CN108003299A - A kind of preparation method of high-specific surface polymer microcapsules - Google Patents
A kind of preparation method of high-specific surface polymer microcapsules Download PDFInfo
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- CN108003299A CN108003299A CN201711263625.7A CN201711263625A CN108003299A CN 108003299 A CN108003299 A CN 108003299A CN 201711263625 A CN201711263625 A CN 201711263625A CN 108003299 A CN108003299 A CN 108003299A
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- Prior art keywords
- specific surface
- glycidyl methacrylate
- preparation
- poly
- polymer microcapsules
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present invention relates to a kind of preparation method of high-specific surface polymer microcapsules, it is macromole emulsifying agent and initiator using the poly (glycidyl methacrylate) at the same time with surface-active and initiation monomer polymerization, utilize inverse emulsion polymerization method, in oil phase as continuous phase, do not add under conditions of small-molecular emulsifier and initiator additionally, trigger the polymerization of hydrophobicity cross-linking monomer, obtain high-specific surface polymer microcapsules.Not only there is the characteristic of capsule; Protective substances are exempted from affected by environment; isolate active ingredient; reduce volatility and toxicity; the regulation and control to surface wrinkles pattern can also be passed through; realize and control sustainable release action, have wide practical use in multiple fields such as medicine, food, spices, cosmetics, coating, pesticide, weaving and energy conservations.
Description
Technical field
The invention belongs to the preparation method of high molecular material, is related to a kind of preparation side of high-specific surface polymer microcapsules
Method.
Background technology
High-specific surface polymer microcapsules not only have the characteristic of capsule, and Protective substances exempt from affected by environment, isolation work
Property component, reduce volatility and toxicity, moreover it is possible to by the regulation and control to surface wrinkles pattern, change the tracking, release, seizure of material
Function and adhesiveness, realize and control sustainable release action, medicine, food, spices, cosmetics, coating, pesticide, weaving and
The multiple fields such as energy conservation are widely used.
It is highly developed that the technology of microcapsules is prepared at present, mainly including template, LBL self-assembly method, spray drying
Method, interfacial polymerization, phase separation method and situ aggregation method.Wherein interfacial polymerization and situ aggregation method are because of simple instrument and equipment
With extensive monomer applicability, be used to prepare polymer microcapsule of the particle diameter from tens nanometers to up to a hundred microns, and can realize
Large-scale industrial production, but it has been reported that polymer microcapsule be mostly surface is smooth or collapses single shape.Surface
Because its pattern Modulatory character is increasingly becoming micro nano structure polymer research hotspot, its preparation method is also in wrinkle polymer particle
Existing diversity, mainly includes ultraviolet radioactive method, micro-fluidic technologies and suspension polymerization, can be with by parameter and the adjustment that is formulated
Meet particular demands using the high-specific surface area of particle well.The hollow structure of surface wrinkles pattern and microcapsules is combined
Come, can realize the cladding buffer action of capsule and realize that apparent property regulates and controls, this multi-functional high-specific surface polymer
The preparation of microcapsules is but rarely reported.High-specific surface polymer microcapsule preparation method according to the present invention belongs to anti-phase breast
Liquid polymerization, is advantageous in that and introduces while have the function of surface-active and trigger the polymethylacrylic acid of monomer polymerization to shrink
Glyceride is macromole emulsifying agent and initiator, in oil phase as continuous phase, does not add small-molecular emulsifier and initiator additionally
Under conditions of, you can trigger the polymerization of hydrophobicity cross-linking monomer in oil-water interfaces, obtain high-specific surface polymer microcapsules.The party
Law system and preparation process are simple, and post processing is easy, and versatile, cost is relatively low, are adapted to industrialization large-scale production.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of preparation of high-specific surface polymer microcapsules
Method, there is surface-active at the same time and trigger the poly (glycidyl methacrylate) of monomer polymerization to be emulsified as macromolecular
Agent and initiator, using inverse emulsion polymerization method, in oil phase as continuous phase, do not add small-molecular emulsifier and initiation additionally
Under conditions of agent, trigger the polymerization of hydrophobicity cross-linking monomer, obtain high-specific surface polymer microcapsules.
Technical solution
A kind of preparation method of high-specific surface polymer microcapsules, it is characterised in that step is as follows：
Step 1：To there is surface-active and trigger the poly (glycidyl methacrylate) of monomer polymerization, hydrophobicity
Cross-linking monomer, water or salting liquid and organic solvent are 0.1~10 in mass ratio:1~20:10~100:10~100 ratio is mixed
Emulsified 10~50 minutes after conjunction and obtain stable water-in-oil emulsion；
Step 2：Above-mentioned emulsion is heated to 60~100 DEG C to trigger the polymerisation of monomer, when insulation 2~24 is small after tie
Shu Fanying
Step 3：Use centrifugation and lotion that the mode that is combined of revolving is fully cleaned after reaction is to remove organic solvent, not
The monomer of reaction, poly (glycidyl methacrylate) soluble in water, obtain high-specific surface polymer microcapsules.
