CN105837840B - A kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere - Google Patents
A kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere Download PDFInfo
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- 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
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Abstract
The invention belongs to the preparation fields of organic/inorganic nano complex microsphere, more particularly to polymer/ZnO/SiO2The preparation method of composite nano-microsphere.Vinyl monomer and organosiloxane are carried out copolymerization using the method for mini-emulsion polymerization first and prepare polymer microballoon of the surface with active silicone hydroxyl by the present invention；Polymer microballoon surface in situ is acted on by the active silicone hydroxyl of organic amine alkali source and polymer surfaces again and generates nano-ZnO, prepare polymer/ZnO nano complex microsphere, finally by the induction nucleation of the ZnO Nanoparticles on polymer microballoon surface, polymerization object/ZnO/SiO is prepared in situ by sol-gal process2Composite nano-microsphere.Polymer/ZnO/SiO produced by the present invention2The particle size and morphology controllable of composite nano-microsphere, the problems such as overcoming ZnO Nanoparticles easily reunion and poor dispersion, the composite nano-microsphere can be used as multi-functional applying filler that can assign the excellent mechanical property of above-mentioned material, ultraviolet-resistent property, antistatic property and durability etc. in fields such as coating, adhesive, ink, plastics, rubber, fibers.
Description
Technical field
The present invention relates to the preparations of organic-inorganic nano composite microsphere, more particularly to polymer/ZnO/SiO2It is nano combined
The preparation method of microballoon belongs to composite nano-microsphere preparation field.
Background technology
Nano zine oxide (ZnO) is common inorganic, metal oxide, and with chemical inertness, thermal stability is good, absorption is purple
The advantages that outside line ability is strong, fluorescence, the preferable mechanical property of material can be assigned, resist by introducing nano-ZnO in the polymeric material
UV protection, heat resistance etc..But since nano-ZnO easily reunites in the polymeric material, poor compatibility and easily makes to connect with its surface
It touches polymer light degradation and influences materials ' durability, thus limit the extensive use of nano-ZnO in the polymeric material.How
Reduce nano-ZnO photocatalytic activity, while the UV absorbing properties for keeping its excellent be nano-ZnO in the polymeric material
Extensively using the critical issue that need to be solved.It is to solve the problems, such as this effective way that surface modification or surface cladding are carried out to nano-ZnO
Diameter, layer of silicon dioxide or pellumina are usually coated on nano-ZnO surface can effectively reduce its photocatalytic activity, but its
Difficult dispersion in organic polymer, with organic polymer compatibility it is bad the problems such as, polymer overmold can effectively solve its dispersibility
And consistency problem, but the problems such as cladding process is complicated, coating efficiency is undesirable.101955613 A of Chinese patent CN are by second
Alkenyl siloxane carries out miniemulsion copolymerization with vinyl monomer, surface-functionalized to polyvinyl progress to make polymer microballoon
Surface carries active silicone hydroxyl, is interacted, polymerize by the alkali source (aminated compounds) of silicone hydroxyl and nano-ZnO presoma
Polymer/ZnO nano complex microsphere is made in object microsphere surface in-situ preparation nano-ZnO.It is received to further suppress polymer/ZnO
The photocatalytic activity of rice complex microsphere, expands its application in organic polymer, and further improve organic polymer
Performance, the present invention is on the basis of polymer/ZnO nano complex microsphere research work, by sol-gel method in polymer/ZnO
Composite nano-microsphere surface in situ generates nano-silicon dioxide particle, forms " strawberry type " polymer/ZnO/SiO2Meter Fu He is micro-
Ball, nano-silicon dioxide particle can effectively inhibit the photocatalytic activity of ZnO, and can organic enhancing polymer.It in addition, should " grass
Certain kind of berries type " polymer/ZnO/SiO2Composite nano-microsphere has amphiphilic, you can is dispersed in water, ethyl alcohol isopolarity solvent, also may be used
It is dispersed in the nonpolar solvents such as toluene, therefore it is compound micro- to be somebody's turn to do " strawberry type " amphiphilic polymers/zinc oxide/silica nanometer
Ball can be applied to various organic polymer systems.
