CN104877166B - A kind of closing of suspension polymerisation original position prepares method of the low-density surface without osmotic polymer microballoon - Google Patents
A kind of closing of suspension polymerisation original position prepares method of the low-density surface without osmotic polymer microballoon Download PDFInfo
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Abstract
The present invention relates to the method that a kind of suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, belong to Functionally structure technical field.This method has the hypotonicity of microchannel porous using surface or hollow microsphere is seed, the characteristics of there is good affinity using monomer and polymer, monomer is set to diffuse to seed microsphere surface formation monomer liquid layer, then home position polymerization reaction formation polymer coating closing microsphere surface duct is carried out, surface permeation-free low-density polymer microsphere is obtained.There is the polymer microballoon closed with the inventive method good insulating properties, light to dissipate the performances such as color, sound insulation, elasticity and compression strength, it is with a wide range of applications in the field such as oil drilling additive, acid mist suppression, ultrasound contrast reagent, photoelectric material, coating, binding agent, papermaking, communication.
Description
Technical field
The present invention relates to the method that a kind of suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere,
Belong to Functionally structure technical field.
Background technology
Polymer microspheres are widely applied to various fields.According to different demands, people can prepare chi
It is very little, form and the different polymer microspheres of microstructure.Wherein, suppress etc. to meet oil drilling additive and acid mist
The specific demand in field, extensive concern is caused with low-density surface without infiltrative hollow or porous polymer microsphere.
At present, on low-density is hollow or research work of porous polymer microsphere be concentrated mainly on using emulsion polymerization,
Prepared by the methods such as suspension polymerisation, dispersin polymerization, precipitation polymerization, microfluid polymerization and templated synthesis have special construction feature（Such as：
Shell-core, phase separation etc.）Polymer microballoon, then aid in again with extract, dialysis, solvent evaporation, etching, spray drying, vacuum
The method such as dry, liquid phase is removed from microballoon, hollow or porous microsphere is obtained.Wherein Chinese patent CN101250244B is reported
It is a kind of with spray drying process prepare it is internal include inside a large amount of hollow microspheres and hollow microsphere be negative pressure polymeric hollow
The method of microballoon, CN1303140C reports a kind of method that use strong acid etching method prepares polymer hollow particles,
CN100562358C report it is a kind of with hydrogel template prepare polymer hollow particles method, 201010543593.8,
201010624786.6,201110040481.5,201110052468.1,201110150863.3,201110150862.9 etc.
Report that multiple polymers are hollow or preparation method of porous microsphere.The polymer microballoon prepared by above method, is needed
From its internal removal pore-foaming agent（Or the material such as solvent, template）To form hole, solvent is directed to inside microballoon to appearance
Face is migrated, therefore the microsphere surface prepared（Or shell）With internal hole（Or cavity）It is through, is oozed with stronger
Permeability, after microballoon is soaked for a long time by liquid, liquid component will enter core inside aperture by the micropore permeation of microsphere surface（Or
Cavity）, cause the density of microballoon to increase rapidly, its floatability be greatly lowered.Further, since need of the pore-foaming agent to external migration
Will, the shell thicknesses of these microballoons often very little, so mechanical performance is generally poor.Accordingly, it would be desirable to improve and optimize it is hollow or
The preparation method of porous polymer microsphere, prepares the low-density surface with good mechanical properties and density retention without permeability
Polymer microballoon.
It is to realize microsphere surface without a kind of infiltrative method that hollow or porous microsphere is prepared based on gas template.Arrive
So far, different research workers wraps up inert gas by using thermoplastic polymer and then solidified to the cold（Sun Yanlin
Deng a kind of surface is without osmotic polymer hollow microsphere and preparation method thereof, Chinese patent CN201310060560.1）, meet water
Solidification of the curing monomer on water vapour microbubble（Toshinori Makuta, et al. Hollow microspheres
fabricated from instant adhesive. Materials Letters, 2011, 65:3415- 3417）, dredge
Absorption and precipitation of the waterborne polymeric nanosphere on microbubble surface（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
Directly it is prepared for polymer hollow particles.In above method, although by controlling reaction condition, its shell density is relatively
It is good, but substantially hole formation still relies on the process such as the transfer of gas and the precipitation deposition of polymer, so, the densification of shell
Property it is still defective, therefore also have permeability.In addition, or the microballoon shell thickness that above method is prepared is limited,
Size is restricted, therefore further limit the utilization of microballoon.
