CN105860123A - Method of preparing temperature-resistant and organic-solvent-resistant polymeric microsphere with non-permeable surface - Google Patents
Method of preparing temperature-resistant and organic-solvent-resistant polymeric microsphere with non-permeable surface Download PDFInfo
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- CN105860123A CN105860123A CN201610320774.1A CN201610320774A CN105860123A CN 105860123 A CN105860123 A CN 105860123A CN 201610320774 A CN201610320774 A CN 201610320774A CN 105860123 A CN105860123 A CN 105860123A
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- microsphere
- organic solvent
- porous
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- crosslinkable prepolymer
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- 239000004005 microsphere Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003960 organic solvent Substances 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 57
- 230000003204 osmotic effect Effects 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000003223 protective agent Substances 0.000 claims description 7
- 230000005070 ripening Effects 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000012662 bulk polymerization Methods 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003595 mist Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000010558 suspension polymerization method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 229920002223 polystyrene Polymers 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 150000005846 sugar alcohols Polymers 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011806 microball Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- C08F214/00—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 a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- 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
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
Abstract
The invention discloses a method of preparing temperature-resistant and organic-solvent-resistant polymeric microsphere with a non-permeable surface. The method comprises the following steps: organic solvent is not used; an oil-soluble initiator is added after crosslinked monomer and non-crosslinked monomer are mixed according to specific proportion; bulk prepolymerization is conducted at a specific temperature; after certain period of reaction, crosslinked prepolymer with appropriate viscosity is obtained; then porous or hollow polymeric microsphere is added into the crosslinked prepolymer; after intensive stirring and even mixing, the suspension polymerization method is adopted in a water phase system for redispersion; after heating and ageing reaction, polymeric microsphere with low density and non-permeable surface which is enclosed in crosslinked polymer is obtained. Through the adjustment of molecular weight and dosage of crosslinked prepolymer, polymeric microspheres with non-permeable surface and low density, which vary in wrapper thickness, are prepared; the polymeric sphere neither is softened when heated nor is dissolved by organic solvent; the polymeric microsphere can be widely applied to the fields such as acid mist inhibition, cosmetics, coating and catalyst loading.
Description
Technical field
The present invention relates to one crosslinkable prepolymer parcel, to prepare heatproof organic solvent-resistant, surface micro-without osmotic polymer
The method of ball, belongs to Functionally structure field.
Background technology
In recent years, polymer microballoon owing to having different forms and microstructure, be widely used in acid mist suppression,
The fields such as household chemicals, biomedicine, electronic information, catalyst loading.Therefore, the method preparing polymer microballoon obtains fast
Hail exhibition, become a kind of effective commercial efforts in many industry fields.Wherein, in order to meet oil drilling additive and acid
The specific demand in the fields such as mist suppression, many researchers are devoted to study surface without infiltrative polyalcohol stephanoporate or hollow
Microsphere.
Prepare the method for polyalcohol stephanoporate or hollow microsphere to be concentrated mainly on and first pass through chemical method preparation there is special construction
The polymer microballoon of (such as shell-core, being separated), then utilizes specific physical method, as solvent evaporates, etches, extracts, sprays
Mist is dried, supercritical fluid technology etc., removes porogen, solvent or template and obtain porous or hollow microsphere from microsphere.This
A little polymer microballoon surfaces are mutually communicated with internal gutter, therefore have stronger permeability.Suppress at oil drilling or acid mist
Deng in the application process of special dimension, when polyalcohol stephanoporate or hollow microsphere soak in a liquid for a long time, liquid component will
The microfacies district within microsphere or cavity is penetrated into so that the density of microsphere increases rapidly, leads by microsphere surface microchannel
Cause its its floatability to be greatly lowered.Accordingly, it would be desirable to prepare a kind of low-density surface without infiltrative porous or hollow polymeric
Thing microsphere.
