CN101250244B - Polymer hollow microsphere and preparation method thereof - Google Patents
Polymer hollow microsphere and preparation method thereof Download PDFInfo
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- CN101250244B CN101250244B CN200810047244XA CN200810047244A CN101250244B CN 101250244 B CN101250244 B CN 101250244B CN 200810047244X A CN200810047244X A CN 200810047244XA CN 200810047244 A CN200810047244 A CN 200810047244A CN 101250244 B CN101250244 B CN 101250244B
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Abstract
The invention relates to a polymer hollow microsphere and a relative preparation method. The preparation method comprises using emulsion polymerization method to prepare water absorbing polymer, using core-shell polymerization to prepare the polymer microsphre coated by water absorbing polymer, using the reaction character of functional monomer at the surface of the polymer microsphere and atomization drying to obtain the polymer hollow microsphere with ideal size, many internal hollow microspheres and negative pressure in the hollow microsphere. The preparation method has low energy consumption, controllable preparation, various products, controllable grain size of hollow microsphere, better size adaptability, high stability, high production efficiency, no generation of waste water, waste gas and waste slag, low pollution and environment protection, whose polymer hollow microspheres have better acie and alkali resistnace. The invention is suitable for construction material and paint, with wide application and practical value.
Description
Technical field
The present invention relates to a kind of polymeric material and preparation method thereof, especially a kind of polymer hollow microsphere and preparation method thereof.
Background technology
Hollow microsphere has been subjected to paying close attention to widely in polymerization studies in recent years, its reason is because hollow microsphere is a kind of polymer materials with special construction, size of particles at micron between the nanometer, have features such as hollow, capsule concurrently, be with a wide range of applications at aspects such as biology, light, magnetics and nuclear physics and electronics.This technology is a hot research in recent years, so far the method that mainly prepares polymer hollow particles is template, self-assembly method and emulsion polymerization, because template and self-assembly method require very high to envrionment conditions, temporarily also there is not to form the technology that really has on the actually operating meaning, and emulsion polymerization is because condition is easy, implement easily to form comparatively sophisticated technology, but the hollow microsphere particle diameter of emulsion polymerization preparation is less, has been subjected to restriction being applied to building material field.In order to enlarge the Application Areas of hollow microsphere, forefathers have done a large amount of work, for example use the method for the inorganic materials of strong acid etch polymers coating; The use that also has adds method of the polymkeric substance that the heat abstraction inorganics coats or the like; but use such method all can produce a large amount of waste water and waste residue; expend a large amount of energy, under China's atmosphere that the energy is comparatively nervous now, environment protection is more and more important, shown certain problem.
Summary of the invention
First purpose of the present invention is to overcome existing method for preparing microsphere energy consumption height, can produce waste water and waste residue and tiny balloon particle diameter smaller defect and deficiency, a kind of waste water and dregs that do not produce is provided, and energy consumption is less, the preparation method of the polymer hollow microsphere that grain size can be controlled.
Second purpose of the present invention is that to overcome existing tiny balloon particle diameter less, and defective that acid-fast alkali-proof is relatively poor and deficiency provide that the big and microballoon of a kind of particle diameter is inner to be negative pressure, the polymer hollow microsphere that acid-fast alkali-proof and heat preservation and insulation are good.