The salting liquid for calcium nitrate tetrahydrate, sodium hydroxide, potassium carbonate, six nitric hydrate ferrous irons, Magnesium dichloride hexahydrate,
Potassium nitrate, sodium nitrate, four hydration calcium bromides, eight nitric hydrate aluminium, sodium chloride, 12 hydrazine aluminum sulfate potassium, sodium carbonate, fluorination
Potassium, 12 hypophosphite monohydrate hydrogen sodium, manganese nitrate hexahydrate, three chloride hydrate zinc, Disodium sulfate decahydrate or ten hydrated sodium borates are water-soluble
Liquid.
The organic solvent is propyl acetate, petroleum ether, glycol ether, n-hexane, toluene, dimethylbenzene, octane, hexamethylene
Alkane, ethyl acetate, dichloromethane, butyl acetate, amyl acetate, chloroform or trichloroethanes.
The hydrophobicity cross-linking monomer is diacetone acrylamide, N hydroxymethyl acrylamide, dimethacrylate second two
Alcohol ester, acetoacetoxyethyl methacrylate, divinylbenzene, diisocyanate, glycidyl methacrylate, peroxide
Change benzoyl, di-tert-butyl peroxide, t-butyl perbenzoate, bismaleimide or triallyl isocyanate.
Beneficial effect
A kind of preparation method of high-specific surface polymer microcapsules proposed by the present invention, using at the same time there is surface-active
Poly (glycidyl methacrylate) with initiation monomer polymerization function is macromole emulsifying agent and initiator, utilizes reversed-phase emulsion
Polymerization, in oil phase as continuous phase, does not add under conditions of small-molecular emulsifier and initiator additionally, triggers hydrophobic sexual intercourse
Join monomer polymerization, obtain high-specific surface polymer microcapsules.Not only there is the characteristic of capsule, Protective substances are from environment shadow
Ring, isolate active ingredient, reduce volatility and toxicity, moreover it is possible to by the regulation and control to surface wrinkles pattern, realize that control is sustainable
Release action, has in multiple fields such as medicine, food, spices, cosmetics, coating, pesticide, weaving and energy conservations and widely should
Use prospect.
Brief description of the drawings
Fig. 1：Poly (glycidyl methacrylate) triggers high-specific surface polymer microcapsules obtained by divinylbenzene
Stereoscan photograph.
Fig. 2：Poly (glycidyl methacrylate) triggers high-ratio surface obtained by divinylbenzene cladding Magnesium dichloride hexahydrate
Gather the stereoscan photograph of complex microcapsule.
Embodiment
In conjunction with embodiment, attached drawing, the invention will be further described：
Embodiment 1：Poly (glycidyl methacrylate) triggers ethylene glycol dimethacrylate polymerization to prepare Gao Bibiao
Area polymer microcapsule
By 6g poly (glycidyl methacrylate)s, 25g ethylene glycol dimethacrylate monomer, 25g water, 30g toluene
After mixing, emulsification 10 minutes is stirred at room temperature, is heated to 60 DEG C, when reaction 12 is small after, fully cleaning removes toluene, unpolymerized
Ethylene glycol dimethacrylate and poly (glycidyl methacrylate) soluble in water, obtain high-specific surface area poly dimethyl
Acrylic acid glycol ester microcapsules.
Embodiment 2：Poly (glycidyl methacrylate) triggers divinyl benzene polymer to prepare high-specific surface polymer
Microcapsules
After 4g poly (glycidyl methacrylate)s, 20g divinylbenzene monomers, 25g water, 30g hexamethylenes are mixed, in
Emulsification 10 minutes is stirred at room temperature, is heated to 70 DEG C, when reaction 12 is small after, fully cleaning removes hexamethylene, unpolymerized divinyl
Base benzene and poly (glycidyl methacrylate) soluble in water, obtain high-specific surface area polydivinylbenezene microcapsules.
Embodiment 3：Poly (glycidyl methacrylate) triggers N hydroxymethyl acrylamide polymerization to prepare high-specific surface area
Polymer microcapsule
4g poly (glycidyl methacrylate)s, 20g N hydroxymethyl acrylamides monomer, 30g water, 30g hexamethylenes are mixed
After conjunction, emulsification 30 minutes is stirred at room temperature, is heated to 70 DEG C, when reaction 12 is small after, fully cleaning removes hexamethylene, unpolymerized
N hydroxymethyl acrylamide and poly (glycidyl methacrylate) soluble in water, obtain high-ratio surface accumulation (N- methylols
Acrylamide) microcapsules.
