CN109456446A - 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 PDF

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Publication number
CN109456446A
CN109456446A CN201811447766.9A CN201811447766A CN109456446A CN 109456446 A CN109456446 A CN 109456446A CN 201811447766 A CN201811447766 A CN 201811447766A CN 109456446 A CN109456446 A CN 109456446A
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China
Prior art keywords
specific surface
monomer
glycidyl methacrylate
poly
polymer microcapsules
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Pending
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CN201811447766.9A
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Chinese (zh)
Inventor
张秋禹
刘锦
刘毅彬
张宝亮
张和鹏
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Northwestern Polytechnical University
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Northwestern Polytechnical University
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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
    • 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
    • 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
    • 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 methods of high-specific surface polymer microcapsules, it is macromole emulsifying agent and initiator using there is surface-active simultaneously and cause the poly (glycidyl methacrylate) of monomer polymerization function, utilize inverse emulsion polymerization method, continuous phase is mutually used as oily, it is not added under conditions of small-molecular emulsifier and initiator additionally, cause the polymerization of hydrophobicity cross-linking monomer, obtains high-specific surface polymer microcapsules.Not only with the characteristic of capsule; Protective substances are exempted from affected by environment; active constituent is isolated; reduce volatility and toxicity; the regulation to surface wrinkles pattern can also be passed through; it realizes and controls sustainable release action, have wide practical use in multiple fields such as medicine, food, fragrance, cosmetics, coating, pesticide, weaving and energy conservations.