The present invention realizes that the technical scheme of first purpose is: a kind of preparation method of particle diameter controllable polymer tiny balloon may further comprise the steps:
A. seed emulsion preparation:
Blending emulsifiers sneaked in the water stir, add water-absorbing polymer monomer and polymer monomers then, stir fast, make monomer whose fully emulsified, be warmed up to 60-80 ℃ then, add the initiator insulation reaction and obtained seed emulsion in 4-6 hour,
The weight part content of described raw material is:
Water 1500-2500
Blending emulsifiers 1.5-2.5
Water-absorbing polymer monomer 5-15
Polymer monomers 4-6
Initiator 0.5-1.5;
B. water-absorbent nuclear polymer preparation:
Under 60-80 ℃, in seed emulsion, slowly drip by the milk sap of forming by water-absorbing polymer monomer, polymer monomers, blending emulsifiers and water, abundant reaction adds alkaline aqueous solution adjusting pH value after 1.5 hours be 8-9, obtains water-absorbent nuclear polymer aqueous dispersions
The weight part content of raw material is in the described milk sap:
Water 140-180
Blending emulsifiers 3-4
Water-absorbing polymer monomer 200-280
Polymer monomers 50-80;
C. prepare polymer shell and introduce functional groups:
Get 1000 parts of above-mentioned water-absorbent nuclear polymer aqueous dispersions, with 1.5-2 times of water it is diluted, then under 60-80 ℃, to wherein dripping the shell milk sap of forming by monomer, blending emulsifiers and the water of polymer monomers, band functional groups, react after 1-2 hour, obtain the aqueous solution of coating water-absorbent polymer microballoon
The weight part content of raw material is in the described shell milk sap:
Water 200-240
Blending emulsifiers 3-5
Polymer monomers 300-400
The monomer 100-140 of band functional groups;
D. interface polymerization reaction:
In the above-mentioned aqueous solution, add and the complete immiscible solvent 1000-1500 part of water, add polycondensation monomer 80-120 part, carry out interface polymerization reaction under the normal temperature, lose promptly to react after active group exists through infrared test and finish;
E. prepare polymer hollow particles:
The previous reaction product is sent in the spray-dryer, and control inlet hot blast temperature is 100-120 ℃, and temperature out 20-60 ℃ is carried out spraying drying, obtain polymer hollow microsphere;
Wherein: described blending emulsifiers is by nonionic emulsifier and ionic emulsifying agent is composite forms, described polymer monomers is a vinylbenzene, methyl methacrylate, polyvinyl pyridine, in vinyl acetate and the polyethylene pyrrolidone one or more, described water-absorbing polymer monomer is a methacrylic acid, vinylformic acid, in methyl methacrylate and the butyl acrylate one or more, described initiator is a Potassium Persulphate, ammonium persulphate, described functional monomer is to have amino, hydroxyl, the acrylic monomer of carboxyl or anhydride group functional groups, described polycondensation monomer be can with the monomer of above-mentioned functions radical reaction.
Nonionic emulsifier is OP series or tween series or class of department series in the emulsifying agent of the present invention, and ionic emulsifying agent is anionic emulsifier or cationic emulsifier.
Nonionic emulsifier of the present invention is OP-10 or OP-15 or OP-20, and ionic emulsifying agent is sodium laurylsulfonate or extraordinary amido silicon oil or Sodium dodecylbenzene sulfonate or palmityl trimethyl ammonium chloride.
Water-absorbing polymer monomer of the present invention is the blend of methacrylic acid and butyl acrylate.
Polycondensation monomer of the present invention is monomer or the oligopolymer or the monomer of melamine class or cyclodextrin that contains isocyanate group.
Among the preparation method of the present invention:
In the described steps A, the weight part content of described raw material is: water 2000, blending emulsifiers 1.8, water-absorbing polymer monomer 10-15, polymer monomers 5-6, initiator 1-1.5, wherein blending emulsifiers is that OP-10 and 2: 1 by weight mixed of sodium laurylsulfonate form, the water-absorbing polymer monomer is to be formed by methacrylic acid and 5: 1 by weight mixed of butyl acrylate, and polymer monomers is a methyl methacrylate, and initiator is a Potassium Persulphate;
Among the described step B, the weight part content of raw material is in the described milk sap: water 160, blending emulsifiers 3.6-4.5, water-absorbing polymer monomer 240-280, polymer monomers 65-100, wherein blending emulsifiers is to be formed by OP-10 and 3: 1 by weight mixed of sodium laurylsulfonate, and the water-absorbing polymer monomer is a methacrylic acid, and polymer monomer is by vinylbenzene and methyl methacrylate by weight 1: the mixed of 1.8-2.2 forms;
Among the described step C, the weight part content of raw material is in the shell milk sap: water 220-240, blending emulsifiers 4-5, polymer monomers 340-400, the monomer 120-140 of band functional groups, wherein blending emulsifiers is to be formed by OP-10 and 3: 1 by weight mixed of sodium laurylsulfonate, polymer monomers be by vinylbenzene and methyl methacrylate by 4: the mixed of 0.8-1.2 forms, the monomer of band functional groups is to have amino, hydroxyl, the acrylic monomer of carboxyl or anhydride group functional groups;
Among the described step D, adding with the complete immiscible solvent of water be higher alkane, alkylbenzene and halohydrocarbon, wherein polycondensation monomer is tolylene diisocyanate or isophorone diisocyanate.
Of the present invention and the complete immiscible solvent of water can be hexanaphthene, dimethylbenzene, chloroform.
Among step B of the present invention, the step C, the drop rate of emulsion and shell emulsion is the 0.6-0.8 ml/min.
The present invention can also be in step e, and the inlet hot blast temperature of spray-dryer is 115 ℃, 40 ℃ of temperature outs.
The present invention realizes that the technical scheme of second purpose is: a kind of according to the prepared polymer hollow microsphere of above-mentioned preparation method.