At present, it is achieved polyalcohol stephanoporate or hollow microsphere surface are the micropores to microsphere surface without infiltrative general way
Road is coated closing.Chinese patent CN102552167A reports a kind of poly-based on supercritical fluid technology surface-closed porous
The method of compound microsphere, by the supercritical carbon dioxide plastication to polymer, micro-to porous polymer microsphere surface
Hole is effectively closed；CN102585279A reports a kind of by gaseous suspension method, to polyalcohol stephanoporate under containing gaseity
Or the micropore on hollow microsphere surface closes, the method obtaining surface permeation-free low-density polymer microsphere, the method can
To prepare that multiple density is adjustable, surface without permeability, can be the most floating polymer microballoon；CN104877166A
Report a kind of suspension polymerisation closing preparation low-density surface in situ and, without the method for osmotic polymer microsphere, effectively enclose poly-
The tiny duct of compound microsphere surface.The method is mainly hypotonicity porous or the hollow microsphere with surface with tiny duct
For seed, utilize monomer and polymer to have the feature of good affinity, carry out in-situ polymerization by monomer at microsphere surface anti-
Polymer coating should be formed, be suitable for the porous to duct≤1, surface μm or hollow microsphere is effectively closed.
CN1045879249A then reports a kind of oligomer precoating and prepares low-density without permeability porous or the method for hollow microsphere,
Uncrosslinked oligomers is dissolved in volatile organic solvent the polymer solution being made into suitable viscosity by this method, is subsequently adding porous
Or hollow microsphere makes organic solvent volatilize while stirring, obtain polyalcohol stephanoporate or the hollow microsphere of precoating surfaces, can be to table
Porous or hollow cross-linked polymer microsphere that face footpath is bigger are effectively closed and improve closing efficiency.
The duct, surface of polyalcohol stephanoporate or hollow microsphere effectively can be closed by above method, but in reality
During, use these methods to close microsphere surface micropore or enclosed layer thickness is limited, or sealing size is limited, or only
Cross linked polymer hollow or porous microsphere can be closed and confining bed is non-cross-linked polymer.Therefore, the surface obtained
The mechanical property of microsphere without osmotic polymer, solvent resistant and high temperature resistant poor, therefore can only use under certain external environment,
It is unfavorable for life-time service.Accordingly, it would be desirable to invent a kind of new preparation method, can be to the polyalcohol stephanoporate with different size duct
Or hollow microsphere effectively closes, obtain that mechanical strength is high, solvent resistance and the good polymer microballoon of temperature tolerance.
The inventive method is just to be effectively closed as purpose to the polymer microballoon in different size duct, by crosslinking
Polymer blocked polymer porous or hollow microsphere obtain low-density surface without osmotic polymer microsphere, and it is simple to operate, suitable
More extensive by property.Meanwhile, this polymer microballoon heatproof organic solvent-resistant, there is higher mechanical strength, it is adaptable to outside various
Portion's condition is the most superior.
Summary of the invention
Technical process is simple, production efficiency is high to the invention provides one, and heatproof organic solvent-resistant surface is gathered without permeability
The preparation method of compound microsphere, the inventive method adds oil after first cross-linking monomer and uncrosslinked monomer being mixed by a certain percentage
Soluble initiator, carries out bulk prepolymerization at a certain temperature, after reaction a period of time, obtains the crosslinking prepolymers that viscosity is suitable
Thing, then adds porous or polymeric hollow microsphere in this crosslinkable prepolymer, and after being thoroughly mixed uniformly, using suspends gathers
Legal in aqueous phase system, it is carried out redispersion, after intensification slaking reaction, obtain the low-density table that cross linked polymer is closed
Face is without osmotic polymer microsphere.
In the method, by controlling the molecular weight of crosslinkable prepolymer and consumption, can high with processing machinery intensity, heatproof is resistance to
Organic solvent, density are adjustable, surface is without infiltrative polymer microballoon.Utilize have between crosslinkable prepolymer and polymer microballoon good
The feature of good affinity, moves to prepolymer polymer microballoon surface and polyreaction occurs, and by regulation prepolymer molecule
Amount is to control solution viscosity, and then effectively closes various sizes of duct.Prepolymer viscosity is relatively low, and reaction system flows
Property is good, therefore preferable to the sealing effect of the less porous of pore size or polymeric hollow microsphere.Otherwise, prepolymer viscosity is relatively
Height, reaction system mobility is poor, poor to the sealing effect of little duct porous or polymeric hollow microsphere, and gathers macropore
The sealing effect of compound microsphere is preferable.But crosslinkable prepolymer viscosity is excessive, mixed liquor in reaction system will be caused to be difficult to disperse, because of
The viscosity of this crosslinkable prepolymer should control between 200～3000mPa s, by regulation stir speed (S.S.), crosslinkable prepolymer
Molecular weight and consumption, can obtain the surface with different coating thickness without infiltrative polymer microballoon.
