the microballoon obtaining is narrower, has following advantage:
(1) uniform particle diameter: dry microspheres diameter is less, the diameter of various different dry microspheres is all within the scope of 200nm-1000nm, and diameter Distribution is very narrow, can be in 4%.
Be easy to large-scale production: under boiling state, system is in isotropy, the heat transfer of storeroom, mass transfer, all in maximum rating, is very beneficial for large-scale polyreaction.
(2) reaction times is short: because polymerization temperature is 82 ° of left and right, the initiation rate of decomposition of initiator and the rate of rise of free radical chain are more much bigger than conventionally, thereby greatly shorten polymerization time, and transformation efficiency reached for 90% needed time.In present method, the whole reaction times only needed about 2 hours.
(3) the different microballoon obtaining has different hydration swelling abilities, after hydration swelling, has obtained four size gradings, 0.3-0.6 μ m, 0.4um-1 μ m, 1-3 μ m, 3um-12 μ m.These different particle diameters can be applicable to the low-permeability oil deposit of different rate of permeation or porosity.
(4) by this kind of distillation precipitator method, can obtain the polymer microballoon of various difference in functionality groups, as polyacrylamide microsphere (PAM), acrylamide and acrylic acid composition polymer microballoon P (AM-AA), the composition polymer microballoon P (AM-MAA) of acrylamide and methacrylic acid, the composition polymer microballoon P (AM-MMA) of acrylamide and methyl methacrylate, the composition polymer microballoon P (AM-AMPS) of acrylamide and 2-acrylamido-methyl propane sulfonic acid (AMPS), acrylamide and vinylformic acid, the composition polymer microballoon P (AM-AA-MMA) of methyl methacrylate terpolymer.Because different monomers has different functional performances, so the different composite polymer microballoon of preparation has different functions, for example, due to the performance of AMPS due to high-temperature resisting and salt-resisting, obtain the performance that P (AM-AMPS) microballoon also has high-temperature-resistant high-salt.
(5) equipment is simple; easy handling: only need condensation reflux unit in the present invention; do not need nitrogen protection device; do not need whipping appts; also do not need accurate temperature-control device, because the boiling point of system is only relevant with extraneous pressure and composing system, under normal pressure, boiling point remains unchanged within the specific limits; thereby the temperature of system is relatively stable, without accurate temperature-control device.Three aspects: integrates, and this polymerization unit is simplified greatly.
(6) environmental protection and economy: owing to needing to use distillation in polymerization process, and still-process is also the purification process of a solvent simultaneously, the solvent distilling can repeat polyreaction next time, not only economy but also environmental protection, and there is no other special purification requirement to participating in reaction medicine, save cost, improved reaction efficiency.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of polyreaction apparatus in the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph (in figure, scale is 5 μ m) of the composite drying microballoon of four groups of different aquation size gradings in the present invention.
1 is round-bottomed flask, and 2 is reaction solution, and 3 is condensing reflux pipe, and 4 is chilled joint, and 5 is receiving vessel, 6 heating units.
embodiment:
Below in conjunction with accompanying drawing and specific embodiment, the invention will be further described:
Embodiment 1:
Get acrylamide 1mol, vinylformic acid 10mol, join single necked round bottom flask 1(reaction vessel) in, in bottle, add the acetonitrile solvent of 35.6mol, after fully mixing, after ultrasonic scattering, toward the N-N methylene-bisacrylamide (MBAA) that adds 0.1mol in round-bottomed flask, the Diisopropyl azodicarboxylate (AIBN) that adds 0.02mol is ultrasonic scattering also; (2) round-bottomed flask that reaction solution 2 is housed is placed in oil bath pan (heating unit 6), and downward-sloping certain angle installs condensing reflux pipe 3, chilled joint 4 and receiving vessel 5 such as 30 °; (3) oil bath pan starts to heat up, and in 15 minutes, from normal temperature, rises to boiling state, and oil bath pan temperature remains on 90 ℃ of left and right, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 110 ℃, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 90 minutes, the solvent in flask almost all distills.In the situation that guaranteeing this distilling effect, can adopt any condensing works set-up mode, the condensing works preferably adopting such as the present invention is set to: keep being back to the solvent in reaction flask and the velocity ratio of the solvent that distills in 2 left and right.(5) stopped reaction, the white solid in flask, by adding, ethanol is ultrasonic to scatter, and centrifugation is out; (6) purify: use again ethanol ultrasonic cleaning, centrifugal twice, purify the microballoon obtaining; (7) then the solid obtaining is put in the baking oven of 40-60 ℃ to 14 hours, dries and obtain the polymer microballoon powder that needs, after grinding, weigh and install.The microballoon that this embodiment obtains is acrylamide and acrylic acid composition polymer microballoon P (AM-AA).
