CN107497484A - A kind of hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst and preparation method thereof - Google Patents

A kind of hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst and preparation method thereof Download PDF

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Publication number
CN107497484A
CN107497484A CN201710565792.0A CN201710565792A CN107497484A CN 107497484 A CN107497484 A CN 107497484A CN 201710565792 A CN201710565792 A CN 201710565792A CN 107497484 A CN107497484 A CN 107497484A
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spheres
sustained
release micro
stirring
supported catalyst
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汪义卉
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Ma Anshan Kexin Network Technology Co Ltd
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Ma Anshan Kexin Network Technology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/51
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04Mixing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00Homopolymers 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
    • C08F120/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10Esters
    • C08F120/12Esters of monohydric alcohols or phenols
    • C08F120/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/32Polymerisation in water-in-oil emulsions

Abstract

The invention discloses hydrophobic type polyvinyl alcohol sustained-release micro-spheres of a kind of supported catalyst and preparation method thereof, it is characterised in that adds distilled water into polyvinyl alcohol, dissolves to obtain poly-vinyl alcohol solution;Poly-vinyl alcohol solution is added drop-wise in vegetable oil, adds Span80, emulsion reaction, crosslinking agent glutaraldehyde is added dropwise, after stirring, adds hydrochloric, after continuing stirring crosslinking reaction, precipitation is centrifuged, washing, acetone dehydration, dries at room temperature, obtain sustained-release micro-spheres;Paraffin heating water bath is melted, adds polysorbate60, sorbester p18, stirs, methylate methyl acrylate, potassium peroxydisulfate, emulsion reaction, filters to obtain complex emulsions waterproofing agent;Butyl titanate is well mixed with absolute ethyl alcohol, is slowly added under stirring in mixed solution, lasting stirring, obtains TiO2Colloidal sol, it is well mixed with complex emulsions waterproofing agent, sustained-release micro-spheres are immersed, be dried in vacuo, obtain the sustained-release micro-spheres of supported catalyst.