It is to have hole to surface without another infiltrative feasible way to realize porous or polymeric hollow microsphere surface
The porous or polymeric hollow microsphere in road implements closing.CN102585279A reports a kind of using gaseous suspension method preparation surface
Method without permeability low-density polymeric microballoon, this method by using meet the dry monomer of water speed have to surface the porous of water or in
Empty microsphere surface hole covering is realized to be closed to it, is prepared for the adjustable surface of a variety of density without osmotic polymer microballoon, tool
Have it is good can long-time floatability.The core element of the inventive method is the organic monomer for meeting water cure, its unique performance
Limit the extensive use of the inventive method；In addition, meeting water cure monomer before contact microsphere surface hydration layer with steam shape
Formula is present, therefore monomer quantity delivered is limited during water cure is met, and is unfavorable for the closing to microsphere surface large aperture duct.Cause
This is, it is necessary to invent a kind of stronger painting method of versatility, so as to realize to polyalcohol stephanoporate or hollow microsphere surface duct
Closing.
Suspension polymerisation of the present invention closing method in situ is more simple with operating, it is not necessary to be set using special
Standby, production cost is relatively low, has greater significance to the popularization and application of polymer microballoon.In addition, using the method for the present invention, passing through
Monomer and crosslinking agent of the selection with different performance feature, can also be while closing, to the coating of microballoon to microballoon
Thickness is adjusted and carries out functional modification to its surface, microballoon is had more superior physical and chemical properties.
The content of the invention
The present invention is in order to overcome the shortcomings of that prior art in terms of surface permeation-free low-density polymer microsphere is prepared, is carried
The method for preparing surface permeation-free low-density polymer microsphere for a kind of suspension polymerisation closing in situ.This method has with surface
The hypotonicity of microchannel is porous or hollow microsphere is seed, and the characteristics of having good affinity using monomer and polymer makes
Monomer diffuses to seed microsphere surface formation monomer liquid layer, then carries out home position polymerization reaction formation polymer coating closing microballoon
Surface duct, obtains surface permeation-free low-density polymer microsphere, and the present invention is achieved through the following technical solutions.
A kind of closing of suspension polymerisation original position prepares method of the low-density surface without osmotic polymer microballoon, has with surface
The hypotonicity microballoon of microchannel is as seed, and the characteristics of having good affinity using monomer and polymer spreads monomer
To seed microsphere surface formation monomer liquid layer, home position polymerization reaction formation polymer coating closing microsphere surface hole is then carried out
Road, obtains surface permeation-free low-density polymer microsphere.
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its specific step
It is rapid as follows：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water, unlatching is stirred
Mix and rotating speed is adjusted to 100 ~ 500 revs/min, the porous or hollow polymer seed for adding surface micropore road diameter≤1.0 μm is micro-
Ball, distilled water is 3~1 with polymer seeds microspheres quality ratio：1, the mixing for being eventually adding monomer, crosslinking agent and initiator is molten
Liquid, then rises to 65 ~ 75 DEG C by temperature of reaction system and reacts 2 ~ 3 hours；
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 400 ~ 1000 revs/min, to step 1
In reaction system in monomer, crosslinking agent and initiator mixed solution is added dropwise, control drop rate makes the mixed solution small 3 ~ 5
When interior completion of dropping, after completion of dropwise addition, by system temperature rise to 85 DEG C continue react 1 hour, stop reaction and Temperature fall, when
System temperature be less than 50 DEG C after, through filtering, water and ethanol washing immersion, dry and screening after, obtain surface-closed without infiltration
Property low-density polymeric microballoon.
Porous or hollow polymer seed microballoon pore volume rate in the step 1 is 1%~70%, and particle diameter is 1.0 μm
~1000.0µm；The polymer seeds microballoon can use emulsion polymerization（Gather comprising seeding polymerization, mini-emulsion polymerization, micro emulsion
Conjunction, emulsifier-free emulsion polymerization, film emulsion polymerization etc.）, suspension polymerisation, dispersin polymerization, precipitation polymerization, microfluid polymerization, templated synthesis
Etc. the porous or polymeric hollow microsphere that prepared by any method in method.