The concrete preparation method of the present invention is as follows:
(1) in the reactor of belt stirrer and heater, cross-linking monomer and uncrosslinked monomer it are separately added into by a certain percentage,
After being uniformly mixed, add monomer gross mass 0.1～the oil-soluble initiator of 3%, be warming up to 55 ~ 75 DEG C and carry out polymerisation in bulk
Reaction, when the viscosity of reaction system reaches desired value (200mPa s～3000mPa s), drops system temperature rapidly with ice bath
As little as 20 ~ 25 DEG C；
(2) take the reactor of another belt stirrer, at room temperature add the crosslinkable prepolymer of certain mass, then add certain
Porous that quality is to be wrapped or polymeric hollow microsphere, be sufficiently stirred for, make microsphere and crosslinkable prepolymer mix homogeneously；Wherein cross-link
The consumption of prepolymer can obtain according to following formula:, in formula: m is the quality of crosslinkable prepolymer, and N is for be wrapped
Covering the quantity of polyalcohol stephanoporate or hollow microsphere, D is the diameter being wrapped polyalcohol stephanoporate or hollow microsphere,For crosslinking prepolymers
The density of thing, thickness d=0.1 of cross linked polymer parcel confining bed～100 μm；
(3) in the reactor with reflux, agitator and heater, add a certain amount of distilled water, add steaming
The colloid protective agent of distilled water quality 0.5 ~ 5.0%, after heated and stirred is completely dissolved to colloid protective agent, is down to room by system temperature
Temperature, adds colloid protective agent solution quality 20～step (2) mixture of 40%, under the rotating speed of 500 ~ 2000 rpm/min
Dispersed with stirring 10 minutes, then heats to 80 ~ 85 DEG C of ripenings 4 hours, cooled, filter, rinse and to obtain crosslinking after drying poly-
The low-density surface that compound is closed is without osmotic polymer microsphere.
Cross-linking monomer and the mass ratio of uncrosslinked monomer that the present invention uses are 5:1～1:10, preferably 2:1～1:2.
The viscosity of crosslinkable prepolymer that the present invention uses between 200～3000mPa s, preferably 500～1000mPa
s。
The cross-linking monomer that the present invention uses is divinylbenzene, glycol methacrylate, tetramethylolmethane three propylene
One in acid esters.
The uncrosslinked monomer that the present invention uses is styrene, vinyl chloride, methyl methacrylate, acrylamide, ethylene vinegar
One or arbitrarily ratio in vinyl acetate are several.
The present invention use wrapped porous or polymeric hollow microsphere can be use emulsion polymerization, suspension polymerisation,
Porous prepared by any one of the methods such as dispersin polymerization, microfluid polymerization conventional method or polymeric hollow microsphere, its particle diameter
Between 1 μm ~ 500 μm, preferably 10 μm ~ 100 μm.
The oil-soluble initiator used in the present invention is conventional reagent, such as azodiisobutyronitrile.
The colloid protective agent used in the present invention is conventional reagent, such as polyvinyl alcohol.
The method have the benefit that and the invention provides a kind of versatility very well, can effectively close microsphere surface duct, heatproof
The surface of organic solvent-resistant is without the preparation method of osmotic polymer microsphere.By controlling molecular weight and the use of crosslinkable prepolymer
Amount, effectively can coat the duct, surface of particle size range polyalcohol stephanoporate between 1 μm ~ 500 μm or hollow microsphere,
The density of controllable adjustment polymer microballoon, it is ensured that it in the solution can be the most floating.Meanwhile, this method uses crosslinkable prepolymer to enter
Row close, non-cross-linked polymer microsphere can be prevented effectively from use, due to bad mechanical strength, be soluble in organic solvent,
It is restricted in industry-by-industry field by shortcomings such as thermal softenings.Meanwhile, this method by control crosslinkable prepolymer molecular weight and
Consumption can also regulate the density of polymer microballoon, effectively closes the polymer microballoon in different size duct, and therefore the suitability is more
Add extensively.The polymer microballoon heatproof organic solvent-resistant prepared by the inventive method, has good mechanical performance, light scattering
The performances such as property, insulating properties, have extensively in fields such as oil drilling additive, acid mist suppression, cosmetics, coating, catalyst loadings
General application prospect.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but scope is not limited to described interior
Hold.