The invention has the beneficial effects as follows: adopted the emulsion polymerization technique of process stabilizing favorable reproducibility to prepare water-absorbing polymer; utilize hud polymerization to prepare the polymer microballoon of coating water-absorbent polymer then; the response characteristic of the functional monomer by the polymer microballoon surface has been prepared polymer hollow microsphere; and by regulating drying process with atomizing; the moisture that remains in the drying process in the water-absorbing polymer is heated becomes steam; the core-shell polymer steam inside is pressed and is become big; outer cover polymer is subjected to temperature gap to become big simultaneously; the comprehensive action of two processes is gone out the moisture evaporation of polymer microballoon inside; while is along with the reduction of particle envrionment temperature; the gap smaller sealing of outer cover polymer; make polymkeric substance internal medium pressure reduce; outer cover polymer gap complete closed when bulk temperature is reduced to room temperature, then the polymkeric substance internal pressure becomes negative pressure.Realized removing simultaneously the process of moisture and the small hole of confining surface, included that a large amount of hollow microspheres and hollow microsphere are inner to be the polymer hollow microsphere of negative pressure thereby obtain size ideal, inside.The material of all inputs all participates in reaction in preparation process of the present invention; after finishing, reaction do not have waste water and dregs to produce; in last spray-drying process, solvent and evaporable moisture all can be reclaimed, also do not have waste gas and waste water to produce, so environmental protection benefit be remarkable.And because the present invention has formed cross-linked polymer at outer cover polymer, so the polymer hollow microsphere of its preparation has good acid-fast alkali-proof performance.Compared with prior art, the advantage that the present invention has that energy consumption is low, preparation process is easy to control, range of product is many.Because the size of its particle diameter can be controlled, prepared tiny balloon has good size adaptability, stability is high, dimension adjustable, the production efficiency height, less energy consumption, pollution are lacked, and be simple to operate, be more suitable for using, and have application prospects and use value at aspects such as building materials and coating.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
A kind of preparation method of polymer hollow microsphere may further comprise the steps:
A. seed emulsion preparation:
Blending emulsifiers sneaked in the water stir, add water-absorbing polymer monomer and polymer monomers then, stir fast, make monomer whose fully emulsified, be warmed up to 60-80 ℃ then, add the initiator insulation reaction and obtained seed emulsion in 4～6 hours,
The weight part content of described raw material is:
Water 1500-2500
Blending emulsifiers 1.5-2.5
Water-absorbing polymer monomer 5-15
Polymer monomers 4-6
Initiator 0.5-1.5;
B. water-absorbent nuclear polymer preparation:
Under 60-80 ℃, in seed emulsion, slowly drip by the milk sap of forming by water-absorbing polymer monomer, polymer monomers, blending emulsifiers and water, abundant reaction adds alkaline aqueous solution adjusting pH value after 1.5 hours be 8～9, obtains water-absorbent nuclear polymer aqueous dispersions
The weight part content of raw material is in the described milk sap:
Water 140-180
Blending emulsifiers 3-4
Water-absorbing polymer monomer 200-280
Polymer monomers 50-80;
C. prepare polymer shell and introduce functional groups:
Get 1000 parts of above-mentioned water-absorbent nuclear polymer aqueous dispersions, with 1.5-2 times of water it is diluted, then under 60-80 ℃, to wherein dripping the shell milk sap of forming by monomer, blending emulsifiers and the water of polymer monomers, band functional groups, react after 1-2 hour, obtain the aqueous solution of coating water-absorbent polymer microballoon
The weight part content of raw material is in the described shell milk sap:
Water 200-240
Blending emulsifiers 3-5
Polymer monomers 300-400
The monomer 100-140 of band functional groups;
D. interface polymerization reaction:
In the above-mentioned aqueous solution, add and the complete immiscible solvent 1000-1500 part of water, add polycondensation monomer 80-120 part, carry out interface polymerization reaction under the normal temperature, lose promptly to react after active group exists through infrared test and finish;
E. prepare polymer hollow particles:
The previous reaction product is sent in the spray-dryer, and control inlet hot blast temperature is 100-120 ℃, and temperature out 20-60 ℃ is carried out spraying drying, obtain polymer hollow microsphere;
Wherein: described blending emulsifiers is by nonionic emulsifier and ionic emulsifying agent is composite forms, described polymer monomers is a vinylbenzene, methyl methacrylate, polyvinyl pyridine, in vinyl acetate and the polyethylene pyrrolidone one or more, described water-absorbing polymer monomer is a methacrylic acid, vinylformic acid, in methyl methacrylate and the butyl acrylate one or more, described initiator is a Potassium Persulphate, ammonium persulphate, the monomer of described band functional groups is to have amino, hydroxyl, the acrylic monomer of carboxyl or anhydride group functional groups, described and the complete immiscible solvent of water is a higher alkane, alkylbenzene and halohydrocarbon, described polycondensation monomer be can with the monomer of above-mentioned functions radical reaction.