Monomer in the step 1 and 2 is styrene, methyl methacrylate, acrylamide, N-N dimethyl allene acyls
One or more of arbitrary proportion mixtures in amine, butyl acrylate, vinylacetate, the addition of monomer is according to initially a closed
Thickness degree and final enclosed layer thickness, which are calculated, to be obtained.The monomer addition of step 1 is calculated according to initially a closed thickness degree and obtained, and is counted
Calculating formula is：, in formula：mFor monomer consumption, g；NFor the quantity of polymer seeds microballoon,
It is individual；D 1For the diameter of polymer seeds microballoon, cm；d 1For beginning enclosed layer thickness, cm；rFor monomer density, g/cm3.It is single in step 2
The addition of body is calculated according to final enclosed layer thickness and obtained, and calculation formula is：, in formula：mFor monomer consumption, g；NIt is individual for the quantity of polymer seeds microballoon；D 2For the diameter of initially a closed post-consumer polymer seed microballoon,
cm；d 2For final enclosed layer thickness, cm；rFor monomer density, g/cm3。
Crosslinking agent in the step 1 and 2 is divinylbenzene, dicyclopentadiene, GDMA or
Methyl cyclopentadiene, the addition of crosslinking agent is the addition of crosslinking agent in the 0%~50% of step 1 monomer mass, step 2 in rapid 1
Measure as the 0%~50% of step 2 monomer mass.
Initiator in the step 1 and 2 is azodiisobutyronitrile, benzoyl peroxide or TBHP, step
The addition of initiator is that the addition of initiator in the 1%~2.5% of step 1 monomer mass, step 2 is step 2 monomer in rapid 1
The 1%~2.5% of quality.
The beneficial effects of the invention are as follows：Very well and easy, quick, economical table is prepared the invention provides a kind of versatility
Method of the face without permeability low-density polymeric microballoon, by suspension polymerization, makes monomer directly poly- in microsphere surface original position
Close, the microchannel progress to microsphere surface is effectively totally-enclosed.Because the inventive method make use of monomer to have well with polymer
The characteristics of compatibility, monomer can be made effectively to diffuse to microballoon channel surfaces formation monomer liquid film layer and carry out in-situ polymerization and form poly-
Compound, therefore effective closing to small size duct can be realized.The present invention method can device to hole volume fraction 1%~70%（V/
V）Between, microchannel diameter≤1.0 μm, particle size range is hollow between 1.0 μm ~ 1000.0 μm（Or it is porous）Polymer microballoon
Surface micropore road effectively closed, the polymer microballoon is prevented effectively from use, because liquid substance passes through it
Surface micropore road is to the infiltration of core inside aperture or cavity, the shortcoming for causing density to change, and makes it before low-density is kept
Put, with the excellent performance such as can float for a long time.Simultaneously as the inventive method is to carry out surface envelope in atmospheric conditions
Close, it is suitable with external atmospheric pressure to be closed air in the hole of microballoon or cavity, therefore will not produce internal stress, in addition this
Inventive method can adjust the thickness of microballoon confining bed by the consumption of monomer, so that prepared low-density surface is without infiltration
Property polymer microballoon has more preferable mechanical performance, and density is adjustable.The polymer microballoon closed with the inventive method has
Good insulating properties, light dissipate the performances such as color, sound insulation, elasticity and compression strength, make it in oil drilling additive, acid mist suppression
The field such as system, ultrasound contrast reagent, photoelectric material, coating, binding agent, papermaking, communication is with a wide range of applications.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
The underlying parameter of seed polymer microballoon to be closed：Average diameter is 10 μm, and pore volume rate is 6.4%（V/V）, put down
Equal a diameter of 0.5 ± 0.08 μm of surface micropore road, density is 0.94g/cm3Polystyrene porous microballoon, microballoon consumption
200.0g, initially a closed coating thickness is about 0.05 μm, and final closing coating thickness is about 0.05 μm.