Description

A kind of hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst and preparation method thereof
Technical field
The present invention relates to sustained-release micro-spheres field, and in particular to a kind of hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst And preparation method thereof.
Background technology
Coal ash fiber is flyash gets rid of the ultra-fine inorganic mineral fibres that a fiber-forming process produces by melting, at present Research for coal ash fiber both at home and abroad and production are still at an early stage, most of research still rest on fiber copy paper with And fiberboard preparation etc..
Wang Cheng is far away from its master thesis《The preparation and water resistance research of coal ash fiberboard》In, using wet method system Plate technology utilization coal ash fiber prepares sheet material, and coal ash fiber is loosened except Slag treatment by water conservancy stirring means, ground The factors such as adhesive polyethylene alcohol, coal ash fiber slurry agitation jitter time, coal ash fiber concentration, additive have been studied carefully to powder The influence of coal ash fiberboard mechanical property, improved by modified coal ash fiber, modified adhesive and using waterproof coating The water resistance of coal ash fiberboard.But combination property, water resistance deficiency be present.
The content of the invention
The present invention solves the technical problem of provide a kind of hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst And preparation method thereof, the sustained-release micro-spheres prepared according to the technique possess good sustained release performance and hydrophobic performance.
The technical problems to be solved by the invention are realized using following technical scheme:
The preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of a kind of supported catalyst, it is characterised in that enter according to the following steps OK:
A. into 40-50 weight account polyethylene alcohol 1:15-20 adds distilled water, is warming up to 80-90 DEG C of heating water bath stirring 1- 2h, it is completely dissolved, obtains transparent polyethylene alcoholic solution;
B. under magnetic agitation, by gained poly-vinyl alcohol solution 1 in a:1-2 is added drop-wise in vegetable oil, adds 0.1-0.2 parts by weight Surfactant Span80,40-60 DEG C of emulsified 30-40min, homogeneous latex emulsion system is formed, 1-2 parts by weight of crosslinking agent penta is added dropwise Dialdehyde, after stirring 10-20min, 0.2-0.5 part by weight of catalyst hydrochloric acid is added, after continuing stirring crosslinking reaction 1-2h, centrifugation point From precipitation, wash 3-5 times, acetone is dehydrated 2-3 times, is dried at room temperature, is obtained sustained-release micro-spheres;
C. by 6-10 parts by weight paraffin, heating water bath, stirring fusing are slow to add 2-3 parts by weight polysorbate60,1-2 at 85-95 DEG C Parts by weight sorbester p18, stirs, and 1:3-5 adds distilled water, continues constant temperature stirring 1-2h, adds 5-8 weight parts of methacrylic acid first Ester, 0.1-0.2 parts by weight potassium peroxydisulfates, 3-4h is reacted in 70-80 DEG C of stirring and emulsifying, room temperature is cooled to, with 100-200 eye mesh screens Filtering and discharging, obtain complex emulsions waterproofing agent;
D. by 5-10 parts by weight butyl titanate and absolute ethyl alcohol 3-2:1 is well mixed, stirring lower 1:2-4 is slowly added to mix molten In liquid, 2-3h is persistently stirred, obtains TiO2Colloidal sol, it is well mixed with material in c, thus obtained microsphere in b is immersed 8- 10h, 85-95 DEG C of vacuum drying 4-6h, obtain the sustained-release micro-spheres of supported catalyst.
Wherein, concentration of hydrochloric acid described in step b is 0.5-1mol/L;Emulsion reaction mixing speed is described in step c 1000-1100rpm;Mixed solution described in step d is hydrochloric acid and deionized water 1:30-40 is mixed.
The present invention reaction mechanism and have the beneficial effect that:
Polyvinyl alcohol (PVA) microballoon is prepared using emulsion-crosslinking method, mixed aqueous phase with oil phase using emulsifying agent, forms Water-In-Oil (W/O) reaction system, PVA contain substantial amounts of hydroxyl, in acid condition can with crosslinking agent glutaraldehyde occur aldolisation, penta After dialdehyde addition system, it can be well mixed in a manner of scattering and permeating with PVA solution, under the catalysis of hydrochloric acid, the two is handed over Connection reaction, solidifies balling-up, using the PVA aqueous solution as aqueous phase, using vegetable oil as oil phase, using Span80 as surfactant, is prepared into To PVA sustained-release micro-spheres;Using sorbester p18 as emulsifying agent, using potassium peroxydisulfate as initiator, using methyl methacrylate as monomer, with stone Wax emulsion carries out emulsion polymerization, obtains complex emulsions waterproofing agent, available for the hydrophobicity and dimensional stability for improving PVA microballoons;It is logical Cross sol-gal process and be prepared for TiO2The hydrosol, it is well mixed with complex emulsions waterproofing agent, PVA sustained-release micro-spheres are immersed it In, obtain the sustained-release micro-spheres of supported catalyst.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below Specific embodiment is closed, the present invention is expanded on further.
Embodiment
The preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of a kind of supported catalyst, it is characterised in that by following step It is rapid to carry out:
A. into 40kg polyvinyl alcohol 1:15 add distilled water, are warming up to 80-90 DEG C of heating water bath stirring 2h, are completely dissolved, obtain Transparent polyethylene alcoholic solution;
B. under magnetic agitation, by gained poly-vinyl alcohol solution 1 in a:2 are added drop-wise in vegetable oil, add 0.2kg surfactants Span80,40-60 DEG C of emulsified 35min, homogeneous latex emulsion system is formed, 1kg crosslinking agent glutaraldehydes are added dropwise, after stirring 15min, added Enter 0.5kg hydrochlorics, after continuing stirring crosslinking reaction 2h, centrifuge precipitation, wash 3 times, acetone is dehydrated 3 times, room temperature Under dry, obtain sustained-release micro-spheres;
C. by 6kg paraffin, heating water bath, stirring fusing, slow plus 2kg polysorbate60s, 1kg sorbester p18s, stirring are equal at 85-95 DEG C It is even, 1:5 add distilled water, continue constant temperature stirring 2h, add 5kg methyl methacrylates, 0.1kg potassium peroxydisulfates, in 70-80 DEG C of stirring Emulsion reaction 3h, is cooled to room temperature, with 100 eye mesh screen filtering and dischargings, obtains complex emulsions waterproofing agent;
D. by 5kg butyl titanates and absolute ethyl alcohol 2:1 is well mixed, stirring lower 1:4 are slowly added in mixed solution, persistently stir 3h is mixed, obtains TiO2Colloidal sol, it is well mixed with material in c, thus obtained microsphere in b is immersed into 10h, 85-95 DEG C of vacuum is done Dry 6h, obtain the sustained-release micro-spheres of supported catalyst.
Wherein, concentration of hydrochloric acid described in step b is 1mol/L;Emulsion reaction mixing speed is described in step c 1100rpm;Mixed solution described in step d is hydrochloric acid and deionized water 1:35 mixing.

Claims (5)

