CN104877166A - Method for low-density polymeric microspheres without surface permeability by suspension polymerization in-situ closing - Google Patents
Method for low-density polymeric microspheres without surface permeability by suspension polymerization in-situ closing Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 title abstract description 5
- 230000035699 permeability Effects 0.000 title abstract 5
- 229920000642 polymer Polymers 0.000 claims abstract description 108
- 239000000178 monomer Substances 0.000 claims abstract description 45
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
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- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention relates to a method for low-density polymeric microspheres without surface permeability by suspension polymerization in-situ closing and belongs to the technical field of polymer functional materials. The low-density polymeric microspheres without surface permeability is prepared by the steps: by taking porous or hollow microspheres with low permeability on the surfaces with microchannels as seeds and by virtue of the characteristic that a monomer and a polymer have good affinity, diffusing the monomer to the surfaces of the seed microspheres to form a monomer liquid layer; and then carrying out an in-situ polymerization reaction to obtain a polymer coating to close microsphere surface channels so as to obtain the low-density polymeric microspheres without surface permeability. The polymeric microspheres closed by the method have good performances such as insulativity, light scattering, sound insulation, elasticity, compressive strength and the like and have a wide application prospect in the field of petroleum drilling additives, acid fog inhibition, ultrasound contrast reagents, photoelectric materials, adhesives, paper-making, communication and the like.
Description
Technical field
The present invention relates to a kind of suspension polymerization original position and close the method preparing surface permeation-free low-density polymer microballoon, belong to Functionally structure technical field.
Background technology
Polymer microspheres is applied to various field widely.According to different demands, people can preparation size, form and the different polymer microspheres of microtexture.Wherein, in order to meet the specific demand in the field such as petroleum drilling additive and acid mist suppression, there is surperficial the causing without infiltrative hollow or porous polymer microsphere of low density and pay close attention to widely.
At present, research work about low density hollow or porous polymer microsphere mainly concentrates on the polymer microballoon that method preparations such as utilizing letex polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, microfluid polymerization and templated synthesis has special construction feature (as: shell-core, be separated), and then it is auxiliary with the method such as extraction, dialysis, solvent evaporation, etching, spraying dry, vacuum-drying, from microballoon, remove liquid phase, obtain hollow or porous microsphere.Wherein Chinese patent CN101250244B reports that the preparation of a kind of spray-drying process is inner includes a large amount of hollow microsphere and hollow microsphere inside is the method for the polymer hollow microsphere of negative pressure, CN1303140C reports a kind of method that strong acid etching method prepares polymer hollow particles, CN100562358C reports a kind of method preparing polymer hollow particles with hydrogel template, 201010543593.8, 201010624786.6, 201110040481.5, 201110052468.1, 201110150863.3, 201110150862.9 etc. the preparation method reporting multiple polymers hollow or porous microsphere.By the polymer microballoon that above method prepares, hole need be formed from its inner pore-creating agent (or the material such as solvent, template) of removing, wherein relate to solvent from the inner exterior surface migration of microballoon, therefore the microsphere surface (or shell) prepared is through with inner hole (or cavity), there is stronger perviousness, after microballoon is soaked for a long time by liquid, micropore permeation by microsphere surface is entered core inside aperture (or cavity) by liquid ingredient, cause the density of microballoon to increase rapidly, its floatability is significantly reduced.In addition, because pore-creating agent is to the needs of external migration, the shell thickness of these microballoons is often very little, so mechanical property is generally poor.Therefore, need the preparation method of improvement and optimization hollow or porous polymer microsphere, preparation has the low density surface of good mechanical properties and density retention without osmotic polymer microballoon.