Nonionic emulsifier is OP series or tween series or class of department series in the emulsifying agent of the present invention, and ionic emulsifying agent is anionic emulsifier or cationic emulsifier.
Nonionic emulsifier of the present invention is OP-10 or OP-15 or OP-20, and ionic emulsifying agent is sodium laurylsulfonate or extraordinary amido silicon oil or Sodium dodecylbenzene sulfonate or palmityl trimethyl ammonium chloride.
Water-absorbing polymer monomer of the present invention is the blend of methacrylic acid and butyl acrylate.
Polycondensation monomer of the present invention is monomer or the oligopolymer or the monomer of melamine class or cyclodextrin that contains isocyanate group.
A kind of preparation method of polymer hollow microsphere specifically,
In the described steps A, the weight part content of described raw material is: water 2000, blending emulsifiers 1.8, water-absorbing polymer monomer 10-15, polymer monomers 5-6, initiator 1-1.5, wherein blending emulsifiers is that OP-10 and 2: 1 by weight mixed of sodium laurylsulfonate form, the water-absorbing polymer monomer is to be formed by methacrylic acid and 5: 1 by weight mixed of butyl acrylate, and polymer monomers is a methyl methacrylate, and initiator is a Potassium Persulphate;
Among the described step B, the weight part content of raw material is in the described milk sap: water 160, blending emulsifiers 3.6-4.5, water-absorbing polymer monomer 240-280, polymer monomers 65-100, wherein blending emulsifiers is to be formed by OP-10 and 3: 1 by weight mixed of sodium laurylsulfonate, and the water-absorbing polymer monomer is a methacrylic acid, and polymer monomer is by vinylbenzene and methyl methacrylate by weight 1: the mixed of 1.8-2.2 forms;
Among the described step C, the weight part content of raw material is in the shell milk sap: water 220-240, blending emulsifiers 4-5, polymer monomers 340-400, the monomer 120-140 of band functional groups, wherein blending emulsifiers is to be formed by OP-10 and 3: 1 by weight mixed of sodium laurylsulfonate, polymer monomers be by vinylbenzene and methyl methacrylate by 4: the mixed of 0.8-1.2 forms, the monomer of band functional groups is to have amino, hydroxyl, the acrylic monomer or the unsaturated monomer of carboxyl or anhydride group functional groups.
Among the described step D, added with the complete immiscible solvent of water be hexanaphthene, dimethylbenzene, chloroform, the polycondensation monomer that is added is the diisocyanates monomer.Preferably tolylene diisocyanate or isophorone diisocyanate.
Among step B of the present invention, the step C, the drop rate of emulsion and shell emulsion is the 0.6-0.8 ml/min.
The present invention can also be in step e, and the inlet hot blast temperature of spray-dryer is 115 ℃, 40 ℃ of temperature outs.
According to the prepared polymer hollow microsphere of the present invention of above-mentioned preparation method, acid-fast alkali-proof and heat preservation and insulation are good, and the big and microballoon of particle diameter is inner be negative pressure, is suitable in the application of aspects such as building materials and coating, and has application prospects and use value.
Embodiment 1
1, in the four-hole boiling flask that reflux condensate device and agitator are housed, adds 2000 gram water, 1.25 gram OP-10 tensio-active agent and 0.65 gram sodium laurylsulfonate (SDS) fully stir, make tensio-active agent soluble in water fully, add 10 gram methacrylic acids (MAA) then, 5 gram methymethacrylates (MMA), 2 gram butyl acrylates (BA), regulating rotating speed is 1100 rev/mins, make monomer fully emulsified, be warmed up to 70 ℃ of Potassium Persulphate (KPS) solution that add 1 gram 2% then, under 70 ℃, carry out letex polymerization, react and obtained seed emulsion in 4-6 hour.The particle diameter of measuring seed emulsion through particle size analyzer is 0.018 micron
2, with the above-mentioned emulsion for preparing is seed, carry out the preparation of water-absorbent shell: the above-mentioned emulsion for preparing is heated to 70 ℃, in system, slowly drip by 244 gram methacrylic acids, 40 gram methymethacrylates, 28 gram vinylbenzene, 3.6 gram blending emulsifiers (OP-10 and sodium laurylsulfonate and water are by solution after 3: 1: 96 mixed), the milk sap that 160 gram water are formed, fixing drop rate 0.7 ml/min, in 6-8 hour, dropwise, and fully react after 1.5 hours and to add alkaline aqueous solution to regulate pH value be 8-9, thereby form water-absorbing polymer.Above-mentioned particle is 0.26 micron at the particle diameter that does not add before the basic solution, becomes 0.86 micron after adding basic solution;
3, after above-mentioned water-absorbing polymer is placed in the system fully suction, particle diameter becomes 1.96 microns, carry out polyreaction on its surface again, with the water-absorbing polymer is nuclear, the preparation polymer shell is also introduced functional groups, concrete preparation process is as follows: after above-mentioned water-absorbing polymer is fully absorbed moisture, get the aqueous polymer dispersion after 1000 grams absorb water, with 1500 gram water it is diluted, system is heated to 70 ℃ then, to wherein dripping 280 gram vinylbenzene, 120 gram functional monomer vinylformic acid uncle amino ester, 60 gram methymethacrylates, 4.2 gram blending emulsifiers, the milk sap that 220 gram water are formed.Fixing drop rate dropwised in 6-8 hour and fully reacts the polymer microballoon that obtained coating water-absorbent polymer in 1-2 hour.
