CN105859935B - A kind of preparation method of cavernous body polymer microballoon of the inside with build reticular structure - Google Patents
A kind of preparation method of cavernous body polymer microballoon of the inside with build reticular structure Download PDFInfo
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- CN105859935B CN105859935B CN201610223723.7A CN201610223723A CN105859935B CN 105859935 B CN105859935 B CN 105859935B CN 201610223723 A CN201610223723 A CN 201610223723A CN 105859935 B CN105859935 B CN 105859935B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention discloses the preparation methods that a kind of inside has the cavernous body polymer microballoon of build reticular structure, organic solvent point is formed oil-in-water microballoon drop by the method by suspended dispersed in aqueous phase system first, then the mixed solution for being mixed with oil-soluble monomer, crosslinking agent and initiator is added drop-wise to suspension system, polymerisation then occurs in oil-in-water microballoon drop；By controlling the dosage and rate of addition of organic solvent, monomer and crosslinking agent, the phase separation of Effective Regulation cross-linked polymer and organic solvent forms the cavernous body polymer microballoon of build reticular structure.The microballoon compares traditional hollow or porous polymer microsphere, its mechanical performance is greatly improved, therefore with good shock resistance, wearability, compressive property, it has lower density, higher elasticity and good light scattering, sound insulation, thermal insulation properties simultaneously, can be widely applied to the fields such as oil drilling, acid mist inhibition, coating.
Description
Technical field
The present invention relates to the preparation methods that a kind of inside has the cavernous body polymer microballoon of build reticular structure, belong to poly-
Close object field of functional materials.
Background technology
Polymer microspheres are widely applied to various fields.People can prepare ruler according to different requirements,
It is very little, form and the different polymer microspheres of microstructure.Wherein, inhibit etc. to meet oil drilling additive and acid mist
There is polymer microballoon of the low-density surface without permeability, high resiliency and good mechanical properties to cause for the specific demand in field
Extensive concern.
Currently, the work about the special dimensions polymer microballoon such as oil drilling additive and acid mist inhibition, main to collect
In on low-density surface without permeability in terms of porous or polymeric hollow microsphere preparation.It emphasizes in having inside polymer microballoon
Empty or porous structure, the purpose is to reduce the density of microballoon to make it have floatability；Emphasize surface without infiltrative purpose in addition
It is polymer microballoon to float for a long time.Up to the present, more commonly used preparation method is using emulsion polymerization, suspends and gather
Splitting or integrating, which dissipates the methods of polymerization, precipitation polymerization, microfluid polymerization and templated synthesis and prepares, has the characteristics that special construction（Such as：Shell-core,
Phase separation etc.）Polymer microballoon, then assist again with extraction, dialysis, evaporation of the solvent, etching, spray drying, vacuum drying etc.
Method removes liquid phase from microballoon, obtains porous or hollow microsphere.The microballoon being prepared by above method, need to be from micro-
Pore-foaming agent is removed inside ball（Or the substances such as solvent, template）Hole is formed, is related to solvent from exterior surface migration inside microballoon,
Therefore the microsphere surface prepared（Or shell）With internal hole（Or cavity）It is through, there is stronger permeability, when
After microballoon is impregnated 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 is made to be greatly lowered.
In addition, low-density surface can also be empty by being prepared based on gas template without the preparation of osmotic polymer microballoon
The heart or porous microsphere.Then different research workers cures to the cold by using thermoplastic polymer package inert gas（Grandson
Man of virtue and ability's beautiful jade etc., a kind of surface is without osmotic polymer hollow microsphere and preparation method thereof, Chinese patent 201310060560.1）, meet
Solidification of the water cure monomer on water vapour microbubble（Toshinori Makuta, et al. Hollow microspheres
fabricated from instant adhesive. Materials Letters,2011,65:3415-3417.）, hydrophobic
Absorption and precipitation of the property polymer nanocomposite ball 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）The 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）The methods of
Directly it is prepared for polymer hollow particles.In above method, although by controlling reaction condition, shell density is relatively
It is good, but substantially hole formation still relies on the processes 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.