Based on gas template, prepare hollow or porous microsphere is realize microsphere surface without a kind of infiltrative method.Up to the present, then different research workers meets cold-curing (Sun Yanlin etc. by utilizing thermoplastic polymer to wrap up rare gas element, a kind of surface is without osmotic polymer hollow microsphere and preparation method thereof, Chinese patent CN201310060560.1), meet the solidification of water cure monomer on water vapor microbubble (Toshinori Makuta, et al. Hollow microspheres fabricated from instant adhesive. Materials Letters, 2011, 65:3415-3417), the absorption of hydrophobic polymer nanometer ball on microbubble surface and precipitation (Wolfgang Schmidt, et al. Novel manufacturing process of hollow polymer microspheres. Chemical Engineering Science, 2006, 61:4973-4981.), spray-drying process (Narayan PM, et al. Optimization of spray drying by factorial design for production of hollow microspheres for ultrasound imaging. Journal of Biomedical Materials Research, 2001, 56:333-341.), W/O/W(or O/W/O) double-deck emulsification mechanism (Kim JW, et al. Multi-hollow polymer microcapsules by water-in-oil-in-water emulsion polymerization:morphological study and entrapment characteristics. Colloid and Polymer Science, 2003, 281:157-163.) and freeze-drying (Sang Hyuk Im, et al. Polymer hollow particles with controllable holes in their surfaces. Nature Materials, 2005, 4:671-675) etc. method has directly prepared polymer hollow particles.In above method, although by controlling reaction conditions, its shell density is relatively better, and hole formation still relies on the process such as the transfer of gas and the precipitation deposition of polymkeric substance in essence, so the compactness still defectiveness of shell, therefore also has perviousness.In addition, the microballoon that above method prepares otherwise shell thickness limited, or size is restricted, and therefore further limit the utilization of microballoon.
Realize porous or polymeric hollow microsphere surface is that effects on surface has the porous in duct or polymeric hollow microsphere is implemented to close without another feasible way infiltrative.CN102585279A reports a kind of gaseous suspension legal system that adopts for the method for surface permeation-free low-density polymer microsphere, the method realizes closing it by utilizing chance water rapid-curing cutback monomer effects on surface to have the porous of water or hollow microsphere surface hole defect to cover, prepared the adjustable surface of multiple density without osmotic polymer microballoon, have good can floatability for a long time.The core element of this inventive method is the organic monomer of meeting water cure, the widespread use of this inventive method of the performance limitations of its uniqueness; In addition, meet water cure monomer and existed in vapour form before contact microsphere surface hydration layer, therefore in chance water cure process, monomer feed rate is limited, is unfavorable for closing duct, microsphere surface wide aperture.Therefore, need to invent the stronger coating method of a kind of versatility, thus realize to polyalcohol stephanoporate or hollow microsphere surface duct close.
Suspension polymerization original position of the present invention closes method, has operation more simple, does not need to use special equipment, and production cost is lower, has greater significance to applying of polymer microballoon.In addition, adopt method of the present invention, by selecting monomer and the linking agent with different performance feature, can also while microballoon be closed, the coating thickness of microballoon regulated and functional modification is carried out to its surface, making microballoon have more superior process based prediction model.
Summary of the invention
The present invention is preparing the deficiency in surface permeation-free low-density polymer microballoon to overcome prior art, provides a kind of suspension polymerization original position to close the method preparing surface permeation-free low-density polymer microballoon.The method has the low-permeability porous of microchannel or hollow microsphere for seed with surface, monomer and polymkeric substance is utilized to have the feature of good affinity, make monomer diffuse to seed microsphere surface and form monomer liquid layer, then carry out home position polymerization reaction formation polymer coating and close microsphere surface duct, obtain surface permeation-free low-density polymer microsphere, the present invention is achieved through the following technical solutions.
A kind of suspension polymerization original position is closed and is prepared the method for low density surface without osmotic polymer microballoon, there is the low-permeability microballoon of microchannel as seed using surface, monomer and polymkeric substance is utilized to have the feature of good affinity, make monomer diffuse to seed microsphere surface and form monomer liquid layer, then carry out home position polymerization reaction formation polymer coating and close microsphere surface duct, obtain surface permeation-free low-density polymer microsphere.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, and its concrete steps are as follows:
Step 1, in the reactor that agitator, reflux condensation mode and heating unit are housed, first distilled water is added, open and stir and rotating speed is adjusted to 100 ~ 500 revs/min, add porous or the hollow polymer seed microballoon of diameter≤1.0, surface micropore road μm, distilled water is 3 ~ 1:1 with polymer seeds microspheres quality ratio, finally add the mixing solutions of monomer, linking agent and initiator, then temperature of reaction system is risen to 65 ~ 75 DEG C of reactions 2 ~ 3 hours;
After step 2, step 1 complete, keep temperature-resistant, mixing speed is heightened to 400 ~ 1000 revs/min, monomer, linking agent and initiator mixing solutions is dripped in reaction system in step 1, controlling drop rate makes this mixing solutions dropwise in 3 ~ 5 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.