Embodiment 2:
Get acrylamide 10mol, 2-acrylamido-methyl propane sulfonic acid (AMPS) 1mol, joins in single necked round bottom flask, in bottle, add the acetonitrile solvent of 173mol, after fully mixing, after ultrasonic scattering, Vinylstyrene toward adding 0.1mol in round-bottomed flask, adds 0.05mol's
2,2'-Azobis(2,4-dimethylvaleronitrile)also ultrasonic scattering; (2) round-bottomed flask that reaction solution is housed is placed in oil bath pan (heating unit), and downward-sloping certain angle installs condensing reflux pipe, chilled joint and receiving vessel such as 30 °; (3) oil bath pan starts to heat up, and in 18 minutes, from normal temperature, rises to boiling state, and oil bath pan temperature remains on 90 ℃ of left and right, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 120 ℃, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 100 minutes, the solvent in flask almost all distills.In the situation that guaranteeing this distilling effect, can adopt any condensing works set-up mode, the condensing works preferably adopting such as the present invention is set to: keep being back to the solvent in reaction flask and the velocity ratio of the solvent that distills in 2 left and right.(5) stopped reaction, the white solid in flask, by adding, ethanol is ultrasonic to scatter, and centrifugation is out; (6) purify: use again ethanol ultrasonic cleaning, centrifugal twice, purify the microballoon obtaining; (7) then the solid obtaining is put in the baking oven of 40-60 ℃ to 10 hours, dries and obtain the polymer microballoon powder that needs, after grinding, weigh and install.The microballoon that this embodiment obtains is the composition polymer microballoon P (AM-AMPS) of acrylamide and 2-acrylamido-methyl propane sulfonic acid (AMPS).
Embodiment 3:
Get acrylamide 1mol, methyl methacrylate (MMA) 5mol, join in single necked round bottom flask, in bottle, add the acetonitrile solvent of 24.4mol, after fully mixing, after ultrasonic scattering, toward the N-N methylene-bisacrylamide (MBAA) that adds 0.05mol in round-bottomed flask, the azo-bis-iso-dimethyl that adds 0.01mol is ultrasonic scattering also; (2) round-bottomed flask that reaction solution is housed is placed in oil bath pan (heating unit), and downward-sloping certain angle installs condensing reflux pipe, chilled joint and receiving vessel such as 30 °; (3) oil bath pan starts to heat up, and in 10 minutes, from normal temperature, rises to boiling state, and oil bath pan temperature remains on 90 ℃ of left and right, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 115 ℃, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 100 minutes, the solvent in flask almost all distills.In the situation that guaranteeing this distilling effect, can adopt any condensing works set-up mode, the condensing works preferably adopting such as the present invention is set to: keep being back to the solvent in reaction flask and the velocity ratio of the solvent that distills in 2 left and right.(5) stopped reaction, the white solid in flask, by adding, ethanol is ultrasonic to scatter, and centrifugation is out; (6) purify: use again ethanol ultrasonic cleaning, centrifugal twice, purify the microballoon obtaining; (7) then the solid obtaining is put in the baking oven of 40-60 ℃ to 12 hours, dries and obtain the polymer microballoon powder that needs, after grinding, weigh and install.The microballoon that this embodiment obtains is the composition polymer microballoon P (AM-MMA) of acrylamide and methyl methacrylate