For problem above-mentioned hollow or that porous polymer microsphere permeability is strong, CN102585279A,
201410785640.8 and 201510197352.5 report respectively using gaseous suspension method, oligomer pre-coating method and suspend poly-
Close the method that closing method in situ prepares surface permeation-free low-density polymer microsphere.Gaseous suspension method（CN102585279A）Profit
There is the porous or hollow microsphere surface hole defect of water to carry out covering realization on surface with the chance dry monomer of water speed to close it, be prepared for more
The adjustable surface of kind density is without osmotic polymer microballoon.Oligomer pre-coating method（201410785640.8）Existed using oligomer
Have the characteristics that poor compared with high viscosity and mobility in organic good solvent, oligomer be dissolved in volatile organic solvent,
It is made into the polymer solution of suitable viscosity, porous or hollow microsphere is then added makes organic solvent volatilize while stirring, obtains table
The closed polyalcohol stephanoporate in face road or hollow microsphere, have it is good can long-time floatability.Method is closed in suspension polymerisation in situ
（201510197352.5）Have the permeability microballoon of microchannel as seed using surface, has using monomer and polymer good
The characteristics of compatibility, makes monomer diffuse to seed microsphere surface and forms monomer liquid layer, and then progress home position polymerization reaction is formed poly-
Object coating closing microsphere surface duct is closed, obtains the closed surface of low-density without permeable hollow or porous microsphere.It is made above
The microballoon that method obtains all have it is good can long-time floatability.
Although above-mentioned preparation method solves the problems, such as hollow or porous polymer microsphere low-density surface without infiltrative.But
It is due to these methods or to be related to needs of the pore-foaming agent to external migration, the shell thickness of microballoon often very little, and cannot hand over
Connection leads to the universal poor problem of mechanical performance；It is related to what polymer controlled by force in bubble surface deposition and bubble inner pressure
Problem leads to microballoon shell thickness and size-constrained, and mechanical performance is poor.However, the mechanical performance of polymer microballoon is just
It is the key property that it is used in the special dimensions such as oil drilling additive and acid mist inhibition.Only polymer microballoon has
Good mechanical performance and stronger elasticity can resist extraneous mechanical force without rupturing, so as to recycle for a long time
It uses.
But up to the present, about the special dimensions polymer microballoon such as oil drilling additive and acid mist inhibition, also
It is not directed to the research report for improving polymer microballoon mechanical performance.Therefore, it is necessary to improve and optimize the preparation of polymer microballoon
Method, to realize that the polymer for preparing and not only having had low-density surface without permeability but also with good mechanical properties and elasticity is micro-
Ball.Exactly build reticular structure is presented inside control polymer microballoon to reach by new preparation method in the method for the present invention, most
Cavernous body polymer microballoon is obtained eventually.For the purpose of realizing that polymer microballoon has good mechanical performance and higher elasticity,
Easy to operate, use scope is more extensive, therefore more superior.
Invention content
The present invention provides the preparation methods that a kind of inside has the cavernous body polymer microballoon of build reticular structure, overcome
Deficiency of the prior art in terms of preparing the special dimensions polymer microballoon such as oil drilling additive and acid mist inhibition（Microballoon machine
Tool performance is poor）.Using mechanical agitation by organic solvent（N-hexane, hexamethylene, petroleum ether, normal heptane, toluene etc.）It suspends and divides
It is dispersed in aqueous phase system and forms oil-in-water organic solvent microballoon suspending drops liquid, then will be mixed with oil-soluble monomer, crosslinking agent
It is added drop-wise in organic solvent microballoon suspending drops liquid with the mixed solution of initiator, then occurs in organic solvent microballoon drop
Polymerisation forms the internal cavernous body polymer microballoon with build reticular structure.
This method is mainly by controlling the amount ratio of organic solvent/oil-soluble monomer, the dosage of oil-soluble monomer/crosslinking agent
Than and rate of addition, the phase-separated state of Effective Regulation cross-linked polymer and organic solvent reach to form build reticular structure
Cavernous body polymer microballoon optimum condition, build mesh sponge body polymer microballoon is finally prepared.
The specific preparation method of the present invention is as follows：
（1）Reactor equipped with blender and reflux condensate device is placed in water-bath, be added a certain amount of distilled water and
Protecting colloid adjusts mixing speed to 300-600 rpm/min, stirs 15 min；Then it is protecting colloid aqueous solution by volume
The organic solvent of volume 1/3-1/10 is added in reactor, opens stirring and water bath heating device, and setting temperature is 60-75
DEG C, mixing speed is 500-3000 rpm/min, stirs 30-60 min, forms stable organic solvent microballoon suspending drops liquid.