Embodiment 4：Poly (glycidyl methacrylate) triggers N hydroxymethyl acrylamide polymerization to prepare high-specific surface area
Polymer microcapsule
6g poly (glycidyl methacrylate)s, 30g N hydroxymethyl acrylamides monomer, 40g water, 20g petroleum ethers are mixed
After conjunction, emulsification 30 minutes is stirred at room temperature, is heated to 70 DEG C, when reaction 10 is small after, it is unpolymerized to remove petroleum ether for fully cleaning
N hydroxymethyl acrylamide and poly (glycidyl methacrylate) soluble in water, obtain high-ratio surface accumulation (N- methylols
Acrylamide) microcapsules.
Embodiment 5：Poly (glycidyl methacrylate) triggers bismaleimide polymerization to prepare high-specific surface area polymerization
Thing microcapsule coated sodium chloride
By 4g poly (glycidyl methacrylate)s, 20g bismaleimide monomers, the sodium chloride that 40g concentration is 20%
After solution, the mixing of 30g n-hexanes, emulsification 30 minutes is stirred at room temperature, is heated to 60 DEG C, when reaction 12 is small after, fully cleaning removes
N-hexane, unpolymerized bismaleimide and poly (glycidyl methacrylate) soluble in water are removed, obtains high-ratio surface
Gather bismaleimide cladding sodium chloride microcapsules.
Embodiment 6：Poly (glycidyl methacrylate) triggers bismaleimide polymerization to prepare high-specific surface area polymerization
Thing microcapsule coated sodium carbonate
By 4g poly (glycidyl methacrylate)s, 20g bismaleimide monomers, the sodium carbonate that 40g concentration is 20%
After solution, the mixing of 30g n-hexanes, emulsification 30 minutes is stirred at room temperature, is heated to 60 DEG C, when reaction 12 is small after, fully cleaning removes
N-hexane, unpolymerized bismaleimide and poly (glycidyl methacrylate) soluble in water are removed, obtains high-ratio surface
Gather bismaleimide cladding sodium carbonate microcapsules.
Embodiment 7：Poly (glycidyl methacrylate) triggers divinyl benzene polymer to prepare high-specific surface polymer
Microcapsule coated Magnesium dichloride hexahydrate
By 4g poly (glycidyl methacrylate)s, 15g divinylbenzene monomers, the six hydration chlorine that 35g concentration is 30%
After changing magnesium solution, the mixing of 25g hexamethylenes, emulsification 10 minutes is stirred at room temperature, is heated to 70 DEG C, when reaction 12 is small after, it is fully clear
Hexamethylene, unpolymerized divinylbenzene and poly (glycidyl methacrylate) soluble in water are removed in washout, obtain Gao Bibiao
Area polydivinylbenezene coats Magnesium dichloride hexahydrate microcapsules.
Embodiment 8：Poly (glycidyl methacrylate) triggers bismaleimide and divinylbenzene combined polymerization to prepare
High-specific surface polymer microcapsule coated sodium phosphate dodecahydrate
By 6g poly (glycidyl methacrylate)s, 10g bismaleimide monomers, 10g divinylbenzene monomers, 35g
Concentration be 30% sodium phosphate dodecahydrate solution, 25g petroleum ethers mixing after, be stirred at room temperature emulsification 20 minutes, be heated to 60
DEG C, when reaction 12 is small after, fully cleaning removes petroleum ether, unpolymerized bismaleimide, divinylbenzene and soluble in water
Poly (glycidyl methacrylate), obtain high-ratio surface accumulation (bismaleimide-divinylbenzene) coat 12 water
Close sodium phosphate microcapsules.
The present invention utilizes the poly (glycidyl methacrylate) at the same time with surface-active and initiation monomer polymerization
For macromole emulsifying agent and initiator, trigger the polymerization of hydrophobic monomer in a heated condition, continuous phase is organic phase, dispersed phase
For inorganic phase, high-specific surface polymer microcapsules are obtained.Compared with existing polymer microcapsule preparation method, without adding
Extra small-molecular emulsifier and initiator etc., can realize the cladding buffer action of capsule and realize that apparent property regulates and controls,
System and preparation process are simple, and post processing is easy, and versatile, cost is relatively low, are adapted to industrialization large-scale production.