Then the total number of seed microballoon is：。
The addition of styrene monomer is calculated according to initially a closed thickness degree and obtained in step 1, and calculation formula is, addition is。
The addition of styrene monomer is calculated according to final closing coating thickness and obtained in step 2, and calculation formula is, addition is。
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its feature exists
In comprising the following steps that：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water 300.0g,
Open and stir and rotating speed is adjusted to 400 revs/min, add above-mentioned polymer seeds microballoon 200.0g, distilled water is with polymerizeing species
Sub- microspheres quality ratio is 1.5:1, it is eventually adding styrene 6.7g, divinylbenzene 3.35g（The 50% of styrene quality）And azo
Bis-isobutyronitrile 0.1g（The 1.5wt% of styrene quality）Mixed solution, temperature of reaction system is then risen into 65 DEG C of reactions 3 small
When.
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 800 revs/min, anti-into step 1
Answer dropwise addition styrene 6.8g, divinylbenzene 3.4g in system（The 50% of styrene quality）With azodiisobutyronitrile 0.068g（Benzene
The 1.0wt% of Ethylene mass）Mixed solution, control drop rate makes mixed solution completion of dropping in 5 hours, knot is added dropwise
Shu Hou, rises to 85 DEG C by system temperature and continues to react 1 hour, stop reaction and Temperature fall, after system temperature is less than 50 DEG C,
Through filtering, water and ethanol washing immersion, dry and screening after, obtain surface-closed without permeability low-density polymeric microballoon.
Above-mentioned density of the surface prepared without osmotic polymer microballoon is 0.96g/cm3.By the polymer microballoon
It is 1 with porous plate press-in water and ethanol volume ratio:Soak 30 days, dried naturally at room temperature after taking-up in 3 mixed solution, it is close
Degree is unchanged, illustrates this polymer microballoon surface without permeability.
Embodiment 2
The underlying parameter of seed polymer microballoon to be closed：Average diameter is 50 μm, and pore volume rate is 23.8%（V/V）, put down
Equal a diameter of 0.2 ± 0.05 μm of surface micropore road, density is 0.68g/cm3Polystyrene hollow microsphere, microballoon consumption
100.0g, initially a closed coating thickness is about 3.0 μm, and final closing coating thickness is about 5.0 μm.
Then the total number of seed microballoon is：。
The addition of styrene and methyl methacrylate monomer is calculated according to initially a closed thickness degree and obtained in step 1,
Calculation formula is, addition is。
The addition of styrene and acrylamide monomer is calculated according to final closing coating thickness and obtained in step 2, is calculated
Formula is, addition is。
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its specific step
It is rapid as follows：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water 300.0g,
Open and stir and rotating speed is adjusted to 500 revs/min, add above-mentioned polymer seeds microballoon 100.0g, distilled water is with polymerizeing species
Sub- microspheres quality ratio is 3:1, it is eventually adding styrene 26.3g, methyl methacrylate 26.3g, dicyclopentadiene 15.78g（Benzene
The 30wt% of ethene and methyl methacrylate quality）With benzoyl peroxide 1.315g（Styrene and methyl methacrylate matter
The 2.5wt% of amount）Mixed solution, then by temperature of reaction system rise to 75 DEG C react 2 hours.
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 1000 revs/min, into step 1
Styrene 65.45g, acrylamide 65.45g, dicyclopentadiene 26.18g are added dropwise in reaction system（Styrene and acrylamide matter
The 20% of amount）With benzoyl peroxide 3.27g（The 2.5wt% of styrene and acrylamide quality）Mixed solution, control be added dropwise
Speed makes mixed solution completion of dropping in 3 hours, after completion of dropwise addition, and system temperature is risen into 85 DEG C continues to react 1 hour,
Stop reaction and Temperature fall, after system temperature is less than 50 DEG C, through filtering, water and ethanol washing immersion, after drying and sieving,
Obtain surface-closed without permeability low-density polymeric microballoon.
Above-mentioned density of the surface prepared without osmotic polymer microballoon is 0.82g/cm3.By the polymer microballoon
It is 1 with porous plate press-in water and ethanol volume ratio:Soak 30 days, dried naturally at room temperature after taking-up in 3 mixed solution, it is close
Degree is unchanged, illustrates this polymer microballoon surface without permeability.
Embodiment 3
The underlying parameter of seed polymer microballoon to be closed：Average diameter is 100 μm, and pore volume rate is 45.6%（V/V）,
A diameter of 0.3 ± 0.05 μm of average surface microchannel, density is 0.51g/cm3Polystyrene hollow microsphere, microballoon consumption
100.0g, initially a closed coating thickness is about 1.0 μm, and final closing coating thickness is about 3.0 μm.