When protecting colloid dosage is certain, dispersed phase amount of aqueous solution used is certain, one timing of mixing speed, the dosage of organic solvent
More, the microballoon drop size that suspended dispersed is formed is larger；Conversely, the microballoon drop size formed is smaller.The use of organic solvent
Amount influences the size of final cavernous body microballoon indirectly, and it coordinates the dosage of monomer and crosslinking agent influence cavernous body micro-
Build reticular structure inside ball.It is thus impossible to excessively can not be very few, to control the 1/3-1/ in protecting colloid aqueous solution volume
It is advisable in 10 ranges.
（2）It load weighted oil-soluble monomer, crosslinking agent, initiator will be uniformly mixed, will be mixed using syringe pump in proportion
Solution is added drop-wise in organic solvent microballoon suspending drops liquid, and mixed solution is gradually transferred to by suspension system in organic solvent microballoon
Portion occurs polymerisation generation phase separation and forms build network cross linked polymers, and time for adding is set as 1h-4h, solution to be mixed
It after being added dropwise to complete, then reacts 2h-8h and carries out further reaction curing, then Temperature fall, after system temperature is less than 50 DEG C, warp
Filtering, water and ethyl alcohol washing are impregnated, and the internal cavernous body polymer microballoon with build reticular structure is obtained after dry, screening.
Wherein, monomer addition is excessive, and the amount of monomer into organic solvent microballoon drop is excessive, is easy in microballoon drop
Portion forms monomer aggregation region, and with the generation of reaction, these regions are subsequently formed the closely knit polymer block structure of structure, no
Effective internal build reticular structure can be formed；Monomer addition is very few, and reaction occurs mainly in the surface of microballoon drop, finally
Form the polymer microballoon of nucleocapsid.Therefore, the addition of monomer is the 100%~200% more suitable of organic solvent volume.
Crosslinking agent addition is excessive, and crosslinking is excessive, is easy to form compact texture inside microballoon；Addition is very few, cannot between polymer
It is effectively crosslinked, the purpose for improving mechanical performance is not achieved.The addition of crosslinking agent is the 10%~100% of monomer volume to be
Preferably.Rate of addition is too fast, monomer aggregation, forms fine and close block structure；Monomer dropping is excessively slow, and build reticular structure is too dredged
Pine, mechanical performance improve limited.Therefore the control of rate of addition can be obtained by controlling time for adding, to be added dropwise in 1h-4h
It is more suitable to complete.
The organic solvent that the present invention uses is a kind of in n-hexane, hexamethylene, normal heptane, cycloheptane, petroleum ether, toluene.
The oil-soluble monomer that the present invention uses is styrene, vinyl chloride, methyl methacrylate, butyl acrylate, ethylene
One kind in vinylacetate, the addition of oil-soluble monomer are the 100%~200% of organic solvent volume.
The crosslinking agent that the present invention uses is divinylbenzene, dicyclopentadiene, ethylene glycol dimethacrylate, trihydroxy methyl
One kind in triacrylate, methyl cyclopentadiene, the addition of crosslinking agent are the 10%~100% of oil-soluble monomer volume.
The initiator that the present invention uses is azodiisobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, benzoyl peroxide
One kind in formyl, peroxocarbonate, the addition of initiator are the 1%~3% of oil-soluble monomer quality
Advantageous effect of the present invention：Be used to prepare fine and easy, quick, economic the present invention provides a kind of versatility is interior
Portion has build reticular structure cavernous body microballoon, to ensure it while have low-density and the preparation method of high-mechanical property.It should
Method obtains organic solvent microballoon drop first with suspended dispersed, then controls monomer/organic solvent, monomer/crosslinking agent and list
The drop rate of body crosslinking agent initiator mixed solution controls polymerisation in organic solvent microballoon drop and is separated, from
And form build mesh sponge body polymer microballoon.It has effectively achieved the characteristic of polymer microballoon low-density, and reaches
Improve the purpose of its mechanical performance.To, such polymer microballoon do not allow in use it is broken, be recycled repeat it is long-term
It uses.In addition, the polymer microballoon interior porosity that the method for the present invention is prepared is larger, therefore it is possible to be used as function
Property filling carrier.Also there is good insulating properties, light scattering, sound insulation, elasticity with polymer microballoon prepared by the method for the present invention
With the performances such as compression strength, make it in oil drilling additive, acid mist inhibition, ultrasound contrast reagent, photoelectric material, coating, viscous
The fields such as knot agent, papermaking, communication are with a wide range of applications.