Embodiment 1: heatproof organic solvent-resistant surface, without the preparation method of osmotic polymer microsphere, specifically comprises the following steps that
Polymer microballoon underlying parameter to be covered: polystyrene hollow microsphere, average diameter is 1.0 μm, and density is 0.94g/cm3,
Microsphere consumption 50.0g, the total number of polystyrene microsphere the most to be covered is:(individual)；
Employing divinylbenzene/styrene crosslinkable prepolymer (≈1.05 g/cm3) be coated with, it is contemplated that parcel confining bed
Thickness is 100nm, then the consumption of crosslinkable prepolymer is:
(g)；
(1) in the there-necked flask of belt stirrer and the 100mL of heater, 30.0 g divinylbenzene and 6.0 g benzene are added
Ethylene, after being uniformly mixed, adds 1.08g azodiisobutyronitrile, is warming up to 55 DEG C and carries out bulk polymerization, work as reactant
When the viscosity of system reaches 200mPa s, rapidly system temperature is reduced to 25 DEG C with ice bath；
(2) in the there-necked flask of the 250mL of belt stirrer, at room temperature add 50.0g polystyrene hollow microsphere, add
Above-mentioned crosslinkable prepolymer 33.63g, is sufficiently stirred for, and makes polystyrene microsphere and crosslinkable prepolymer mix homogeneously；
(3) in the 1000mL there-necked flask with reflux, agitator and heater, 415g distilled water and 2.1g are added
Polyvinyl alcohol (1788), after heated and stirred is completely dissolved to polyvinyl alcohol, is down to room temperature by system temperature.Above-mentioned 83.63g is gathered
Phenylethylene micro ball and crosslinkable prepolymer mixture are transferred in reaction system, dispersed with stirring 10 under the rotating speed of 500 rpm/min
Minute, then heat to 80 DEG C of ripenings 4 hours, cooled, filter, rinse and obtain after drying that cross linked polymer closes is low close
Degree surface is without infiltrative polystyrene hollow microsphere.
This microsphere porous plate is respectively pressed in the mixed solution that dichloromethane and water are 1:3 with ethanol volume ratio and soaks
30 days, the most naturally drying after taking-up, density is unchanged, illustrates that this polymer microballoon is to dichloromethane and water and ethanol
Mixed solution is respectively provided with good toleration, and surface is without permeability.
Embodiment 2: heatproof organic solvent-resistant surface, without the preparation method of osmotic polymer microsphere, specifically comprises the following steps that
Polymer microballoon underlying parameter to be covered: polystyrene porous microsphere, average diameter is 10.0 μm, and density is 0.85g/
cm3, microsphere consumption 100.0g, the total number of polystyrene microsphere the most to be covered is:
(individual)；
Employing glycol methacrylate/styrene crosslinkable prepolymer (≈1.16 g/cm3) be coated with, it is contemplated that
Parcel enclosed layer thickness is 500nm, then the consumption of crosslinkable prepolymer is:
(g)；
(1) in the there-necked flask of belt stirrer and the 100mL of heater, 40.0g glycol methacrylate is added
With 10.0 g styrene, after being uniformly mixed, adding 0.5g azodiisobutyronitrile, being warming up to 55 DEG C, to carry out polymerisation in bulk anti-
Should, when the viscosity of reaction system reaches 500mPa s, rapidly system temperature is reduced to 22 DEG C with ice bath.
(2) in the there-necked flask of the 250mL of belt stirrer, 100.0g polystyrene porous microsphere is at room temperature added,
Add above-mentioned crosslinkable prepolymer 41.00g, be sufficiently stirred for, make polystyrene microsphere and crosslinkable prepolymer mix homogeneously.