Then the total number of seed microballoon is：。
The addition of N-N DMAAs and Butyl Acrylate Monomer is according to initially a closed layer thickness gauge in step 1
Obtain, calculation formula is, addition is。
The addition of styrene and acrylamide monomer is calculated according to final closing coating thickness and obtained in step 2, is calculated
Formula is, addition is。
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its specific step
It is rapid as follows：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water 100.0g,
Open and stir and rotating speed is adjusted to 100 revs/min, add above-mentioned polymer seeds microballoon 100.0g, distilled water is with polymerizeing species
Sub- microspheres quality ratio is 1:1, it is eventually adding N-N DMAAs 5.5g, butyl acrylate 5.5g, dimethacrylate second
Diol ester 4.4g（Addition is the 40% of N-N DMAAs and butyl acrylate quality）And TBHP
0.11g（Addition is N-N DMAAs and the 1.0wt% of butyl acrylate quality）Mixed solution, then will reaction
System temperature rises to 70 DEG C and reacted 2.5 hours.
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 400 revs/min, anti-into step 1
Answer and styrene 21.8g, acrylamide 21.8g, GDMA 8.72g are added dropwise in system（Addition is benzene second
The 20wt% of alkene and acrylamide quality）With TBHP 1.09g（Addition is styrene and acrylamide quality
2.5wt%）Mixed solution, control drop rate make mixed solution completion of dropping in 5 hours, after completion of dropwise addition, by system
Temperature rise to 85 DEG C continue react 1 hour, stop reaction and Temperature fall, when system temperature be less than 50 DEG C after, through filtering, water and
Ethanol washing immersion, dry and screening after, obtain surface-closed without permeability low-density polymeric microballoon.
Above-mentioned density of the surface prepared without osmotic polymer microballoon is 0.68g/cm3.By the polymer microballoon
It is 1 with porous plate press-in water and ethanol volume ratio:Soak 30 days, dried naturally at room temperature after taking-up in 3 mixed solution, it is close
Degree is unchanged, illustrates this polymer microballoon surface without permeability.
Embodiment 4
The underlying parameter of seed polymer microballoon to be closed：Average diameter is 500 μm, and pore volume rate is 70.0%（V/V）,
A diameter of 0.5 ± 0.05 μm of average surface microchannel, density is 0.31g/cm3Polymethyl methacrylate hollow microsphere, it is micro-
Ball consumption 100.0g, initially a closed coating thickness is about 0.5 μm, and final closing coating thickness is about 1.5 μm.
Then the total number of seed microballoon is：
The addition of methyl methacrylate monomer is calculated according to initially a closed thickness degree and obtained in step 1, calculation formula
For, addition is。
The addition of methyl methacrylate monomer is calculated according to final closing coating thickness and obtained in step 2, calculates public
Formula is, addition is。
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its specific step
It is rapid as follows：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water 200.0g,
Open and stir and rotating speed is adjusted to 350 revs/min, add above-mentioned polymer seeds microballoon 100.0g, distilled water is with polymerizeing species
Sub- microspheres quality ratio is 2:1, it is eventually adding methyl methacrylate 1.8g, methyl cyclopentadiene 0.9g（Addition is methyl-prop
The 50% of e pioic acid methyl ester quality）With TBHP 0.018g（Addition is the 1.0wt% of methyl methacrylate quality）
Mixed solution, then by temperature of reaction system rise to 70 DEG C react 2.5 hours.
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 700 revs/min, anti-into step 1
Answer and methyl methacrylate 5.5g, methyl cyclopentadiene 2.75g are added dropwise in system（Addition is methyl methacrylate quality
50wt%）With TBHP 0.11g（Addition is the 2.0wt% of methyl methacrylate quality）Mixed solution, control
Drop rate processed makes mixed solution completion of dropping in 5 hours, after completion of dropwise addition, and system temperature is risen into 85 DEG C continues to react
1 hour, stop reaction and Temperature fall, when system temperature be less than 50 DEG C after, through filtering, water and ethanol washing immersion, dry and
After screening, obtain surface-closed without permeability low-density polymeric microballoon.