Description of the drawings
Fig. 1 is the scanning electron microscope schematic diagram for the cavernous body polymer microballoon outer surface that the embodiment of the present invention 1 is prepared；
Fig. 2 is the scanning electron microscope schematic diagram for the cavernous body polymer microballoon outer surface that the embodiment of the present invention 2 is prepared；
Fig. 3 is that the cavernous body polymer microballoon that the embodiment of the present invention 3 is prepared is crushed rear internal structure schematic diagram.
Specific implementation mode
Below by embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1：Inside has the preparation method of the cavernous body polystyrene microsphere of build reticular structure, and specific steps are such as
Under：
（1）By the three-necked flask equipped with blender and reflux condensate device（1000mL）It is placed in water-bath, 300mL is added and steams
Distilled water and 3g polyvinyl alcohol adjust mixing speed to 300rpm/min, stir 15min；Then 100mL normal heptanes are added to
In reactor, stirring and water bath heating device are opened, setting temperature is 75 DEG C, mixing speed 1000rpm/min, stirring
30min forms stable organic solvent microballoon suspending drops liquid；
（2）100mL styrene monomers, 50mL divinylbenzenes and 2.74g azodiisobutyronitriles are uniformly mixed, injection is utilized
Mixed solution is added drop-wise in suspension by pump, and time for adding is set as 4h；After solution to be mixed is added dropwise to complete, then 8h is reacted, so
Temperature fall afterwards, after system temperature is less than 50 DEG C, through filtering, water and ethyl alcohol washing are impregnated, and internal tool is obtained after dry, screening
There is the cavernous body polymer microballoon of build reticular structure.
The polystyrene microsphere being prepared, build mesh sponge body structure is apparent, density 0.83g/cm3, pore volume
Rate is 43.2%.Acid mist, which is carried out, using the polystyrene sponge body microballoon inhibits covering, 30 days microsphere breakage rate≤1.0%；Equally
Under the conditions of, it carries out acid mist using polystyrene hollow microsphere and covering, 30 days microsphere breakage rate >=10% is inhibited to illustrate polystyrene
Build reticular structure cavernous body microballoon mechanical performance is compared polystyrene hollow microsphere and is remarkably reinforced（See Fig. 1）.
Embodiment 2：Inside has the preparation method of the cavernous body poly (methyl methacrylate) micro-sphere of build reticular structure, tool
Steps are as follows for body：
（1）By the three-necked flask equipped with blender and reflux condensate device（500 mL）It is placed in water-bath, 200 mL are added
Distilled water and 2.0 g polyvinyl alcohol adjust mixing speed to 400 rpm/min, stir 30 min；Then by 50 mL n-hexanes
It is added in reactor, opens stirring and water bath heating device, setting temperature is 70 DEG C, and mixing speed is 600 rpm/min, is stirred
30 min are mixed, stable organic solvent microballoon suspending drops liquid is formed；
（2）By 50 mL methyl methacrylate monomers, 5 mL ethylene glycol dimethacrylate and 1.32 g tertiary butyl mistakes
Hydrogen oxide is uniformly mixed, and mixed solution is added drop-wise in suspension using syringe pump, time for adding is set as 1h, solution to be mixed
After being added dropwise to complete, then react 2h；Then Temperature fall, after system temperature is less than 50 DEG C, through filtering, water and ethyl alcohol washing leaching
Bubble obtains the internal cavernous body poly (methyl methacrylate) micro-sphere with build reticular structure after dry, screening.
The poly (methyl methacrylate) micro-sphere being prepared, build mesh sponge body structure is apparent, and density is 0.59 g/
cm3, pore volume rate is 48.2%.The polymethyl methacrylate cavernous body microballoon is used as oil drilling additive, 30 days microballoons
Breakage rate≤5.0%；Under similarity condition, using polymethyl methacrylate porous microsphere as oil drilling additive, 30 days micro-
Ball breakage rate >=20% illustrates that polymethyl methacrylate build reticular structure cavernous body microballoon mechanical performance compares poly- methyl-prop
E pioic acid methyl ester porous microsphere is remarkably reinforced（See Fig. 2）.