The pore volume rate of the porous in described step 1 or hollow polymer seed microballoon is 1% ~ 70%, and particle diameter is 1.0 μm ~ 1000.0 μm; This polymer seeds microballoon can be adopt letex polymerization (comprising seeding polymerization, mini-emulsion polymerization, microemulsion, emulsifier-free emulsion polymerization, film letex polymerization etc.), suspension polymerization, dispersion polymerization, precipitation polymerization, microfluid is polymerized, the porous that in the methods such as templated synthesis prepared by any one method or polymeric hollow microsphere.
Monomer in described step 1 and 2 is one or more the arbitrary proportion mixtures in vinylbenzene, methyl methacrylate, acrylamide, N-N DMAA, butyl acrylate, vinyl acetate, and the add-on of monomer calculates according to initial enclosed layer thickness and final enclosed layer thickness.The monomer add-on of step 1 calculates according to initial enclosed layer thickness, and calculation formula is:
, in formula:
mfor monomer consumption, g;
nfor the quantity of polymer seeds microballoon, individual;
d 1for the diameter of polymer seeds microballoon, cm;
d 1for beginning enclosed layer thickness, cm;
rfor monomer density, g/cm
3.In step 2, the add-on of monomer calculates according to final enclosed layer thickness, and calculation formula is:
, in formula:
mfor monomer consumption, g;
nfor the quantity of polymer seeds microballoon, individual;
d 2for initially closing the diameter of post-consumer polymer seed microballoon, cm;
d 2for final enclosed layer thickness, cm;
rfor monomer density, g/cm
3.
Linking agent in described step 1 and 2 is Vinylstyrene, dicyclopentadiene, Ethylene glycol dimethacrylate or methyl cyclopentadiene, in rapid 1, the add-on of linking agent is 0% ~ 50% of step 1 monomer mass, and in step 2, the add-on of linking agent is 0% ~ 50% of step 2 monomer mass.
Initiator in described step 1 and 2 is Diisopropyl azodicarboxylate, benzoyl peroxide or tertbutyl peroxide; in step 1, the add-on of initiator is 1% ~ 2.5% of step 1 monomer mass, and in step 2, the add-on of initiator is 1% ~ 2.5% of step 2 monomer mass.
The invention has the beneficial effects as follows: the invention provides a kind of method preparing surface permeation-free low-density polymer microballoon that versatility is fine and easy, quick, economic, pass through suspension polymerization, make monomer directly at microsphere surface in-situ polymerization, carry out effectively totally-enclosed to the microchannel of microsphere surface.Make use of monomer due to the inventive method and polymkeric substance has good affinity, monomer can be made effectively to diffuse to microballoon channel surfaces and form monomer liquid rete and carry out in-situ polymerization and form polymkeric substance, therefore can realize effectively closing small size duct.Method of the present invention can to pore volume rate at 1% ~ 70%(V/V) between, microchannel diameter≤1.0 μm, the surface micropore road of hollow (or porous) polymer microballoon of particle size range between 1.0 μm ~ 1000.0 μm is effectively closed, effectively avoid this polymer microballoon in use, because liquid substance is by the infiltration of its surface micropore road to core inside aperture or cavity, cause the shortcoming that density changes, make it under the low-density prerequisite of maintenance, have excellent can the performance such as floating for a long time.Simultaneously, because the inventive method carries out surface-closed in atmospheric conditions, be closed air in the hole of microballoon or cavity suitable with external atmospheric pressure, therefore internal stress can not be produced, in addition the inventive method can regulate the thickness of microballoon sealer coat by the consumption of monomer, thus make prepared low density surface have better mechanical property without osmotic polymer microballoon, and density is adjustable.With the polymer microballoon that the inventive method is closed there is good insulativity, the performance such as light falls apart look, sound insulation, elasticity and ultimate compression strength, make it be with a wide range of applications in the field such as petroleum drilling additive, acid mist suppression, ultrasound contrast reagent, photoelectric material, coating, binding agent, papermaking, communication.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The underlying parameter of seed polymer microballoon to be closed: mean diameter is 10 μm, pore volume rate is 6.4%(V/V), average surface microchannel diameter is 0.5 ± 0.08 μm, and density is 0.94g/cm
3polystyrene porous microballoon, microballoon consumption 200.0g, initial coating thickness of closing is about 0.05 μm, and final coating thickness of closing is about 0.05 μm.