4, in above-mentioned system, add and complete immiscible solvent hexanaphthene 3000 grams of water, and adding polycondensation monomer tolylene diisocyanate (MDI) 100 restrains in solvent, utilize the polymkeric substance preferentially adsorbed to solvent---the characteristics of water termination, at solvent---carry out interface polymerization reaction on the water termination, this reaction can rapid reaction at normal temperatures or under lesser temps (30-50 ℃) condition, among the present invention in this preparation engineering reaction 2-3 hour after infrared test lose and be reaction after active group exists and finish.
5, regulating the inlet hot blast temperature in spray-dryer is 105 ℃, after temperature out is 40 ℃, above-mentioned reaction product is entered in the spray-dryer by the constant flow pump pumping, utilize solvent to separate solvent recuperation in the exit and utilize again with the different thawing points of water, water vapor directly discharges, utilize in the spray-dryer high cryogenic graded to finish the evaporation of moisture in the water-absorbing polymer and the sealing of polymer surfaces hole, the polymer hollow microsphere that can on material of construction, use that finally obtains having ideal dimensions.Measuring its particle diameter through particle size analyzer is 2.69 microns
Embodiment 2:
1, in the four-hole boiling flask that reflux condensate device and agitator are housed, adds 2000 gram water, 1.25 gram OP-10 tensio-active agent and 0.65 gram sodium laurylsulfonate fully stir, make tensio-active agent soluble in water fully, add 15 gram methacrylic acids then, 8 gram methymethacrylates, 3 gram butyl acrylates, regulating rotating speed is 1100 rev/mins, make monomer fully emulsified, be warmed up to 70 ℃ of potassium persulfate solutions that add 2 grams 2% then, under 70 ℃, carry out letex polymerization, react and obtained seed emulsion in 4-6 hour.The particle diameter of measuring seed emulsion through particle size analyzer is 0.026 micron
2, with the above-mentioned emulsion for preparing is seed, carry out the preparation of water-absorbent shell: the above-mentioned emulsion for preparing is heated to 70 ℃, in system, slowly drip by 356 gram methacrylic acids, 50 gram methymethacrylates, 45 gram vinylbenzene, 4.8 gram blending emulsifiers (OP-10 and sodium laurylsulfonate and water are by solution after 3: 1: 96 mixed), the milk sap that 240 gram water are formed, fixedly drop rate is 0.6 ml/min, in 6-8 hour, dropwise, and fully react after 1.5 hours and to add alkaline aqueous solution to regulate pH value be 8-9, thereby form water-absorbing polymer.Above-mentioned particle is 0.34 micron at the particle diameter that does not add before the basic solution, becomes 1.12 microns after adding basic solution;
3, after above-mentioned water-absorbing polymer is placed in the system fully suction, particle diameter becomes 2.48 microns, carry out polyreaction on its surface again, with the water-absorbing polymer is nuclear, the preparation polymer shell is also introduced functional groups, concrete preparation process is as follows: after above-mentioned water-absorbing polymer is fully absorbed moisture, get the aqueous polymer dispersion after 1000 grams absorb water, with 1500 gram water it is diluted, system is heated to 70 ℃ then, to wherein dripping 360 gram vinylbenzene, 140 gram functional monomer methacrylic acid hydroxyl esters, 90 gram methymethacrylates, 5.3 the milk sap that gram blending emulsifiers 360 gram water are formed.Fixedly drop rate is 0.6 ml/min, dropwises in 6-8 hour and fully reacts the polymer microballoon that obtained coating water-absorbent polymer in 1-2 hour.