(3) in the 1500mL there-necked flask with reflux, agitator and heater, add 690g distilled water and
13.8g polyvinyl alcohol (1788), after heated and stirred is completely dissolved to polyvinyl alcohol, is down to room temperature by system temperature.By above-mentioned
141g polystyrene microsphere and crosslinkable prepolymer mixture are transferred in reaction system, stir under the rotating speed of 1000 rpm/min
Disperse 10 minutes, then heat to 80 DEG C of ripenings 4 hours, cooled, filter, rinse and obtain after drying cross linked polymer and close
Low-density surface without infiltrative polystyrene porous microsphere.
This microsphere porous plate is respectively pressed in the mixed solution that dichloromethane and water are 1:3 with ethanol volume ratio and soaks
30 days, the most naturally drying after taking-up, density is unchanged, illustrates that this polymer microballoon is to dichloromethane and water and ethanol
Mixed solution is respectively provided with good toleration, and surface is without permeability.
Embodiment 3: heatproof organic solvent-resistant surface, without the preparation method of osmotic polymer microsphere, specifically comprises the following steps that
Polymer microballoon underlying parameter to be covered: polymethyl methacrylate porous microsphere, average diameter is 500.0 μm, density
For 0.96g/cm3, microsphere consumption 200.0g, the total number of poly (methyl methacrylate) micro-sphere the most to be covered is:
(individual)；
Employing glycol methacrylate/vinyl chloride crosslinkable prepolymer (≈1.08 g/cm3) be coated with, it is contemplated that
Parcel enclosed layer thickness is 2.0 μm, then the consumption of crosslinkable prepolymer is:
(g)；
(1) in the there-necked flask of belt stirrer and the 100mL of heater, add 5.0g glycol methacrylate and
10.0 g vinyl chloride, after being uniformly mixed, add 0.3g azodiisobutyronitrile, are warming up to 60 DEG C and carry out bulk polymerization,
When the viscosity of reaction system reaches 1000mPa s, rapidly system temperature is reduced to 25 DEG C with ice bath.
(2) in the there-necked flask of the 500mL of belt stirrer, 200.0g polymethyl methacrylate is at room temperature added many
Hole microsphere, adds above-mentioned crosslinkable prepolymer 5.39g, is sufficiently stirred for, and makes poly (methyl methacrylate) micro-sphere and prepolymer mixing
Uniformly.
(3) in the 1500mL there-necked flask with reflux, agitator and heater, add 800g distilled water and
20.0g polyvinyl alcohol (1788), after heated and stirred is completely dissolved to polyvinyl alcohol, is down to room temperature by system temperature.By above-mentioned
205.39g poly (methyl methacrylate) micro-sphere and crosslinkable prepolymer mixture are transferred in reaction system, at 1000 rpm/min
Rotating speed under dispersed with stirring 10 minutes, then heat to 83 DEG C of ripenings 4 hours, cooled, filter, rinse and handed over after drying
The low-density surface that linked polymer is closed is without infiltrative polymethyl methacrylate porous microsphere.
This microsphere porous plate is respectively pressed in the mixed solution that dichloromethane and water are 1:3 with ethanol volume ratio and soaks
30 days, the most naturally drying after taking-up, density is unchanged, illustrates that this polymer microballoon is to dichloromethane and water and ethanol
Mixed solution is respectively provided with good toleration, and surface is without permeability.
Embodiment 4: heatproof organic solvent-resistant surface, without the preparation method of osmotic polymer microsphere, specifically comprises the following steps that
Polymer microballoon underlying parameter to be covered: poly-tripolycyanamide hollow microsphere, average diameter is 200.0 μm, and density is
0.83g/cm3, microsphere consumption 300.0g, the poly-total number of tripolycyanamide microsphere the most to be covered is:
(individual)；
Employing divinylbenzene/methyl methacrylate crosslinkable prepolymer (≈1.17 g/cm3) be coated with, it is contemplated that bag
Wrapping up in enclosed layer thickness is 1.0 μm, then the consumption of crosslinkable prepolymer is:
(g)；
(1) in the there-necked flask of belt stirrer and the 100mL of heater, 10.0g divinylbenzene and 5.0 g methyl are added
Acrylic acid methyl ester., after being uniformly mixed, adds 0.45g azodiisobutyronitrile, is warming up to 65 DEG C and carries out bulk polymerization, when
When the viscosity of reaction system reaches 2500mPa s, rapidly system temperature is reduced to 23 DEG C with ice bath.