Then total number of seed microballoon is:
.
In step 1, the add-on of styrene monomer calculates according to initial enclosed layer thickness, and calculation formula is
, add-on is
.
In step 2, the add-on of styrene monomer calculates according to final coating thickness of closing, and calculation formula is
, add-on is
.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, it is characterized in that concrete steps are as follows:
Step 1, in the reactor that agitator, reflux condensation mode and heating unit are housed, first distilled water 300.0g is added, open and stir and rotating speed is adjusted to 400 revs/min, add above-mentioned polymer seeds microballoon 200.0g again, distilled water and polymer seeds microspheres quality are than being 1.5:1, finally add vinylbenzene 6.7g, Vinylstyrene 3.35g(vinylbenzene quality 50%) and the 1.5wt% of Diisopropyl azodicarboxylate 0.1g(vinylbenzene quality) mixing solutions, then temperature of reaction system is risen to 65 DEG C of reactions 3 hours.
Step 2, after step 1 completes, keep temperature-resistant, mixing speed is heightened to 800 revs/min, vinylbenzene 6.8g is dripped in reaction system in step 1, 50% of Vinylstyrene 3.4g(vinylbenzene quality) and the 1.0wt% of Diisopropyl azodicarboxylate 0.068g(vinylbenzene quality) mixing solutions, controlling drop rate makes this mixing solutions dropwise in 5 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.
The above-mentioned surface prepared is 0.96g/cm without the density of osmotic polymer microballoon
3.By the press-in of this polymer microballoon porous plate water and ethanol contend than be 1:3 mixing solutions in soak 30 days, at room temperature naturally dry after taking-up, density is unchanged, illustrates that this polymer microballoon is surperficial without perviousness.
Embodiment 2
The underlying parameter of seed polymer microballoon to be closed: mean diameter is 50 μm, pore volume rate is 23.8%(V/V), average surface microchannel diameter is 0.2 ± 0.05 μm, and density is 0.68g/cm
3polystyrene hollow microsphere, microballoon consumption 100.0g, initial coating thickness of closing is about 3.0 μm, and final coating thickness of closing is about 5.0 μm.
Then total number of seed microballoon is:
.
In step 1, the add-on of vinylbenzene and methyl methacrylate monomer calculates according to initial enclosed layer thickness, and calculation formula is
, add-on is
.
In step 2, the add-on of vinylbenzene and acrylamide monomer calculates according to final coating thickness of closing, and calculation formula is
, add-on is
.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, and its concrete steps are as follows:
Step 1, agitator is being housed, in the reactor of reflux condensation mode and heating unit, first distilled water 300.0g is added, open and stir and rotating speed is adjusted to 500 revs/min, add above-mentioned polymer seeds microballoon 100.0g again, distilled water and polymer seeds microspheres quality are than being 3:1, finally add vinylbenzene 26.3g, methyl methacrylate 26.3g, the 30wt% of dicyclopentadiene 15.78g(vinylbenzene and methyl methacrylate quality) and the 2.5wt% of benzoyl peroxide 1.315g(vinylbenzene and methyl methacrylate quality) mixing solutions, then temperature of reaction system is risen to 75 DEG C of reactions 2 hours.
Step 2, after step 1 completes, keep temperature-resistant, mixing speed is heightened to 1000 revs/min, vinylbenzene 65.45g is dripped in reaction system in step 1, acrylamide 65.45g, 20% of dicyclopentadiene 26.18g(vinylbenzene and acrylamide quality) and the 2.5wt% of benzoyl peroxide 3.27g(vinylbenzene and acrylamide quality) mixing solutions, controlling drop rate makes this mixing solutions dropwise in 3 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.