4, in above-mentioned system, add and complete immiscible chloroform solvent 3000 grams of water, and adding polycondensation monomer isophorone diisocyanate (IPDI) 150 restrains in solvent, utilize the polymkeric substance preferentially adsorbed to solvent---the characteristics of water termination, at solvent---carry out interface polymerization reaction on the water termination, this reaction can rapid reaction at normal temperatures or under lesser temps (30-50 ℃) condition, among the present invention in this preparation engineering reaction 2-3 hour after infrared test lose and be reaction after active group exists and finish.
5, regulating the inlet hot blast temperature in spray-dryer is 115 ℃, after temperature out is 50 ℃, above-mentioned reaction product is entered in the spray-dryer by the constant flow pump pumping, utilize solvent to separate solvent recuperation in the exit and utilize again with the different thawing points of water, water vapor directly discharges, utilize in the spray-dryer high cryogenic graded to finish the evaporation of moisture in the water-absorbing polymer and the sealing of polymer surfaces hole, the polymer hollow microsphere that can on material of construction, use that finally obtains having ideal dimensions.Measuring its particle diameter through particle size analyzer is 3.46 microns
Embodiment 3:
1, in the four-hole boiling flask that reflux condensate device and agitator are housed, adds 3000 gram water, 2.25 gram OP-10 tensio-active agent and 1.15 gram sodium laurylsulfonates fully stir, make tensio-active agent soluble in water fully, add 20 gram methacrylic acids then, 10 gram methymethacrylates, 5 gram butyl acrylates, regulating rotating speed is 1100 rev/mins, make monomer fully emulsified, be warmed up to 70 ℃ of potassium persulfate solutions that add 4 grams 2% then, under 70 ℃, carry out letex polymerization, react and obtained seed emulsion in 4-6 hour.The particle diameter of measuring seed emulsion through particle size analyzer is 0.34 micron
2, with the above-mentioned emulsion for preparing is seed, carry out the preparation of water-absorbent shell: the above-mentioned emulsion for preparing is heated to 70 ℃, in system, slowly drip by 488 gram methacrylic acids, 80 gram methymethacrylates, 56 gram vinylbenzene, 7.2 gram blending emulsifiers (OP-10 and sodium laurylsulfonate and water are by solution after 3: 1: 96 mixed), the milk sap that 480 gram water are formed, fixedly drop rate is 0.8 ml/min, in 6-8 hour, dropwise, and fully react after 1.5 hours and add alkaline aqueous solution, the adjusting pH value is 8-9, thereby forms water-absorbing polymer.Above-mentioned particle is 1.34 microns at the particle diameter that does not add before the basic solution, becomes 2.16 microns after adding basic solution;
3, after above-mentioned water-absorbing polymer is placed in the system fully suction, particle diameter becomes 3.89 microns, carry out polyreaction on its surface again, with the water-absorbing polymer is nuclear, the preparation polymer shell is also introduced functional groups, concrete preparation process is as follows: after above-mentioned water-absorbing polymer is fully absorbed moisture, get the aqueous polymer dispersion after 1000 grams absorb water, with 1500 gram water it is diluted, system is heated to 70 ℃ then, to the 60 gram vinylbenzene of Dropwise 5 wherein, 250 gram functional monomer Hydroxyethyl acrylates, 120 gram methymethacrylates, 6.4 gram blending emulsifiers, the milk sap that 600 gram water are formed.Fixedly drop rate is 0.75 ml/min, dropwises in 6-8 hour and fully reacts the polymer microballoon that obtained coating water-absorbent polymer in 1-2 hour.
4, in above-mentioned system, add and complete immiscible xylene solvent 3500 grams of water, and adding polycondensation monomer tolylene diisocyanate (TDI) oligopolymer 160 restrains in solvent, utilize the polymkeric substance preferentially adsorbed to solvent---the characteristics of water termination, at solvent---carry out interface polymerization reaction on the water termination, this reaction can rapid reaction at normal temperatures or under lesser temps (30～50 ℃) condition, reacts in this preparation engineering 2～3 hours among the present invention after infrared test loses and is reaction after active group exists and finishes.
5, regulating the inlet hot blast temperature in spray-dryer is 115 ℃, after temperature out is 50 ℃, above-mentioned reaction product is entered in the spray-dryer by the constant flow pump pumping, utilize solvent to separate solvent recuperation in the exit and utilize again with the different thawing points of water, water vapor directly discharges, utilize in the spray-dryer high cryogenic graded to finish the evaporation of moisture in the water-absorbing polymer and the sealing of polymer surfaces hole, the polymer hollow microsphere that can on material of construction, use that finally obtains having ideal dimensions.Measuring its particle diameter through particle size analyzer is 34.89 microns.