  1. A kind of 1. preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst, it is characterised in that:
    Add distilled water into polyvinyl alcohol, dissolve to obtain poly-vinyl alcohol solution;Poly-vinyl alcohol solution is added drop-wise in vegetable oil, added Span80, emulsion reaction, crosslinking agent glutaraldehyde is added dropwise, after stirring, adds hydrochloric, after continuing stirring crosslinking reaction, centrifugation Precipitation and separation, washing, acetone dehydration, dry at room temperature, obtain sustained-release micro-spheres;Paraffin heating water bath is melted, adds polysorbate60, sapn 60, stir, methylate methyl acrylate, potassium peroxydisulfate, emulsion reaction, filter to obtain complex emulsions waterproofing agent;By metatitanic acid fourth Ester is well mixed with absolute ethyl alcohol, is slowly added under stirring in mixed solution, lasting stirring, obtains TiO2Colloidal sol, by its with it is compound Emulsion water-proof agent is well mixed, and sustained-release micro-spheres are immersed, vacuum drying, obtains the sustained-release micro-spheres of supported catalyst.
  2. A kind of 2. preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst, it is characterised in that:
    A. into 40-50 weight account polyethylene alcohol 1:15-20 adds distilled water, is warming up to 80-90 DEG C of heating water bath stirring 1- 2h, it is completely dissolved, obtains transparent polyethylene alcoholic solution;
    B. under magnetic agitation, by gained poly-vinyl alcohol solution 1 in a:1-2 is added drop-wise in vegetable oil, adds 0.1-0.2 parts by weight Surfactant Span80,40-60 DEG C of emulsified 30-40min, homogeneous latex emulsion system is formed, 1-2 parts by weight of crosslinking agent penta is added dropwise Dialdehyde, after stirring 10-20min, 0.2-0.5 part by weight of catalyst hydrochloric acid is added, after continuing stirring crosslinking reaction 1-2h, centrifugation point From precipitation, wash 3-5 times, acetone is dehydrated 2-3 times, is dried at room temperature, is obtained sustained-release micro-spheres;
    C. by 6-10 parts by weight paraffin, heating water bath, stirring fusing are slow to add 2-3 parts by weight polysorbate60,1-2 at 85-95 DEG C Parts by weight sorbester p18, stirs, and 1:3-5 adds distilled water, continues constant temperature stirring 1-2h, adds 5-8 weight parts of methacrylic acid first Ester, 0.1-0.2 parts by weight potassium peroxydisulfates, 3-4h is reacted in 70-80 DEG C of stirring and emulsifying, room temperature is cooled to, with 100-200 eye mesh screens Filtering and discharging, obtain complex emulsions waterproofing agent;
    D. by 5-10 parts by weight butyl titanate and absolute ethyl alcohol 3-2:1 is well mixed, stirring lower 1:2-4 is slowly added to mix molten In liquid, 2-3h is persistently stirred, obtains TiO2Colloidal sol, it is well mixed with material in c, thus obtained microsphere in b is immersed 8- 10h, 85-95 DEG C of vacuum drying 4-6h, obtain the sustained-release micro-spheres of supported catalyst.
  3. 3. a kind of preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst according to claim 2, its It is characterised by, concentration of hydrochloric acid described in step b is 0.5-1mol/L.
  4. 4. a kind of preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst according to claim 2, its It is characterised by, emulsion reaction mixing speed described in step c is 1000-1100rpm.
  5. 5. a kind of preparation method of the hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst according to claim 2, its It is characterised by, mixed solution described in step d is hydrochloric acid and deionized water 1:30-40 is mixed.
CN201710565792.0A 2017-07-12 2017-07-12 A kind of hydrophobic type polyvinyl alcohol sustained-release micro-spheres of supported catalyst and preparation method thereof Pending CN107497484A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108744020A (en) * 2018-06-12 2018-11-06 杭州艾力康医药科技有限公司 A kind of preparation method of ion-exchange type polyvinyl alcohol microparticles
CN111097522A (en) * 2019-12-31 2020-05-05 江南大学 Preparation method of controllable slow-release catalyst
CN111205614A (en) * 2019-07-29 2020-05-29 杭州金州高分子科技有限公司 Flame-retardant antibacterial PC alloy material for intelligent closestool and preparation method thereof
CN111229139A (en) * 2020-01-15 2020-06-05 四川大学华西医院 Iodine 131-loaded collagen-polyvinyl alcohol embolism microsphere and preparation method thereof

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CN106496609A (en) * 2016-11-28 2017-03-15 陕西品达石化有限公司 The preparation method of polyvinyl alcohol microparticles

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CN106496609A (en) * 2016-11-28 2017-03-15 陕西品达石化有限公司 The preparation method of polyvinyl alcohol microparticles

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108744020A (en) * 2018-06-12 2018-11-06 杭州艾力康医药科技有限公司 A kind of preparation method of ion-exchange type polyvinyl alcohol microparticles
CN111205614A (en) * 2019-07-29 2020-05-29 杭州金州高分子科技有限公司 Flame-retardant antibacterial PC alloy material for intelligent closestool and preparation method thereof
CN111205614B (en) * 2019-07-29 2021-12-28 杭州金州高分子科技有限公司 Flame-retardant antibacterial PC alloy material for intelligent closestool and preparation method thereof
CN111097522A (en) * 2019-12-31 2020-05-05 江南大学 Preparation method of controllable slow-release catalyst
CN111097522B (en) * 2019-12-31 2023-09-01 江南大学 Preparation method of controllable slow-release catalyst
CN111229139A (en) * 2020-01-15 2020-06-05 四川大学华西医院 Iodine 131-loaded collagen-polyvinyl alcohol embolism microsphere and preparation method thereof
CN111229139B (en) * 2020-01-15 2020-11-24 四川大学华西医院 Iodine 131-loaded collagen-polyvinyl alcohol embolism microsphere and preparation method thereof

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