The above-mentioned surface prepared is 0.82g/cm without the density of osmotic polymer microballoon
3.By the press-in of this polymer microballoon porous plate water and ethanol contend than be 1:3 mixing solutions in soak 30 days, at room temperature naturally dry after taking-up, density is unchanged, illustrates that this polymer microballoon is surperficial without perviousness.
Embodiment 3
The underlying parameter of seed polymer microballoon to be closed: mean diameter is 100 μm, pore volume rate is 45.6%(V/V), average surface microchannel diameter is 0.3 ± 0.05 μm, and density is 0.51g/cm
3polystyrene hollow microsphere, microballoon consumption 100.0g, initial coating thickness of closing is about 1.0 μm, and final coating thickness of closing is about 3.0 μm.
Then total number of seed microballoon is:
.
In step 1, the add-on of N-N DMAA and Butyl Acrylate Monomer calculates according to initial enclosed layer thickness, and calculation formula is
, add-on is
.
In step 2, the add-on of vinylbenzene and acrylamide monomer calculates according to final coating thickness of closing, and calculation formula is
, add-on is
.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, and its concrete steps are as follows:
Step 1, agitator is being housed, in the reactor of reflux condensation mode and heating unit, first distilled water 100.0g is added, open and stir and rotating speed is adjusted to 100 revs/min, add above-mentioned polymer seeds microballoon 100.0g again, distilled water and polymer seeds microspheres quality are than being 1:1, finally add N-N DMAA 5.5g, butyl acrylate 5.5g, Ethylene glycol dimethacrylate 4.4g(add-on is 40% of N-N DMAA and butyl acrylate quality) and tertbutyl peroxide 0.11g(add-on be the 1.0wt% of N-N DMAA and butyl acrylate quality) mixing solutions, then temperature of reaction system is risen to 70 DEG C of reactions 2.5 hours.
Step 2, after step 1 completes, keep temperature-resistant, mixing speed is heightened to 400 revs/min, vinylbenzene 21.8g is dripped in reaction system in step 1, acrylamide 21.8g, Ethylene glycol dimethacrylate 8.72g(add-on is the 20wt% of vinylbenzene and acrylamide quality) and tertbutyl peroxide 1.09g(add-on be the 2.5wt% of vinylbenzene and acrylamide quality) mixing solutions, controlling drop rate makes this mixing solutions dropwise in 5 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.
The above-mentioned surface prepared is 0.68g/cm without the density of osmotic polymer microballoon
3.By the press-in of this polymer microballoon porous plate water and ethanol contend than be 1:3 mixing solutions in soak 30 days, at room temperature naturally dry after taking-up, density is unchanged, illustrates that this polymer microballoon is surperficial without perviousness.
Embodiment 4
The underlying parameter of seed polymer microballoon to be closed: mean diameter is 500 μm, pore volume rate is 70.0%(V/V), average surface microchannel diameter is 0.5 ± 0.05 μm, and density is 0.31g/cm
3polymethylmethacrylate hollow microsphere, microballoon consumption 100.0g, initial coating thickness of closing is about 0.5 μm, and final coating thickness of closing is about 1.5 μm.
Then total number of seed microballoon is:
In step 1, the add-on of methyl methacrylate monomer calculates according to initial enclosed layer thickness, and calculation formula is
, add-on is
.
In step 2, the add-on of methyl methacrylate monomer calculates according to final coating thickness of closing, and calculation formula is
, add-on is
.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, and its concrete steps are as follows:
Step 1, agitator is being housed, in the reactor of reflux condensation mode and heating unit, first distilled water 200.0g is added, open and stir and rotating speed is adjusted to 350 revs/min, add above-mentioned polymer seeds microballoon 100.0g again, distilled water and polymer seeds microspheres quality are than being 2:1, finally add methyl methacrylate 1.8g, methyl cyclopentadiene 0.9g(add-on is 50% of methyl methacrylate quality) and tertbutyl peroxide 0.018g(add-on be the 1.0wt% of methyl methacrylate quality) mixing solutions, then temperature of reaction system is risen to 70 DEG C of reactions 2.5 hours.