(2) in the there-necked flask of the 500mL of belt stirrer, 300.0g poly-tripolycyanamide hollow is at room temperature added micro-
Ball, adds above-mentioned crosslinkable prepolymer 12.68 g, is sufficiently stirred for, make poly-tripolycyanamide microsphere and crosslinkable prepolymer mix homogeneously.
(3) in the 2000mL there-necked flask with reflux, agitator and heater, 1000g distilled water is added
With 30.0g polyvinyl alcohol (1788), after heated and stirred is completely dissolved to polyvinyl alcohol, system temperature is down to room temperature.By above-mentioned
312.68g poly-tripolycyanamide microsphere and crosslinkable prepolymer mixture are transferred in reaction system, at the rotating speed of 1200 rpm/min
Lower dispersed with stirring 10 minutes, then heats to 83 DEG C of ripenings 4 hours, cooled, filter, rinse and obtain cross-linked polymeric after drying
The low-density surface that thing is closed is without infiltrative poly-tripolycyanamide hollow microsphere.
This microsphere porous plate is respectively pressed in the mixed solution that dichloromethane and water are 1:3 with ethanol volume ratio and soaks
30 days, the most naturally drying after taking-up, density is unchanged, illustrates that this polymer microballoon is to dichloromethane and water and ethanol
Mixed solution is respectively provided with good toleration, and surface is without permeability.
Embodiment 5: heatproof organic solvent-resistant surface, without the preparation method of osmotic polymer microsphere, specifically comprises the following steps that
Polymer microballoon underlying parameter to be covered: poly-tripolycyanamide porous microsphere, average diameter is 100.0 μm, and density is
0.92g/cm3, microsphere consumption 150.0g, the poly-total number of tripolycyanamide microsphere the most to be covered is:
(individual)；
Employing pentaerythritol triacrylate/acrylamide/ethylene vinyl acetate crosslinkable prepolymer (≈1.26 g/cm3)
Be coated with, it is contemplated that parcel enclosed layer thickness be 3.0 μm, then the consumption of crosslinkable prepolymer is:
(g)；
(1) in the there-necked flask of belt stirrer and the 100mL of heater, addition 5.0g pentaerythritol triacrylate,
20.0 g acrylamides and 30.0g ethylene vinyl acetate, after being uniformly mixed, add 0.055g azodiisobutyronitrile, rise
Temperature carries out bulk polymerization, when the viscosity of reaction system reaches 3000mPa s, with ice bath rapidly by system temperature to 75 DEG C
It is reduced to 20 DEG C.
(2) in the there-necked flask of the 500mL of belt stirrer, 150.0g poly-tripolycyanamide porous is at room temperature added micro-
Ball, adds above-mentioned crosslinkable prepolymer 37.03 g, is sufficiently stirred for, make poly-tripolycyanamide microsphere and crosslinkable prepolymer mix homogeneously.
(3) in the 1000mL there-necked flask with reflux, agitator and heater, add 450g distilled water and
22.5g polyvinyl alcohol (1788), after heated and stirred is completely dissolved to polyvinyl alcohol, is down to room temperature by system temperature.By above-mentioned
187.03g poly-tripolycyanamide microsphere and crosslinkable prepolymer mixture are transferred in reaction system, at the rotating speed of 2000 rpm/min
Lower dispersed with stirring 10 minutes, then heats to 85 DEG C of ripenings 4 hours, cooled, filter, rinse and obtain cross-linked polymeric after drying
The low-density surface that thing is closed is without infiltrative poly-tripolycyanamide porous microsphere.