Invention content
The present invention easily reunites in organic polymer material for nano-ZnO, poor compatibility and easily makes to contact with its surface
Polymer light degradation problem proposes a kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere.The technical side of the present invention
Case：A kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere, first passes through vinyl monomer and organosiloxane
Mini-emulsion polymerization prepares the polymer microballoon of silicone hydroxyl surface functionalization, then by sol-gel method in polymer microballoon table
Face in-situ preparation nano-ZnO and Nano-meter SiO_22, polymer/ZnO/SiO is made2Composite nano-microsphere, specific preparation method are as follows：
(1) surface silanol group functionalized polymeric microballoon is prepared with fine emulsion polymerization, forms and be：Vinyl monomer has
Organic siloxane, emulsifier, co-stabilizer, initiator, pH adjusting agent and deionized water, quality dosage are as follows：
Vinyl monomer 0-90,
Organosiloxane 10-100
(percentage amount for accounting for vinyl monomer and organosiloxane quality sum is for other components：
Preparation process is as follows：
Emulsifier, pH adjusting agent are dissolved in deionized water by proportioning and are uniformly mixed (component A)；By proportioning by vinyl
Monomer, organosiloxane, co-stabilizer and initiator are uniformly mixed (B component)；B component is slowly dropped at ambient temperature
In component A, the stirring and emulsifying when being added dropwise；Continue stirring 0.5h after dripping slightly to be emulsified；Ultrasonic wave fine crankshaft is used again
10min, it is room temperature to keep emulsion temperature with water-bath in the process；It polymerize 4h under the conditions of 70 DEG C after fine crankshaft, silicon hydroxyl is made
The functionalized polymer microballoon of primary surface；
The vinyl monomer is styrene, methyl methacrylate, vinyl acetate, acrylonitrile, acrylamide；
The organosiloxane is 3- methacryloxypropyl trimethoxy silanes, methacryloxypropyl
Triethoxysilane, methacryloxymethyl dimethoxysilane, vinyltriethoxysilane, vinyl trimethoxy
Silane, vinyl three ('beta '-methoxy ethyoxyl) silane；
The emulsifier is dodecyl sodium sulfate, lauryl sodium sulfate, dodecyl trimethyl ammonium bromide；It is described
Co-stabilizer for hexadecanol, lauryl mercaptan, Stearyl mercaptan, hexadecane；
The initiator is：Potassium peroxydisulfate (KPS), ammonium persulfate (APS), azodiisobutyronitrile (AIBN), azo two
Different heptonitrile (ABVN), dibenzoyl peroxide (BPO)；
The pH adjusting agent for sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate it
It is a kind of or two kinds；
(2) preparation of polymer/ZnO nano complex microsphere adds in organic amine into a certain amount of above-mentioned polymer emulsion,
The alcoholic solution of zinc compound is added, polymer/ZnO nano complex microsphere is prepared by sol-gel method；
Quality dosage is as follows：
Preparation process is as follows：
The above-mentioned polymer emulsion in part is taken out, dilute ultrasonic disperse with deionized water and temperature is raised to 45 DEG C -60 DEG C, is delayed
It is slow that organic amine compound is added dropwise, 0.5h (C components) is reacted after dripping off；By zinc compound ultrasonic dissolution in ethanol (D components), will
D components are slowly added dropwise in C components, 0.5h are reacted after dripping off, polymer/ZnO nano complex emulsions are made, lotion is centrifuged,
Washing purifying obtains polymer/ZnO nano complex microsphere powder；
The organic amine compound is triethanolamine, diethanol amine, monoethanolamine, triisopropanolamine；
The zinc compound is Zinc diacetate dihydrate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride；
(3) polymer/ZnO/SiO2The preparation of composite nano-microsphere, above-mentioned a certain amount of polymer/ZnO nano is compound
Microsphere powder is dispersed in alcohol solvent, adds in ammonium hydroxide, and ethyl orthosilicate ethanol solution is then added dropwise, and polymer/ZnO/ is made
SiO2Composite nano-microsphere；
Quality dosage is as follows：
Preparation process is as follows：
Polymer after above-mentioned centrifugal purification/ZnO nano composite powder is scattered in absolute ethyl alcohol, at room temperature slowly
Ammonia spirit is added dropwise, reacts 0.5h after dripping off；Then ethyl orthosilicate ethanol solution is slowly added dropwise, the reaction was continued 4h.It will dispersion
Liquid carries out centrifugation washing, isolates and purifies and obtains polymer/ZnO/SiO2Composite nano-microsphere.
