CN105754046A - Initiator microcapsule preparation method - Google Patents
Initiator microcapsule preparation method Download PDFInfo
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- CN105754046A CN105754046A CN201610151393.5A CN201610151393A CN105754046A CN 105754046 A CN105754046 A CN 105754046A CN 201610151393 A CN201610151393 A CN 201610151393A CN 105754046 A CN105754046 A CN 105754046A
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- initiator
- polyethylene glycol
- deionized water
- preparation
- microcapsule
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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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
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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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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)
- Cosmetics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an initiator microcapsule preparation method and belongs to the technical field of materials, energy and chemical industry.The initiator microcapsule preparation method includes mixing sodium dodecyl sulfate, polyethylene glycol 6000, initiators and deionized water, and then mechanically stirring for pre-emulsification.By stirring, sodium dodecyl sulfate and polyethylene glycol 6000 are dissolved in deionized water completely.Since the sodium dodecyl sulfate and polyethylene glycol 6000 which are taken as emulsifiers are dissolved in the water, the mixed solution is emulsified while the initiators can be dispersed in solvent well, and a stable system is formed.
Description
Technical field
The invention belongs to material, the energy, technical field of chemistry and chemical engineering.
Background technology
Organic peroxide and azo-compound (BP, cumyl peroxide, peroxidized t-butyl perbenzoate, azodiisobutyronitrile etc.) are the initiators of alkene class, the radical polymerization of double; two vinyl monomer and copolymerization, simultaneously can be used for the crosslinking curing of unsaturated polyester (UP) and high molecular crosslink reaction, the research and production of adhesive and sealant act on very big, whether initiator adds the amount put into initiator directly affects the carrying out of polyreaction and the speed of polyreaction, also can affect the storage phase of product.In order to realize organic initiators in above-mentioned production can slow releasing, reach the effect of time and the reaction rate efficiently controlling reaction.The present invention proposes by initiator micro encapsulation, and discharge from microcapsule under specific time with condition, the above-mentioned purpose wanted can be reached.
At present, under the work of forefathers, existing by inorganic salt oxidant (Ammonium persulfate., potassium peroxydisulfate, cerium oxide etc.), micro encapsulation, but there is the deficiency of several respects in this invention, and have a degree of difference with the present invention.(1) both character are different, and inorganic oxidizer mostly is water solublity, and organic initiators mostly is oil-soluble;(2) both applications are different, and inorganic oxidizer is used for emulsion and aqueous solution polymerization reaction, and organic initiators is used for emulsion and oil solution polyreaction, especially with the obvious advantage in unsaturated polyester resin crosslinking curing etc.;(3) azo-initiator relatively inorganic oxidizer stability is strong, and side reaction is few, and efficiency of initiation is high, polyreaction is easily-controllable, conversion rate of products advantages of higher.(4) economic and environment-friendly aspect;Microcapsule prepared by inorganic oxide is in the middle of chloroform, hexamethylene, and microcapsule prepared by the present invention prepares in deionized water, compares the former, more economically environmental protection.(5) encapsulation ratio;Inorganic oxidizer encapsulation rate is up to 91%, and in the present invention, organic initiators encapsulation rate is up to 92.15%.
Summary of the invention
It is an object of the invention to propose a kind of encapsulation ratio higher, a kind of preparation method of the initiator microcapsule of environmental protection more economically.
Technical scheme step is as follows;
1) sodium lauryl sulphate, polyethylene glycol 6000, initiator and deionized water being mixed, mechanical agitation carries out pre-emulsification;
2) dropping butanol and ethanol in the solution that pre-emulsification obtains, react under nitrogen protection;
3) dropping sorbester p17 in the mixed system that reaction obtains, after stirring is warming up to 70 DEG C, drips styrene and butyl acrylate, continues stirring to reacting completely;
4) wash after the system after complete reaction being cooled down room temperature, dry, obtain initiator microcapsule.
Sodium lauryl sulphate, polyethylene glycol 6000, initiator and deionized water are first mixed by the present invention, mechanical agitation carries out pre-emulsification, sodium lauryl sulphate, polyethylene glycol 6000 can be made to be completely dissolved in deionized water, sodium lauryl sulphate, polyethylene glycol 6000 are dissolved in the water as emulsifying agent, solution can be made on the one hand to form emulsion, initiator can also be made well to be distributed in the middle of solvent on the other hand, form stable system.
It addition, in the present invention, dropping butanol has been mainly the effect of cosurfactant, in aqueous; whipping process there is emulsifying agent exist, foam can be produced, drip ethanol; the effect of froth breaking can be played, pass into nitrogen and be primarily to the air removed in reaction environment, with nitrogen for protection gas.Sorbester p17 is oil soluble surfactant, and its lipophilic group can stretch to oil-soluble styrene and butyl acrylate well, and its hydrophilic group also can stretch in the middle of deionized water well, makes styrene and butyl acrylate be aggregated in initiator surface better.