Embodiment 3：Inside has the preparation method of the cavernous body polyethyl methacrylate microballoon of build reticular structure, tool
Steps are as follows for body：
（1）By the three-necked flask equipped with blender and reflux condensate device（1000mL）It is placed in water-bath, 250 mL are added
Distilled water and 2.5 g polyvinyl alcohol adjust mixing speed to 600 rpm/min, stir 30 min；Then by 100mL n-hexanes
It is added in reactor, opens stirring and water bath heating device, setting temperature is 65 DEG C, and mixing speed is 600 rpm/min, is stirred
30 min are mixed, stable organic solvent microballoon suspending drops liquid is formed；
（2）100 mL polyethyl acrylates, 30mL dicyclopentadienes and 1.8g azobisisoheptonitrile are uniformly mixed, utilized
Mixed solution is added drop-wise in suspension by syringe pump, and time for adding is set as 2h；After solution to be mixed is added dropwise to complete, then react
4h；Then Temperature fall, after system temperature is less than 50 DEG C, through filtering, water and ethyl alcohol washing are impregnated, and are obtained after dry, screening
Inside has the cavernous body polyethyl acrylate microballoon of build reticular structure.
The polyethyl acrylate microballoon being prepared, build mesh sponge body structure is apparent, and density is 0.74 g/cm3, hole
Volume fraction is 35.9%.Acid mist is carried out using the polyethyl acrylate cavernous body microballoon to inhibit to cover, 30 days microsphere breakage rates≤
1.0%；Under similarity condition, carries out acid mist using polyethyl acrylate hollow microsphere and inhibit to cover, 30 days microsphere breakage rate >=10%,
Illustrate that polyethyl acrylate build reticular structure cavernous body microballoon mechanical performance is compared polyethyl acrylate hollow microsphere and obviously increased
By force（See Fig. 3）.
Embodiment 4：Inside has the preparation method of the cavernous body butyl polyacrylate microballoon of build reticular structure, specific to walk
It is rapid as follows：
（1）By the three-necked flask equipped with blender and reflux condensate device（500mL）It is placed in water-bath, 200 mL are added and steam
Distilled water and 2.0g polyvinyl alcohol adjust mixing speed to 300rpm/min, stir 30min；Then 20mL n-hexanes are added to
In reactor, stirring and water bath heating device are opened, setting temperature is 75 DEG C, and mixing speed is 600 rpm/min, stirring 30
Min forms stable organic solvent microballoon suspending drops liquid；
（2）50mL Butyl Acrylate Monomers, 50mL divinylbenzenes and 0.90g benzoyl peroxides are uniformly mixed, profit
Mixed solution is added drop-wise in suspension with syringe pump, time for adding is set as 1h, after solution to be mixed is added dropwise to complete, then reacts
2h, then Temperature fall, after system temperature is less than 50 DEG C, through filtering, water and ethyl alcohol washing are impregnated, and are obtained after dry, screening
Inside has the cavernous body butyl polyacrylate microballoon of build reticular structure.
The butyl polyacrylate microballoon being prepared, build mesh sponge body structure is apparent, and density is 0.51 g/cm3, hole
Volume fraction is 50.2%.By the butyl polyacrylate cavernous body microballoon be used as oil drilling additive, 30 days microsphere breakage rates≤
5.0%；Under similarity condition, using butyl polyacrylate porous microsphere as oil drilling additive, 30 days microsphere breakage rates >=
20%, it is bright to illustrate that butyl polyacrylate build reticular structure cavernous body microballoon mechanical performance compares butyl polyacrylate porous microsphere
Aobvious enhancing.