Description

A kind of preparation method of high-specific surface polymer microcapsules
Technical field
The invention belongs to the preparation methods of high molecular material, are related to a kind of preparation side of high-specific surface polymer microcapsules Method.
Background technique
High-specific surface polymer microcapsules not only have the characteristic of capsule, and Protective substances exempt from affected by environment, isolation work Property ingredient, reduce volatility and toxicity, moreover it is possible to by the regulation to surface wrinkles pattern, change the tracking, release, capture of substance Function and adhesiveness realize and control sustainable release action, medicine, food, fragrance, cosmetics, coating, pesticide, weaving and The multiple fields such as energy conservation are widely used.
The technology for preparing microcapsules at present is highly developed, mainly includes 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 It with extensive monomer applicability, be used to prepare polymer microcapsule of the partial size from tens nanometers to up to a hundred microns, and be able to achieve Large-scale industrial production, however 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, 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 the adjustment of parameter and formula Meet particular demands using the high-specific surface area of particle well.The hollow structure of surface wrinkles pattern and microcapsules is combined Come, be not only able to achieve the cladding buffer action of capsule, but also is able to achieve apparent property regulation, 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 reverse phase cream Liquid polymerization is advantageous in that the polymethylacrylic acid shrink for introducing while having surface-active and cause monomer polymerization function Glyceride is macromole emulsifying agent and initiator, is mutually used as continuous phase oily, small-molecular emulsifier and initiator are not added additionally Under conditions of, the polymerization of hydrophobicity cross-linking monomer can be caused 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 suitble to industrialization large-scale production.
Summary 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 is emulsified using having surface-active simultaneously and causing the poly (glycidyl methacrylate) of monomer polymerization function as macromolecular Agent and initiator are mutually used as continuous phase oily, small-molecular emulsifier and initiation are not added additionally using inverse emulsion polymerization method Under conditions of agent, causes 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 steps are as follows:
Step 1: by the poly (glycidyl methacrylate) with surface-active and initiation monomer polymerization function, hydrophobicity Cross-linking monomer, water or salting liquid and organic solvent are that 0.1~10:1~20:10~100:10~100 ratio is mixed in mass ratio It is emulsified 10~50 minutes after conjunction and obtains stable water-in-oil emulsion；
Step 2: above-mentioned emulsion being heated to 60~100 DEG C of polymerization reactions to cause monomer, heat preservation is tied after 2~24 hours Shu Fanying
Step 3: the lotion for using centrifugation and the mode that combines of revolving sufficiently cleans after reacting 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 be 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, methylene chloride, 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
The preparation method of a kind of high-specific surface polymer microcapsules proposed by the present invention, using there is surface-active simultaneously It is macromole emulsifying agent and initiator with the poly (glycidyl methacrylate) for causing monomer polymerization function, utilizes reversed-phase emulsion Polymerization is mutually used as continuous phase oily, is not added under conditions of small-molecular emulsifier and initiator additionally, causes hydrophobic sexual intercourse Join monomer polymerization, obtains high-specific surface polymer microcapsules.Not only with the characteristic of capsule, Protective substances are from environment shadow It rings, active constituent is isolated, reduce volatility and toxicity, moreover it is possible to by the regulation to surface wrinkles pattern, realize that control is sustainable Release action has in multiple fields such as medicine, food, fragrance, cosmetics, coating, pesticide, weaving and energy conservations and widely answers Use prospect.
Detailed description of the invention
Fig. 1: poly (glycidyl methacrylate) causes high-specific surface polymer microcapsules obtained by divinylbenzene Stereoscan photograph.
Fig. 2: poly (glycidyl methacrylate) causes high-ratio surface obtained by divinylbenzene cladding Magnesium dichloride hexahydrate Gather the stereoscan photograph of complex microcapsule.
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
Embodiment 1: poly (glycidyl methacrylate) causes ethylene glycol dimethacrylate polymerization preparation Gao Bibiao Area polymer microcapsule
By 6g poly (glycidyl methacrylate), 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, after reaction 12 hours, sufficiently 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) causes divinyl benzene polymer and prepares high-specific surface polymer Microcapsules
After 4g poly (glycidyl methacrylate), 20g divinylbenzene monomers, 25g water, 30g hexamethylene are mixed, in Emulsification 10 minutes is stirred at room temperature, after being heated to 70 DEG C, reaction 12 hours, sufficiently 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) causes N hydroxymethyl acrylamide polymerization and prepares high-specific surface area Polymer microcapsule
4g poly (glycidyl methacrylate), 20g N hydroxymethyl acrylamide monomer, 30g water, 30g hexamethylene are mixed After conjunction, emulsification 30 minutes is stirred at room temperature, is heated to 70 DEG C, after reaction 12 hours, sufficiently cleaning removes hexamethylene, unpolymerized N hydroxymethyl acrylamide and poly (glycidyl methacrylate) soluble in water obtain high-ratio surface accumulation (N- methylol Acrylamide) microcapsules.
Embodiment 4: poly (glycidyl methacrylate) causes N hydroxymethyl acrylamide polymerization and prepares high-specific surface area Polymer microcapsule
6g poly (glycidyl methacrylate), 30g N hydroxymethyl acrylamide monomer, 40g water, 20g petroleum ether are mixed After conjunction, emulsification 30 minutes is stirred at room temperature, after being heated to 70 DEG C, reaction 10 hours, it is unpolymerized to remove petroleum ether for sufficiently cleaning N hydroxymethyl acrylamide and poly (glycidyl methacrylate) soluble in water obtain high-ratio surface accumulation (N- methylol Acrylamide) microcapsules.
Embodiment 5: poly (glycidyl methacrylate) causes bismaleimide polymerization and prepares high-specific surface area polymerization Object microcapsule coated sodium chloride
By 4g poly (glycidyl methacrylate), 20g bismaleimide monomer, the sodium chloride that 40g concentration is 20% After solution, the mixing of 30g n-hexane, emulsification 30 minutes is stirred at room temperature, after being heated to 60 DEG C, reaction 12 hours, sufficiently cleaning is removed N-hexane, unpolymerized bismaleimide and poly (glycidyl methacrylate) soluble in water are removed, high-ratio surface is obtained It gathers bismaleimide and coats sodium chloride microcapsules.
Embodiment 6: poly (glycidyl methacrylate) causes bismaleimide polymerization and prepares high-specific surface area polymerization Object microcapsule coated sodium carbonate
By 4g poly (glycidyl methacrylate), 20g bismaleimide monomer, the sodium carbonate that 40g concentration is 20% After solution, the mixing of 30g n-hexane, emulsification 30 minutes is stirred at room temperature, after being heated to 60 DEG C, reaction 12 hours, sufficiently cleaning is removed N-hexane, unpolymerized bismaleimide and poly (glycidyl methacrylate) soluble in water are removed, high-ratio surface is obtained It gathers bismaleimide and coats sodium carbonate microcapsules.
Embodiment 7: poly (glycidyl methacrylate) causes divinyl benzene polymer and prepares high-specific surface polymer Microcapsule coated Magnesium dichloride hexahydrate
By 4g poly (glycidyl methacrylate), 15g divinylbenzene monomers, the six hydration chlorine that 35g concentration is 30% After changing magnesium solution, the mixing of 25g hexamethylene, emulsification 10 minutes is stirred at room temperature, it is sufficiently clear after being heated to 70 DEG C, reaction 12 hours 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) causes bismaleimide and divinylbenzene combined polymerization preparation High-specific surface polymer microcapsule coated sodium phosphate dodecahydrate
By 6g poly (glycidyl methacrylate), 10g bismaleimide monomer, 10g divinylbenzene monomers, 35g Concentration be 30% sodium phosphate dodecahydrate solution, 25g petroleum ether mixing after, be stirred at room temperature emulsification 20 minutes, be heated to 60 DEG C, after reaction 12 hours, sufficiently 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 while having surface-active and causes the poly (glycidyl methacrylate) of monomer polymerization function For macromole emulsifying agent and initiator, cause 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 being added Additional small-molecular emulsifier and initiator etc., be not only able to achieve the cladding buffer action of capsule, but also were able to achieve apparent property regulation, System and preparation process are simple, and post-processing is easy, and versatile, cost is relatively low, are suitble to industrialization large-scale production.

Claims (4)

1. a kind of preparation method of high-specific surface polymer microcapsules, it is characterised in that steps are as follows:
Step 1: the poly (glycidyl methacrylate) with surface-active and initiation monomer polymerization function, hydrophobicity are crosslinked Monomer, water or salting liquid and organic solvent are after 0.1~10:1~20:10~100:10~100 ratio mixes in mass ratio Emulsification obtains stable water-in-oil emulsion in 10~50 minutes；
Step 2: above-mentioned emulsion being heated to 60~100 DEG C of polymerization reactions to cause monomer, is terminated after heat preservation 2~24 hours anti- It answers
Step 3: the mode for using centrifugation and revolving to combine cleans the lotion after reaction sufficiently 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: 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.
CN201811447766.9A 2017-12-05 2018-11-29 A kind of preparation method of high-specific surface polymer microcapsules Pending CN109456446A (en)

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CN111886071B (en) * 2018-06-21 2023-10-27 弗门尼舍有限公司 Method for preparing mineralized microcapsules
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017008040A (en) * 2015-06-23 2017-01-12 大阪ガスケミカル株式会社 Particle, mixture, kneaded material, 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017008040A (en) * 2015-06-23 2017-01-12 大阪ガスケミカル株式会社 Particle, mixture, kneaded material, 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

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Application publication date: 20190312