Further, initiator of the present invention is any one in benzoyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described initiator, sodium lauryl sulphate, polyethylene glycol 6000, butanol, ethanol and sorbester p17 account for respectively and always feed intake the 5~10% of quality, 0.5~0.8%, 1~3%, 0.5~1.5%, 1~3% and 0.5~0.8%;The total quality of styrene and butyl acrylate accounts for the 10~15% of the quality that always feeds intake, and all the other are deionized water, amounts to 100%.
The present invention is by above technical scheme, and adds amount of medicament in scope defined above, it is possible to initiator realizes micro encapsulation well, and its highest encapsulation ratio can reach 92.15%, by the control of temperature can realize the time controlled released of microcapsule.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the benzoyl peroxide microcapsule of preparation.
Fig. 2 is the benzoyl peroxide microcapsule outside drawing of preparation.
Specific embodiments
Describing the present invention below in conjunction with specific embodiment, it is necessary to explanation, protection scope of the present invention is not limited in following embodiment.
Illustrate: the medicine used in the present invention is commercially available prod or laboratory conventional medication.
One, preparation technology:
First weigh a certain amount of initiator, sodium lauryl sulphate, polyethylene glycol 6000, deionized water place 100ml there-necked flask under room temperature mechanical agitation (600r/min) pre-emulsification 1h; continue dropping butanol, ethanol and pass into nitrogen; make it react to carry out under nitrogen protection; then sorbester p17 is dripped; it is warming up to 70 DEG C; it is slowly added dropwise styrene (polymerization inhibitor is distilled off) and butyl acrylate mixture; continue stirring; (when rotating speed is too fast, temperature is too high or drips monomer excessive velocities, monomer is susceptible to sudden and violent poly-.After question response is complete, stopping stirring and be cooled to room temperature, pour out product, washing is dry.
Each Materials Example that each scheme adopts is as follows:
Embodiment 1: benzoyl peroxide (or any one in cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)) 5%, sodium lauryl sulphate 0.5%, polyethylene glycol 6000 3%, butanol 0.5%, ethanol 1%, sorbester p17 0.5%, styrene and butyl acrylate 10%, all the other are deionized water, amount to 100%.
Embodiment 2: benzoyl peroxide (or any one in cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)) 10%, sodium lauryl sulphate 0.8%, polyethylene glycol 6000 1%, butanol 1.5%, ethanol 3%, sorbester p17 0.8%, styrene and butyl acrylate 15%, all the other are deionized water, amount to 100%.
Embodiment 3: benzoyl peroxide (or any one in cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)) 10%, sodium lauryl sulphate 0.8%, polyethylene glycol 6000 1%, butanol 0.5%, ethanol 1%, sorbester p17 0.5%, styrene and butyl acrylate 15%, all the other are deionized water, amount to 100%.
Embodiment 4: benzoyl peroxide (or any one in cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)) 5%, sodium lauryl sulphate 0.6%, polyethylene glycol 6000 2%, butanol 1%, ethanol 2%, sorbester p17 0.6%, styrene butyl acrylate 15%, all the other are deionized water, amount to 100%.
Embodiment 5: benzoyl peroxide (or any one in cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile)) 8%, sodium lauryl sulphate 0.6%, polyethylene glycol 6000 3%, butanol 0.5%, ethanol 2%, sorbester p17 0.6%, styrene and butyl acrylate 15%, all the other are deionized water, amount to 100%.
Two, result verification:
1, the product made when sudden and violent gathering occurs initiator microcapsule prepared by the present invention is as in figure 2 it is shown, be big particle diameter shape capsule.
2, can clearly see that microcapsule is spherical structure by Fig. 1, and there is atrament clearly the inside, illustrates that the nucleocapsid structure of microcapsule is obvious.
3, encapsulation ratio measures;
By taking ultraviolet absorption spectrophotometry, because organic compound has good ultraviolet absorption group or good double bond structure can produce ultraviolet absorption peak, when its content is more many, its uv absorption peak value is also more big, by the power of absworption peak, what we can be similar to calculates the encapsulation ratio of microcapsule.Weighing microcapsule prepared by a certain amount of present invention, do uv absorption and characterize, its minima is I1,Its maximum is I2.Encapsulation rate W is calculated through lower section formula.
W=(I2-I1)/I2×100%
Through checking;The encapsulation ratio of initiator microcapsule prepared by above-mentioned 5 schemes is respectively;63.3%、75.4%、80.5%、82.4%、92.15%.