Step 2, after step 1 completes, keep temperature-resistant, mixing speed is heightened to 700 revs/min, methyl methacrylate 5.5g is dripped in reaction system in step 1, methyl cyclopentadiene 2.75g(add-on is the 50wt% of methyl methacrylate quality) and tertbutyl peroxide 0.11g(add-on be the 2.0wt% of methyl methacrylate quality) mixing solutions, controlling drop rate makes this mixing solutions dropwise in 5 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.
The above-mentioned surface prepared is 0.38g/cm without the density of osmotic polymer microballoon
3.By the press-in of this polymer microballoon porous plate water and ethanol contend than be 1:3 mixing solutions in soak 30 days, at room temperature naturally dry after taking-up, density is unchanged, illustrates that this polymer microballoon is surperficial without perviousness.
Embodiment 5
The underlying parameter of seed polymer microballoon to be closed: mean diameter is 1 μm, pore volume rate is 1.0%(V/V), average surface microchannel diameter is 0.02 ± 0.005 μm, and density is 0.91g/cm
3poly-melamino-formaldehyde porous microsphere, microballoon consumption 100.0g, initial coating thickness of closing is about 0.01 μm, and final coating thickness of closing is about 0.02 μm.
Then total number of seed microballoon is:
.
In step 1, the add-on of Vinyl Acetate Monomer calculates according to initial enclosed layer thickness, and calculation formula is
, add-on is
.
In step 2, the add-on of styrene monomer calculates according to final coating thickness of closing, and calculation formula is
, add-on is
.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, and its concrete steps are as follows:
Step 1, in the reactor that agitator, reflux condensation mode and heating unit are housed, first distilled water 300.0g is added, open and stir and rotating speed is adjusted to 400 revs/min, add above-mentioned polymer seeds microballoon 100.0g again, distilled water and polymer seeds microspheres quality are than being 3:1, finally add the 2.5wt% that vinyl acetate 6.1g and benzoyl peroxide 0.153g(add-on are vinyl acetate quality) mixing solutions, then temperature of reaction system is risen to 70 DEG C of reactions 3 hours, not containing linking agent;
Step 2, after step 1 completes, keep temperature-resistant, mixing speed is heightened to 900 revs/min, drip the 2.5wt% that vinylbenzene 14.4g and benzoyl peroxide 0.36g(add-on are vinylbenzene quality in reaction system in step 1) mixing solutions, controlling drop rate makes this mixing solutions dropwise in 3 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.Not containing linking agent.
The above-mentioned surface prepared is 0.96g/cm without the density of osmotic polymer microballoon
3.By the press-in of this polymer microballoon porous plate water and ethanol contend than be 1:3 mixing solutions in soak 30 days, at room temperature naturally dry after taking-up, density is unchanged, illustrates that this polymer microballoon is surperficial without perviousness.
Embodiment 6
The underlying parameter of seed polymer microballoon to be closed: mean diameter is 1000 μm, pore volume rate is 21.5%(V/V), average surface microchannel diameter is 0.9 ± 0.1 μm, and density is 0.83g/cm
3polymethylmethacrylate porous microsphere, microballoon consumption 100.0g, initial coating thickness of closing is about 10.0 μm, and final coating thickness of closing is about 30.0 μm.
Then total number of seed microballoon is:
.
In step 1, the add-on of styrene esters monomer calculates according to initial enclosed layer thickness, and calculation formula is
, add-on is
.
In step 2, the add-on of styrene monomer calculates according to final coating thickness of closing, and calculation formula is
, add-on is
.
Above-mentioned suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, and its concrete steps are as follows:
Step 1, in the reactor that agitator, reflux condensation mode and heating unit are housed, first distilled water 3200.0g is added, open and stir and rotating speed is adjusted to 400 revs/min, add above-mentioned polymer seeds microballoon 100.0g again, distilled water and polymer seeds microspheres quality are than being 3:1, finally add vinylbenzene 7.6g, Vinylstyrene 3.8g(add-on be 50% of vinylbenzene quality) and Diisopropyl azodicarboxylate 0.076g(add-on be the 1.0wt% of vinylbenzene quality) mixing solutions, then temperature of reaction system is risen to 75 DEG C of reactions 3 hours.