Above-mentioned density of the surface prepared without osmotic polymer microballoon is 0.38g/cm3.By the polymer microballoon
It is 1 with porous plate press-in water and ethanol volume ratio:Soak 30 days, dried naturally at room temperature after taking-up in 3 mixed solution, it is close
Degree is unchanged, illustrates this polymer microballoon surface without permeability.
Embodiment 5
The underlying parameter of seed polymer microballoon to be closed：Average diameter is 1 μm, and pore volume rate is 1.0%（V/V）, it is average
A diameter of 0.02 ± 0.005 μm of surface micropore road, density is 0.91g/cm3Poly- melamino-formaldehyde porous microsphere, microballoon use
100.0g is measured, initially a closed coating thickness is about 0.01 μm, final closing coating thickness is about 0.02 μm.
Then the total number of seed microballoon is：。
The addition of Vinyl Acetate Monomer is calculated according to initially a closed thickness degree and obtained in step 1, and calculation formula is, addition is。
The addition of styrene monomer is calculated according to final closing coating thickness and obtained in step 2, and calculation formula is, addition is。
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its specific step
It is rapid as follows：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water 300.0g,
Open and stir and rotating speed is adjusted to 400 revs/min, add above-mentioned polymer seeds microballoon 100.0g, distilled water is with polymerizeing species
Sub- microspheres quality ratio is 3:1, it is eventually adding vinylacetate 6.1g and benzoyl peroxide 0.153g（Addition is vinyl acetate
The 2.5wt% of ester quality）Mixed solution, then by temperature of reaction system rise to 70 DEG C react 3 hours, without crosslinking agent；
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 900 revs/min, anti-into step 1
Answer dropwise addition styrene 14.4g and benzoyl peroxide 0.36g in system（Addition is the 2.5wt% of styrene quality）Mixing
Solution, control drop rate makes mixed solution completion of dropping in 3 hours, and after completion of dropwise addition, system temperature is risen into 85 DEG C
Continue to react 1 hour, stop reaction and Temperature fall, after system temperature is less than 50 DEG C, through filtering, water and ethanol washing leaching
Bubble, dry and screening after, obtain surface-closed without permeability low-density polymeric microballoon.Without crosslinking agent.
Above-mentioned density of the surface prepared without osmotic polymer microballoon is 0.96g/cm3.By the polymer microballoon
It is 1 with porous plate press-in water and ethanol volume ratio:Soak 30 days, dried naturally at room temperature after taking-up in 3 mixed solution, it is close
Degree is unchanged, illustrates this polymer microballoon surface without permeability.
Embodiment 6
The underlying parameter of seed polymer microballoon to be closed：Average diameter is 1000 μm, and pore volume rate is 21.5%（V/V）,
A diameter of 0.9 ± 0.1 μm of average surface microchannel, density is 0.83g/cm3Polymethyl methacrylate porous microsphere, microballoon
Consumption 100.0g, initially a closed coating thickness is about 10.0 μm, and final closing coating thickness is about 30.0 μm.
Then the total number of seed microballoon is：。
The addition of styrene esters monomer is calculated according to initially a closed thickness degree and obtained in step 1, and calculation formula is, addition is。
The addition of styrene monomer is calculated according to final closing coating thickness and obtained in step 2, and calculation formula is, addition is。
The method that above-mentioned suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, its specific step
It is rapid as follows：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water
3200.0g, opens to stir rotating speed simultaneously is adjusted into 400 revs/min, adds above-mentioned polymer seeds microballoon 100.0g, distilled water with
Polymer seeds microspheres quality ratio is 3:1, it is eventually adding styrene 7.6g, divinylbenzene 3.8g（Addition is styrene matter
The 50% of amount）With azodiisobutyronitrile 0.076g（Addition is the 1.0wt% of styrene quality）Mixed solution, then will reaction
System temperature rises to 75 DEG C and reacted 3 hours.
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 900 revs/min, anti-into step 1
Answer and styrene 23.7g, divinylbenzene 2.37g are added dropwise in system（Addition is the 10% of styrene quality）With the isobutyl of azo two
Nitrile 0.474g（Addition is the 2.0wt% of styrene quality）Mixed solution, control drop rate make the mixed solution small 4
When interior completion of dropping, after completion of dropwise addition, by system temperature rise to 85 DEG C continue react 1 hour, stop reaction and Temperature fall, when
System temperature be less than 50 DEG C after, through filtering, water and ethanol washing immersion, dry and screening after, obtain surface-closed without infiltration
Property low-density polymeric microballoon.