4, the mensuration of release time:
The time that the microcapsule prepared by conductivity meter observation station is discharged in the middle of isopropanol, weigh the microcapsule 5 parts in equal in quality embodiment 5 as in the beaker of 100ml, discharge respectively at 40,50,60,70,80 DEG C, the electrical conductivity in solution is measured at set intervals with conductivity meter, after balance to be released, observe the release time of microcapsule finally by conductivity variations curve.
Through checking;The release time of initiator microcapsule prepared by above-mentioned 5 schemes is respectively;17h、10h、8h、7h、4h.
Conclusion;According to above technical scheme, add amount of medicament within above-mentioned scope, can successfully by initiator micro encapsulation, by embodiment 1,2,3,4,5 it can be seen that its optimum formula is initiator 8%, sodium lauryl sulphate 0.6%, polyethylene glycol 6000 3%, butanol 0.5%, ethanol 2%, sorbester p17 0.6%, styrene and butyl acrylate 15%, all the other are deionized water, amount to 100%.The encapsulation rate that this formula obtains is the highest, by changing temperature, can control microcapsule and complete release in 4h.
Claims (3)
1. a kind of preparation method of initiator microcapsule according to claim 1, it is characterised in that step is as follows;
1) sodium lauryl sulphate, polyethylene glycol 6000, initiator and deionized water being mixed, mechanical agitation carries out pre-emulsification;
2) dropping butanol and ethanol in the solution that pre-emulsification obtains, react under nitrogen protection;
3) dropping sorbester p17 in the mixed system that reaction obtains, after stirring is warming up to 70 DEG C, drips styrene and butyl acrylate, continues stirring to reacting completely;
4) wash after the system after complete reaction being cooled down room temperature, dry, obtain initiator microcapsule.
2. a kind of preparation method of initiator microcapsule according to claim 1, it is characterised in that: described initiator is any one in benzoyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
3. a kind of preparation method of initiator microcapsule according to claim 1 or claim 2, it is characterised in that: described initiator, sodium lauryl sulphate, polyethylene glycol 6000, butanol, ethanol and sorbester p17 account for respectively and always feed intake the 5~10% of quality, 0.5~0.8%, 1~3%, 0.5~1.5%, 1~3% and 0.5~0.8%;The total quality of styrene and butyl acrylate accounts for the 10~15% of the quality that always feeds intake, and all the other are deionized water, amounts to 100%.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106311099A (en) * | 2016-08-17 | 2017-01-11 | 常熟理工学院 | Preparation method of oil-soluble initiator microcapsule |
CN106883324A (en) * | 2017-01-22 | 2017-06-23 | 扬州工业职业技术学院 | Controllable sustained release phase transfer catalysis (PTC) microcapsules of one kind and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030064106A1 (en) * | 2000-03-04 | 2003-04-03 | Josep Garces | Microcapsules-vi |
US20130078308A1 (en) * | 2011-09-28 | 2013-03-28 | Seiko Epson Corporation | Encapsulation device, medical capsules, and encapsulation method |
CN103846069A (en) * | 2014-03-21 | 2014-06-11 | 扬州大学 | Preparation method of oxidizing agent microcapsule |
CN105330826A (en) * | 2015-12-04 | 2016-02-17 | 扬州大学 | Method for synthesizing polypyrrole microcapsules |
-
2016
- 2016-03-17 CN CN201610151393.5A patent/CN105754046B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030064106A1 (en) * | 2000-03-04 | 2003-04-03 | Josep Garces | Microcapsules-vi |
US20130078308A1 (en) * | 2011-09-28 | 2013-03-28 | Seiko Epson Corporation | Encapsulation device, medical capsules, and encapsulation method |
CN103846069A (en) * | 2014-03-21 | 2014-06-11 | 扬州大学 | Preparation method of oxidizing agent microcapsule |
CN105330826A (en) * | 2015-12-04 | 2016-02-17 | 扬州大学 | Method for synthesizing polypyrrole microcapsules |
Non-Patent Citations (1)
Title |
---|
林春霞: "过氧化苯甲酰微胶囊的制备与应用", 《化学与黏合》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106311099A (en) * | 2016-08-17 | 2017-01-11 | 常熟理工学院 | Preparation method of oil-soluble initiator microcapsule |
CN106311099B (en) * | 2016-08-17 | 2018-11-27 | 常熟理工学院 | A kind of preparation method of oil-soluble initiator microcapsules |
CN106883324A (en) * | 2017-01-22 | 2017-06-23 | 扬州工业职业技术学院 | Controllable sustained release phase transfer catalysis (PTC) microcapsules of one kind and preparation method thereof |
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