Claims (4)
1. a kind of preparation method of high-specific surface polymer microcapsules, it is characterised in that step is as follows：
Step 1：To there is surface-active and trigger the poly (glycidyl methacrylate) of monomer polymerization, hydrophobicity crosslinking
Monomer, water or salting liquid and organic solvent are 0.1~10 in mass ratio:1~20:10~100:After 10~100 ratio mixing
Emulsification obtains stable water-in-oil emulsion in 10~50 minutes；
Step 2：Above-mentioned emulsion is heated to 60~100 DEG C to trigger the polymerisation of monomer, when insulation 2~24 is small after terminate it is anti-
Should
Step 3：The lotion that the mode for centrifuging and rotating and be combined fully is cleaned after reaction is used to remove organic solvent, unreacted
Monomer, poly (glycidyl methacrylate) soluble in water, obtain high-specific surface polymer microcapsules.
2. the preparation method of high-specific surface polymer microcapsules according to claim 1, it is characterised in that：The salting liquid
For calcium nitrate tetrahydrate, sodium hydroxide, potassium carbonate, six nitric hydrate ferrous irons, Magnesium dichloride hexahydrate, potassium nitrate, sodium nitrate, four water
Close calcium bromide, eight nitric hydrate aluminium, sodium chloride, 12 hydrazine aluminum sulfate potassium, sodium carbonate, potassium fluoride, 12 hypophosphite monohydrate hydrogen sodium,
Manganese nitrate hexahydrate, three chloride hydrate zinc, Disodium sulfate decahydrate or ten hydrated sodium borate aqueous solutions.
3. the preparation method of high-specific surface polymer microcapsules according to claim 1, it is characterised in that：It is described organic molten
Agent is propyl acetate, petroleum ether, glycol ether, n-hexane, toluene, dimethylbenzene, octane, hexamethylene, ethyl acetate, dichloromethane
Alkane, butyl acetate, amyl acetate, chloroform or trichloroethanes.
4. the preparation method of high-specific surface polymer microcapsules according to claim 1, it is characterised in that：The hydrophobicity
Cross-linking monomer is diacetone acrylamide, N hydroxymethyl acrylamide, ethylene glycol dimethacrylate, acetoacetate ylmethyl
Ethyl acrylate, divinylbenzene, diisocyanate, glycidyl methacrylate, benzoyl peroxide, di-t-butyl mistake
Oxide, t-butyl perbenzoate, bismaleimide or triallyl isocyanate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711263625.7A CN108003299A (en) | 2017-12-05 | 2017-12-05 | A kind of preparation method of high-specific surface polymer microcapsules |
| CN201811447766.9A CN109456446A (en) | 2017-12-05 | 2018-11-29 | A kind of preparation method of high-specific surface polymer microcapsules |
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| CN201711263625.7A CN108003299A (en) | 2017-12-05 | 2017-12-05 | A kind of preparation method of high-specific surface polymer microcapsules |
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| CN201811447766.9A Pending CN109456446A (en) | 2017-12-05 | 2018-11-29 | A kind of preparation method of high-specific surface polymer microcapsules |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111886071A (en) * | 2018-06-21 | 2020-11-03 | 弗门尼舍有限公司 | Method for preparing mineralized microcapsules |
| CN114797697A (en) * | 2021-01-27 | 2022-07-29 | 北京化工大学 | Bismaleimide resin hollow polymer microsphere, preparation method thereof and method for modifying cyanate resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6741487B2 (en) * | 2015-06-23 | 2020-08-19 | 大阪ガスケミカル株式会社 | Particle, mixture, kneaded product, molded body and method for producing particle |
| CN106632874A (en) * | 2016-10-11 | 2017-05-10 | 西北工业大学 | Preparation method for polymer microcapsule |
| CN107337745A (en) * | 2017-08-04 | 2017-11-10 | 西北工业大学 | A kind of preparation method of water-in-oil type polymer microcapsule |
-
2017
- 2017-12-05 CN CN201711263625.7A patent/CN108003299A/en active Pending
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- 2018-11-29 CN CN201811447766.9A patent/CN109456446A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111886071A (en) * | 2018-06-21 | 2020-11-03 | 弗门尼舍有限公司 | Method for preparing mineralized microcapsules |
| CN111886071B (en) * | 2018-06-21 | 2023-10-27 | 弗门尼舍有限公司 | Method for preparing mineralized microcapsules |
| CN114797697A (en) * | 2021-01-27 | 2022-07-29 | 北京化工大学 | Bismaleimide resin hollow polymer microsphere, preparation method thereof and method for modifying cyanate resin |
| CN114797697B (en) * | 2021-01-27 | 2024-04-12 | 北京化工大学 | Hollow polymer microsphere of bismaleimide resin, preparation method thereof and method for modifying cyanate resin |
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| CN109456446A (en) | 2019-03-12 |
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