The hollow polymer microsphere of the present invention's preparation has good heat-proof quality and possesses the good mechanical performance simultaneously, after measured, hollow polymer microsphere cylindrical compress strength of the present invention reaches 0.6～1.2MPa, and thermal conductivity is 0.022W/m.K, and tap density is 200～500kg/m
3Simultaneously because polymer shell polymer formation of the present invention cross-linked polymer, therefore has good acid-fast alkali-proof performance, after measured, acid resistance can reach 96 hours does not have any variation (1M concentration sulphuric acid soln, 60 ℃), alkaline resistance properties can reach 96 hours does not have any variation (1M concentration hydrogen sodium hydroxide solution, 60 ℃).Compare existing polymer hollow microsphere and have good alkaline resistance properties and heat preservation and insulation, and its particle diameter of hollow polymer of the present invention can and be adjusted source material mixture ratio by the adjusting process condition, can adjust the size of water-absorbent nuclear suction back particle diameter by the add-on of adjusting water absorbent polymer material in the water-absorbent nuclear, for example, the add-on that improves water absorbent polymer can cause core copolymer suction back volume to become big, just can obtain the bigger hollow polymer material of particle diameter if carry out follow-up processing on this basis, also can obtain the polymkeric substance of different-grain diameter by the adjusting process condition, it mainly is the rotating speed that mixes in the emulsion polymerization process by adjusting, reducing rotating speed can cause the mutual coalescence of emulsion particle and produce reuniting, thereafter will obtain particle diameter than particle big but that reunion is comparatively severe, also has hollow structure after the drying, but it is different adjusting the method for water absorbent polymer nuclear add-on and the microtexture of the hollow polymer particle that method obtained of adjusting process condition, before a kind of method obtains is the hollow polymer particle of a large amount of single hollow structure, that is to say, resulting hollow particle inside is one or two to three cavities, but a kind of method in back obtains is reunite mutually together hollow microspheres of a large amount of little cavities, briefly, a kind of method obtains exactly is to obtain the bigger microballoon of particle diameter that two or three bigger microballoons of particle diameter are formed for one or two, the microballoon of the big particle diameter of being made up of a large amount of small particle size hollow microspheres that then a kind of method obtains.Therefore, by adjusting feed ratio and processing condition its particle diameter can be controlled in the 2-50 micrometer range.Comparing existing polymer hollow microsphere particle diameter single is a much progress, compare with existing polymer hollow microsphere dried forms, the present invention adopts spray-dired method, and utilizes that variation of temperature makes the inner negative pressure that forms in spray-dired process, and its pressure values is 0.2046 * 10 after measured
5KPa.This also is that existing polymer hollow microsphere institute is unapproachable.Compare existing other tiny balloons, as hollow glass micro-ball, it is low that tiny balloon of the present invention has energy consumption, and particle diameter is little, the characteristics of applied range, and do not have waste water and dregs to produce.Compare closed perlite, hollow polymer microsphere of the present invention has that cylindrical compress strength is bigger, and thermal conductivity is lower, and heat-proof quality is characteristics preferably.
Specific embodiment described herein only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of this specification sheets.