Embodiment 5：Inside has the preparation method of the cavernous body plastic of poly vinyl acetate microballoon of build reticular structure, tool
Steps are as follows for body：
（1）By the three-necked flask equipped with blender and reflux condensate device（500mL）It is placed in water-bath, 200 mL are added and steam
Distilled water and 2.0g polyvinyl alcohol adjust mixing speed to 300rpm/min, stir 30min；Then 60 mL n-hexanes are added
Into reactor, stirring and water bath heating device are opened, setting temperature is 75 DEG C, and mixing speed is 600 rpm/min, stirring 30
Min forms stable organic solvent microballoon suspending drops liquid；
（2）90mL ethylene vinyl acetates monomer, 30mL divinylbenzenes and 1.86g benzoyl peroxides are mixed equal
It is even, mixed solution is added drop-wise in suspension using syringe pump, time for adding is set as 3h, after solution to be mixed is added dropwise to complete,
6h is reacted again.Then Temperature fall, after system temperature is less than 50 DEG C, through filtering, water and ethyl alcohol washing are impregnated, dry, screening
The internal cavernous body plastic of poly vinyl acetate microballoon with build reticular structure is obtained afterwards.
The plastic of poly vinyl acetate microballoon being prepared, build mesh sponge body structure is apparent, and density is 0.79 g/
cm3, pore volume rate is 34.9%.The plastic of poly vinyl acetate cavernous body microballoon is used as oil drilling additive, 30 days microballoons
Breakage rate≤5.0%；Under similarity condition, using ethylene vinyl acetate porous microsphere as oil drilling additive, 30 days microballoons
Breakage rate >=20% illustrates that plastic of poly vinyl acetate build reticular structure cavernous body microballoon mechanical performance compares polyvinyl acetate
Vinyl acetate porous microsphere is remarkably reinforced.
Claims (5)
1. a kind of inside has the preparation method of the cavernous body polymer microballoon of build reticular structure, it is characterised in that：Utilize machine
Organic solvent is dispersed in suspension in aqueous phase system by tool stirring forms oil-in-water organic solvent microballoon suspending drops liquid, then will
The mixed solution for being mixed with oil-soluble monomer, crosslinking agent and initiator is added drop-wise in organic solvent microballoon suspending drops liquid, then
Polymerisation occurs in organic solvent microballoon drop and forms the internal cavernous body polymer microballoon with build reticular structure；
The above method is as follows：
（1）Reactor equipped with blender and reflux condensate device is placed in water-bath, distilled water and protecting colloid is added, is adjusted
Mixing speed is saved to 300-600 rpm/min, stirs 15 min；Then it is protecting colloid aqueous solution volume 1/3-1/10 by volume
Organic solvent be added in reactor, open stirring and water bath heating device, setting temperature is 60-75 DEG C, and mixing speed is
500-3000 rpm/min stir 30-60 min, form organic solvent microballoon suspending drops liquid；
（2）Oil-soluble monomer, crosslinking agent, initiator are uniformly mixed, mixed solution, which is added drop-wise to organic solvent microballoon drop, to be hanged
In supernatant liquid, time for adding 1h-4h；After solution to be mixed is added dropwise to complete, then react 2h-8h；Then Temperature fall, when system temperature
After degree is less than 50 DEG C, through filtering, water and ethyl alcohol wash immersion successively, are obtained after dry, screening internal with build reticular structure
Cavernous body polymer microballoon；
The addition of the oil-soluble monomer is the 100%~200% of organic solvent volume；
The addition of the crosslinking agent is the 10%~100% of oil-soluble monomer volume.
2. inside according to claim 1 has the preparation method of the cavernous body polymer microballoon of build reticular structure,
It is characterized in that：Organic solvent is a kind of in n-hexane, hexamethylene, normal heptane, cycloheptane, petroleum ether, toluene.
3. inside according to claim 1 has the preparation method of the cavernous body polymer microballoon of build reticular structure,
It is characterized in that：Oil-soluble monomer is styrene, methyl methacrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer
In one kind.
4. inside according to claim 1 has the preparation method of the cavernous body polymer microballoon of build reticular structure,
It is characterized in that：Crosslinking agent be divinylbenzene, dicyclopentadiene, ethylene glycol dimethacrylate, tri methylol triacrylate,
One kind in methyl cyclopentadiene.
5. inside according to claim 1 has the preparation method of the cavernous body polymer microballoon of build reticular structure,
It is characterized in that：Initiator is azodiisobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide, benzoyl peroxide, percarbonic acid
One kind in ester, the addition of initiator are the 1%~3% of oil-soluble monomer quality.
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