This microsphere porous plate is respectively pressed in the mixed solution that dichloromethane and water are 1:3 with ethanol volume ratio and soaks
30 days, the most naturally drying after taking-up, density is unchanged, illustrates that this polymer microballoon is to dichloromethane and water and ethanol
Mixed solution is respectively provided with good toleration, and surface is without permeability.
Claims (6)
1. a heatproof organic solvent-resistant surface is without the preparation method of osmotic polymer microsphere, it is characterised in that: by single for crosslinking
Add oil-soluble initiator after body and uncrosslinked monomer mixing, carry out bulk prepolymerization, after having reacted, obtain crosslinkable prepolymer,
Then in this crosslinkable prepolymer, add porous or polymeric hollow microsphere, after being thoroughly mixed uniformly, use suspension polymerisation
Method carries out redispersion to it in aqueous phase system, after intensification slaking reaction, obtains the low-density surface that cross linked polymer is closed
Microsphere without osmotic polymer.
Heatproof organic solvent-resistant surface the most according to claim 1 is without the preparation method of osmotic polymer microsphere, and it is special
Levy and be to carry out by step in detail below:
(1), after cross-linking monomer and uncrosslinked monomer being uniformly mixed, the oil-soluble adding monomer gross mass 0.1 ~ 3% causes
Agent, is warming up to 55 ~ 75 DEG C and carries out bulk polymerization, when the viscosity of reaction system reaches 200mPa s ~ 3000mPa s, uses ice
System temperature is reduced to 20 ~ 25 DEG C rapidly by bath；
(2), under room temperature, crosslinkable prepolymer adds porous or polymeric hollow microsphere, is sufficiently stirred for, makes polymer microballoon and friendship
Connection prepolymer mix homogeneously, wherein the consumption of crosslinkable prepolymer can obtain according to following formula:, in formula: m is
The quality of crosslinkable prepolymer, N is the quantity being wrapped by porous or polymeric hollow microsphere, and D is for being wrapped porous or hollow polymeric
The diameter of thing microsphere,For the density of crosslinkable prepolymer, thickness d=0.1 ~ 100 μm of cross linked polymer parcel confining bed；
(3) adding the colloid protective agent of distilled water quality 0.5 ~ 5.0% in distilled water, heated and stirred is the most molten to colloid protective agent
Xie Hou, cools the temperature to room temperature, adds colloid protective agent solution quality 20～step (2) mixture of 40%, 500 ~
Dispersed with stirring 10 minutes under the rotating speed of 2000rpm/min, then heat to 80 ~ 85 DEG C of ripenings 4 hours, cooled, filter, rinse
Obtain the surface of cross linked polymer closing after drying without osmotic polymer microsphere.
Heatproof organic solvent-resistant surface the most according to claim 1 and 2 without the preparation method of osmotic polymer microsphere, its
It is characterised by: the mass ratio of cross-linking monomer and uncrosslinked monomer is 5:1 ~ 1:10.
Heatproof organic solvent-resistant surface the most according to claim 1 and 2 without the preparation method of osmotic polymer microsphere, its
It is characterised by: cross-linking monomer is in divinylbenzene, glycol methacrylate, pentaerythritol triacrylate
Kind.
Heatproof organic solvent-resistant surface the most according to claim 1 and 2 without the preparation method of osmotic polymer microsphere, its
It is characterised by: uncrosslinked monomer is in styrene, vinyl chloride, methyl methacrylate, acrylamide, ethylene vinyl acetate
One or more.
Heatproof organic solvent-resistant surface the most according to claim 1 and 2 without the preparation method of osmotic polymer microsphere, its
It is characterised by: the particle diameter of porous or polymeric hollow microsphere is 1 μm ~ 500 μm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453724A (en) * | 2018-11-21 | 2019-03-12 | 广州中科检测技术服务有限公司 | A kind of inside is the preparation method of the slow-release type microcapsule of multicore |
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| CN1927913A (en) * | 2006-08-24 | 2007-03-14 | 中国科学院合肥物质科学研究院 | Chemical preparation method of hollow polymer microsphere with controllable open pores |
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| CN109453724A (en) * | 2018-11-21 | 2019-03-12 | 广州中科检测技术服务有限公司 | A kind of inside is the preparation method of the slow-release type microcapsule of multicore |
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