Step 2, after step 1 completes, keep temperature-resistant, mixing speed is heightened to 900 revs/min, vinylbenzene 23.7g is dripped in reaction system in step 1, Vinylstyrene 2.37g(add-on is 10% of vinylbenzene quality) and Diisopropyl azodicarboxylate 0.474g(add-on be the 2.0wt% of vinylbenzene quality) mixing solutions, controlling drop rate makes this mixing solutions dropwise in 4 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol are soaked, after dry and screening, obtain surface-closed without perviousness low-density polymer microballoon.
The above-mentioned surface prepared is 0.92g/cm without the density of osmotic polymer microballoon
3.By the press-in of this polymer microballoon porous plate water and ethanol contend than be 1:3 mixing solutions in soak 30 days, at room temperature naturally dry after taking-up, density is unchanged, illustrates that this polymer microballoon is surperficial without perviousness.
Above the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (6)
1. a suspension polymerization original position closes the method preparing surface permeation-free low-density polymer microballoon, it is characterized in that: there is the low-permeability microballoon of microchannel for seed with surface, monomer and polymkeric substance is utilized to have the feature of good affinity, make monomer diffuse to seed microsphere surface and form monomer liquid layer, then carry out home position polymerization reaction formation polymer coating and close microsphere surface duct, obtain surface permeation-free low-density polymer microsphere.
2. suspension polymerization original position according to claim 1 closes the method preparing surface permeation-free low-density polymer microballoon, it is characterized in that concrete steps are as follows:
Step 1, in the reactor that agitator, reflux condensation mode and heating unit are housed, first distilled water is added, open and stir and rotating speed is adjusted to 100 ~ 500 revs/min, add porous or the hollow polymer seed microballoon of diameter≤1.0, surface micropore road μm, distilled water is 3 ~ 1:1 with polymer seeds microspheres quality ratio, finally add the mixing solutions of monomer, linking agent and initiator, then temperature of reaction system is risen to 65 ~ 75 DEG C of reactions 2 ~ 3 hours;
After step 2, step 1 complete, keep temperature-resistant, mixing speed is heightened to 400 ~ 1000 revs/min, monomer, linking agent and initiator mixing solutions is dripped in reaction system in step 1, controlling drop rate makes this mixing solutions dropwise in 3 ~ 5 hours, after dropping terminates, system temperature is risen to 85 DEG C and continue reaction 1 hour, stopped reaction Temperature fall, after system temperature is lower than 50 DEG C, after filtration, water and washing with alcohol, after dry and screening, obtain surface permeation-free low-density polymer microsphere.
3. suspension polymerization original position according to claim 1 and 2 closes the method preparing surface permeation-free low-density polymer microballoon, it is characterized in that: the pore volume rate of the porous in described step 1 or hollow polymer seed microballoon is 1% ~ 70%, particle diameter is 1.0 μm ~ 1000.0 μm.
4. suspension polymerization original position according to claim 1 and 2 closes the method preparing surface permeation-free low-density polymer microballoon, it is characterized in that: the monomer in described step 1 and 2 is one or more the arbitrary proportion mixtures in vinylbenzene, methyl methacrylate, acrylamide, N-N DMAA, butyl acrylate, vinyl acetate, and the add-on of monomer calculates according to initial enclosed layer thickness and final enclosed layer thickness.
5. suspension polymerization original position according to claim 1 and 2 closes the method preparing surface permeation-free low-density polymer microballoon, it is characterized in that: the linking agent in described step 1 and 2 is Vinylstyrene, dicyclopentadiene, Ethylene glycol dimethacrylate or methyl cyclopentadiene, the add-on of each step linking agent is 0% ~ 50% of monomer mass in this step.
6. suspension polymerization original position according to claim 1 and 2 closes the method preparing surface permeation-free low-density polymer microballoon; it is characterized in that: the initiator in described step 1 and 2 is Diisopropyl azodicarboxylate, benzoyl peroxide or tertbutyl peroxide, the add-on of each step initiator is 1% ~ 2.5% of monomer mass in this step.
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| CN107540863B (en) * | 2017-07-28 | 2020-05-15 | 昆明理工大学 | Preparation method of totally-enclosed polymer microspheres with hollow or porous structures inside |
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