Above-mentioned density of the surface prepared without osmotic polymer microballoon is 0.92g/cm3.By the polymer microballoon
It is 1 with porous plate press-in water and ethanol volume ratio:Soak 30 days, dried naturally at room temperature after taking-up in 3 mixed solution, it is close
Degree is unchanged, illustrates this polymer microballoon surface without permeability.
The embodiment to the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula, in the knowledge that those of ordinary skill in the art possess, can also make on the premise of present inventive concept is not departed from
Go out various change.
Claims (5)
1. the method that a kind of suspension polymerisation closing in situ prepares surface permeation-free low-density polymer microsphere, it is characterised in that：
There is the hypotonicity microballoon of microchannel as seed using surface, the characteristics of having good affinity using monomer and polymer makes
Monomer diffuses to seed microsphere surface formation monomer liquid layer, then carries out home position polymerization reaction formation polymer coating closing microballoon
Surface duct, obtains surface permeation-free low-density polymer microsphere；
The hypotonicity microballoon is the porous or hollow polymer seed microballoon of surface micropore road diameter≤1.0 μm；It is porous or
The pore volume rate of hollow polymer seed microballoon is 1%~70%, and particle diameter is 1.0 μm ~ 1000.0 μm.
2. suspension polymerisation according to claim 1 closing in situ prepares the side of surface permeation-free low-density polymer microsphere
Method, it is characterised in that comprise the following steps that：
Step 1, in the reactor equipped with agitator, reflux condensation mode and heater, be firstly added distilled water, open stirring simultaneously
Rotating speed is adjusted to 100 ~ 500 revs/min, the porous or hollow polymer seed microballoon of surface micropore road diameter≤1.0 μm is added, steamed
Distilled water is 3~1 with polymer seeds microspheres quality ratio：1, the mixed solution of monomer, crosslinking agent and initiator is eventually adding, then
Temperature of reaction system is risen into 65 ~ 75 DEG C to react 2 ~ 3 hours；
After the completion of step 2, step 1, keeping temperature is constant, and speed of agitator is heightened to 400 ~ 1000 revs/min, into step 1
Monomer, crosslinking agent and initiator mixed solution are added dropwise in reaction system, control drop rate made the mixed solution in 3 ~ 5 hours
Completion of dropping, after completion of dropwise addition, rises to 85 DEG C by system temperature and continues to react 1 hour, stop reaction and Temperature fall, work as system
Temperature is less than after 50 DEG C, through filtering, water and ethanol washing, after drying and sieving, obtains surface permeation-free low-density polymer
Microballoon.
3. suspension polymerisation according to claim 2 closing in situ prepares the side of surface permeation-free low-density polymer microsphere
Method, it is characterised in that：Monomer in the step 1 and 2 is styrene, methyl methacrylate, acrylamide, N-N dimethyl
One or more of arbitrary proportion mixtures in acrylamide, butyl acrylate, vinylacetate, the addition of monomer is according to just
Beginning enclosed layer thickness and final enclosed layer thickness, which are calculated, to be obtained.
4. suspension polymerisation according to claim 2 closing in situ prepares the side of surface permeation-free low-density polymer microsphere
Method, it is characterised in that：Crosslinking agent in the step 1 and 2 is divinylbenzene, dicyclopentadiene, dimethacrylate second two
Alcohol ester or methyl cyclopentadiene, the addition of each step crosslinking agent are 0%~50% of monomer mass in the step.
5. suspension polymerisation according to claim 2 closing in situ prepares the side of surface permeation-free low-density polymer microsphere
Method, it is characterised in that：Initiator in the step 1 and 2 is azodiisobutyronitrile, benzoyl peroxide or tert-butyl hydroperoxide
Hydrogen, the addition of each step initiator is 1%~2.5% of monomer mass in the step.
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| CN103131040A (en) * | 2013-02-27 | 2013-06-05 | 昆明理工大学 | Hollow microsphere of polymer having non-permeable surface, and its preparation method |
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