Embodiment 4:
Get acrylamide 1mol, vinylformic acid 1mol, methyl methacrylate 3mol, join in single necked round bottom flask, in bottle, add the acetonitrile solvent of 36.5mol, after fully mixing, after ultrasonic scattering, toward the N-N methylene-bisacrylamide (MBAA) that adds 0.08mol in round-bottomed flask, the Diisopropyl azodicarboxylate (AIBN) that adds 0.007mol is ultrasonic scattering also; (2) round-bottomed flask that reaction solution is housed is placed in oil bath pan (heating unit), and downward-sloping certain angle installs condensing reflux pipe, chilled joint and receiving vessel such as 30 °; (3) oil bath pan starts to heat up, and in 20 minutes, from normal temperature, rises to boiling state, and oil bath pan temperature remains on 90 ℃ of left and right, keeps this state 15 minutes; (4) regulate oil bath pan temperature to 110-120 ℃, strengthen distillation intensity, the solvent in flask constantly flow in receiving vessel, and after about 100 minutes, the solvent in flask almost all distills.In the situation that guaranteeing this distilling effect, can adopt any condensing works set-up mode, the condensing works preferably adopting such as the present invention is set to: keep being back to the solvent in reaction flask and the velocity ratio of the solvent that distills in 2 left and right.(5) stopped reaction, the white solid in flask, by adding, ethanol is ultrasonic to scatter, and centrifugation is out; (6) purify: use again ethanol ultrasonic cleaning, centrifugal twice, purify the microballoon obtaining; (7) then the solid obtaining is put in the baking oven of 40-60 ℃ to 14 hours, dries and obtain the polymer microballoon powder that needs, after grinding, weigh and install.The microballoon that this embodiment obtains is the composition polymer microballoon P (AM-AA-MMA) of acrylamide and vinylformic acid, methyl methacrylate terpolymer.
Although the present invention has provided four kinds of embodiment, can not be interpreted as limitation of the present invention.Although reaction solvent has adopted acetonitrile solvent.But any is that oil-dissolving solvent can be applied in the present invention, as methyl alcohol, ethanol, ethyl acetate, one or more in methyl ethyl ketone and tetrahydrofuran (THF).Although the present invention has adopted N-N methylene-bisacrylamide as linking agent, also can adopt any linking agent, such as adopting Vinylstyrene, chemical pure rank, does not contain the impurity that stops the free radical in polymerization process; Although the present invention has adopted Diisopropyl azodicarboxylate (AIBN) as initiator, also can adopt any oil-soluble azo-initiator, as Diisopropyl azodicarboxylate,
2,2'-Azobis(2,4-dimethylvaleronitrile)or azo-bis-iso-dimethyl.In the present invention, in polymerization process, adopt oil bath pan as well heater, but any type heater is all fine, such as can also sand-bath, warm air bath, electric furnace or other can provide the well heater of thermal source; Although the present invention has adopted round-bottomed flask as reaction vessel, it should be appreciated by those skilled in the art that the common container in any this area can be as reaction vessel; Condensation reflux unit is downward-sloping certain angle, such as the condensing reflux pipe that 30 degree are installed, chilled joint and receiving vessel, or directly use a liebig's condensing tube, but also can adopt any common condensation reflux unit in this area, as long as can guarantee distilling effect.