Claims (8)
1. the preparation method of a polymer hollow microsphere is characterized in that may further comprise the steps:
A. seed emulsion preparation:
Blending emulsifiers sneaked in the water stir, add water-absorbing polymer monomer and polymer monomers then, stir fast, make monomer whose fully emulsified, be warmed up to 60-80 ℃ then, add the initiator insulation reaction and obtained seed emulsion in 4-6 hour,
The weight part content of described raw material is:
Water 1500-2500
Blending emulsifiers 1.5-2.5
Water-absorbing polymer monomer 5-15
Polymer monomers 4-6
Initiator 0.5-1.5;
B. water-absorbent nuclear polymer preparation:
Under 60-80 ℃, in seed emulsion, slowly drip by the milk sap of forming by water-absorbing polymer monomer, polymer monomers, blending emulsifiers and water, abundant reaction adds alkaline aqueous solution adjusting pH value after 1.5 hours be 8-9, obtains water-absorbent nuclear polymer aqueous dispersions
The weight part content of raw material is in the described milk sap:
Water 140-180
Blending emulsifiers 3-4
Water-absorbing polymer monomer 200-280
Polymer monomers 50-80;
C. prepare polymer shell and introduce functional groups:
Get 1000 parts of above-mentioned water-absorbent nuclear polymer aqueous dispersions, with 1.5-2 times of water it is diluted, then under 60-80 ℃, to wherein dripping the shell milk sap of forming by monomer, blending emulsifiers and the water of polymer monomers, band functional groups, react after 1-2 hour, obtain the aqueous solution of coating water-absorbent polymer microballoon
The weight part content of raw material is in the described shell milk sap:
Water 200-240
Blending emulsifiers 3-5
Polymer monomers 300-400
The monomer 100-140 of band functional groups;
D. interface polymerization reaction:
In the above-mentioned aqueous solution, add and the complete immiscible solvent 1000-1500 part of water, add polycondensation monomer 80-120 part, carry out interface polymerization reaction under the normal temperature, lose promptly to react after active group exists through infrared test and finish;
E. prepare polymer hollow microsphere:
The previous reaction product is sent in the spray-dryer, and control inlet hot blast temperature is 100-120 ℃, and temperature out 20-60 ℃ is carried out spraying drying, obtain polymer hollow microsphere;
Wherein: described blending emulsifiers is by nonionic emulsifier OP-10 and the ionic emulsifying agent sodium laurylsulfonate is composite forms, described polymer monomers is a vinylbenzene, methyl methacrylate, polyvinyl pyridine, in vinyl acetate and the polyethylene pyrrolidone one or more, described water-absorbing polymer monomer is a methacrylic acid, vinylformic acid, in methyl methacrylate and the butyl acrylate one or more, described initiator is a Potassium Persulphate, ammonium persulphate, described functional monomer is to have amino, hydroxyl, the acrylic monomer of carboxyl or anhydride group functional groups, described polycondensation monomer be can with the monomer of above-mentioned functions radical reaction.
2. the preparation method of a kind of polymer hollow microsphere according to claim 1, it is characterized in that: the water-absorbing polymer monomer is the blend of methacrylic acid and butyl acrylate.
3. the preparation method of a kind of polymer hollow microsphere according to claim 1, it is characterized in that: described polycondensation monomer is monomer or the oligopolymer or the monomer of melamine class or cyclodextrin that contains isocyanate group.
4. the preparation method of a kind of polymer hollow microsphere according to claim 1 is characterized in that:
In the described steps A, the weight part content of described raw material is: water 2000, blending emulsifiers 1.8, water-absorbing polymer monomer 10-15, polymer monomers 5-6, initiator 1-1.5, wherein blending emulsifiers is that OP-10 and 2: 1 by weight mixed of sodium laurylsulfonate form, the water-absorbing polymer monomer is to be formed by methacrylic acid and 5: 1 by weight mixed of butyl acrylate, and polymer monomers is a methyl methacrylate, and initiator is a Potassium Persulphate;
Among the described step B, the weight part content of raw material is in the described milk sap: water 160, blending emulsifiers 3.6-4.5, water-absorbing polymer monomer 240-280, polymer monomers 65-100, wherein blending emulsifiers is to be formed by OP-10 and 3: 1 by weight mixed of sodium laurylsulfonate, and the water-absorbing polymer monomer is a methacrylic acid, and polymer monomer is by vinylbenzene and methyl methacrylate by weight 1: the mixed of 1.8-2.2 forms;
Among the described step C, the weight part content of raw material is in the shell milk sap: water 220-240, blending emulsifiers 4-5, polymer monomers 340-400, the monomer 120-140 of band functional groups, wherein blending emulsifiers is to be formed by OP-10 and 3: 1 by weight mixed of sodium laurylsulfonate, polymer monomers be by vinylbenzene and methyl methacrylate by 4: the mixed of 0.8-1.2 forms, the monomer of band functional groups is to have amino, hydroxyl, the acrylic monomer of carboxyl or anhydride group functional groups;
Among the described step D, adding with the complete immiscible solvent of water be higher alkane, alkylbenzene and halohydrocarbon, wherein polycondensation monomer is tolylene diisocyanate or isophorone diisocyanate.
5. the preparation method of a kind of polymer hollow microsphere according to claim 1 is characterized in that: described and the complete immiscible solvent of water are hexanaphthene or dimethylbenzene or chloroform.
6. the preparation method of a kind of polymer hollow microsphere according to claim 1, it is characterized in that: in step B, step C, the drop rate of emulsion and shell emulsion is the 0.6-0.8 ml/min.
7. the preparation method of a kind of polymer hollow microsphere according to claim 1, it is characterized in that: in step e, the inlet hot blast temperature of spray-dryer is 115 ℃, 40 ℃ of temperature outs.
8. one kind according to the prepared polymer hollow microsphere of each described preparation method among the claim 1-7.
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