Claims (2)
1. a preparation method for complex microsphere, is characterized in that, the method comprises the steps:
(1) get acrylamide, several mixture with vinylformic acid and derivative thereof, wherein the mol ratio of several mixture of acrylamide and vinylformic acid and derivative thereof is 1:10-10:1, join in reaction vessel, in reaction vessel, add solvent, fully mix, then ultrasonic scattering, in reaction vessel, add linking agent and initiator, also ultrasonic scattering;
(2) heater heats heats up, and in 10-18 minute, heats to boiling state, then oil bath temperature is remained on to 90 ℃ of left and right, keeps this state 15 minutes;
(3) regulate heater temperature to 110-120 ℃, strengthen distillation intensity, the solvent in reaction vessel constantly flow in receiving vessel, and after 90-100 minute, the solvent in reaction vessel all distills;
(4) stop heating, in reaction vessel, add ethanol, and ultrasonic dispersion, then centrifugation goes out the microballoon that reaction obtains; (5) purify: use again the ultrasonic dispersion of ethanol, centrifugal twice, to purify resulting microballoon;
(6) then the described microballoon obtaining after purifying is put in to 10-14 hour in the baking oven of 40-60 ℃, dries and obtain the microballoon that needs; Wherein, acrylic acid derivative is methyl methacrylate (MMA), and the mol ratio of vinylformic acid and methyl methacrylate is 1:3;
Wherein, described solvent is methyl alcohol, ethanol, one or more in ethyl acetate and tetrahydrofuran (THF), and consumption is 17.3-36.5 times of acrylamide molar mass;
Wherein, described linking agent is Vinylstyrene, and consumption is the 1-10% of acrylamide mol per-cent;
Wherein, described initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl, and consumption is the 0.5-2% of acrylamide mol per-cent;
Wherein, microspherulite diameter distribution homogeneous, microballoon is controlled between 200nm to 1 μ m, the different complex microsphere obtaining has different hydration swelling abilities, after hydration swelling, four size gradings have been obtained: 0.3-0.6 μ m, 0.4-1 μ m, 1-3 μ m and 3 μ m-12 μ m, these different particle diameters are applicable to different rate of permeation or the low-permeability oil deposit of porosity.
2. a preparation method for complex microsphere, is characterized in that, the method comprises the steps:
(1) get acrylamide and acrylic acid derivative, wherein the mol ratio of acrylamide and acrylic acid derivative is 1:10-10:1, join in reaction vessel, in reaction vessel, add solvent, fully mix, then ultrasonic scattering adds linking agent and initiator, also ultrasonic scattering in reaction vessel;
(2) heater heats heats up, and in 10-18 minute, heats to boiling state, then oil bath temperature is remained on to 90 ℃ of left and right, keeps this state 15 minutes;
(3) regulate heater temperature to 110-120 ℃, strengthen distillation intensity, the solvent in reaction vessel constantly flow in receiving vessel, and after 90-100 minute, the solvent in reaction vessel all distills;
(4) stop heating, in reaction vessel, add ethanol, and ultrasonic dispersion, then centrifugation goes out the microballoon that reaction obtains;
(5) purify: use again the ultrasonic dispersion of ethanol, centrifugal twice, to purify resulting microballoon;
(6) then the described microballoon obtaining after purifying is put in to 10-14 hour in the baking oven of 40-60 ℃, dries and obtain the microballoon that needs; Wherein, acrylic acid derivative is 2-acrylamide-2-methyl propane sulfonic (AMPS);
Wherein, described solvent is methyl alcohol, ethanol, one or more in ethyl acetate and tetrahydrofuran (THF), and consumption is 17.3-36.5 times of acrylamide molar mass;
Wherein, described linking agent is Vinylstyrene, and consumption is the 1-10% of acrylamide mol per-cent;
Wherein, described initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl, and consumption is the 0.5-2% of acrylamide mol per-cent;
Wherein, microspherulite diameter distribution homogeneous, microballoon is controlled between 200nm to 1 μ m, the different complex microsphere obtaining has different hydration swelling abilities, after hydration swelling, four size gradings have been obtained: 0.3-0.6 μ m, 0.4-1 μ m, 1-3 μ m and 3 μ m-12 μ m, these different particle diameters are applicable to different rate of permeation or the low-permeability oil deposit of porosity.
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