Beneficial effects of the present invention：
(1) polymer/ZnO/SiO prepared by the present invention2Composite nano-microsphere form be " strawberry type ", and its grain size with
And the ZnO Nanoparticles and SiO on polymer microballoon surface2Particle shape is controllable；
It (2) should " strawberry type " polymer/ZnO/SiO2Composite nano-microsphere has amphiphilic, you can is dispersed in water, ethyl alcohol
In isopolarity solvent, also it is dispersed in the nonpolar solvents such as toluene,
It therefore should " strawberry type " polymer/ZnO/SiO2Composite nano-microsphere can be applied to various organic polymer systems.
It (3) should " strawberry type " polymer/ZnO/SiO2The Nano-meter SiO_2 on composite nano-microsphere surface2Nanometer can effectively be inhibited
The photocatalytic activity of ZnO
Description of the drawings
The TEM figures of the functionalized polymer microballoon of Fig. 1 silicone hydroxyls
The TEM figures of Fig. 2 polymer/ZnO nano complex microsphere
Fig. 3 polymer/ZnO/SiO2The TEM figures of composite nano-microsphere
Specific embodiment：
Below in conjunction with example, the present invention will be described：
Embodiment 1
0.1g SDS, 0.1g sodium bicarbonates are weighed, 0.1g sodium dihydrogen phosphates are diluted with 90g deionized waters, are moved into carry and be stirred
Device is mixed, in the 250ml four-hole bottles of thermometer and reflux condensate device (component A)；Weigh 7.5g styrene monomers, 2.5g 3-
Methacrylic acid propyl trimethoxy silicane (MEMO), 0.5g HD, 0. 1g AIBN (B component) move into dropping liquid after stirring evenly
In funnel.B component is slowly dropped in component A under room temperature, continues stirring 0.5h after adding and is emulsified.It takes out above-mentioned
Mixed composition, ultrasonic wave fine crankshaft 10min.Continue to be transferred to the 250ml equipped with agitating device, thermometer and reflux condensate device
In four-hole bottle, temperature is slowly risen to 70 DEG C, polyase 13 h, prepares the PS microballoons of surface silanol group, microballoon pattern such as Fig. 1
It is shown.
The above-mentioned PS lotions of 5g are taken out, is diluted, is transferred to agitating device, thermometer and returned cold with 40g deionized waters
In the 250ml four-hole bottles of solidifying device, temperature is slowly raised to 55 DEG C；8 g triethanolamines are slowly added dropwise into four-hole bottle, side is added dropwise
Side is stirred, and continues to stir 0.5h (C components) after adding；Bis- water of 0.2g and zinc acetate are weighed, is dissolved with 30g absolute ethyl alcohols, completely
It is transferred in dropping funel after dissolving (D components)；D components are slowly dropped in C components, the reaction was continued 0.5h after adding will
Purifying (rotating speed is 8000-10000 revs/min, time 0.5h) is centrifuged in lotion, and it is nano combined micro- that PS/ZnO is made
Ball, PS microsphere surfaces shown in Fig. 2 transmission electron microscopes (TEM) figure have uniformly coated one layer of ZnO Nanoparticles.
The PS/ZnO nano-particles after 0.5g centrifugations are taken out, 45g absolute ethyl alcohols are transferred to agitating device, thermometer
In the 250ml four-necked bottles of reflux condensate device；Weigh 2.5g deionized waters, 0.2gNH3·H2O is slowly added dropwise after rocking uniformly
It is stirred into four-necked bottle when being added dropwise, continues to stir 0.5h after adding；Weigh 7.5g absolute ethyl alcohols, 0.1gTEOS (0.008mol/
L), be slowly dropped in bottle, after adding the reaction was continued 4h. by lotion be centrifuged purifying (rotating speed for 8000-10000 turns/
Minute, time 0.5h), obtain PS/ZnO/ SiO2Composite nano-microsphere, PS/ZnO microballoons shown in Fig. 3 transmission electron microscopes (TEM)
Coated with uniform Nano-meter SiO_22Particle forms " strawberry " type complex microsphere.
Claims (1)
1. a kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere, it is characterised in that：First by vinyl monomer and
Organosiloxane prepares the polymer microballoon of silicone hydroxyl surface functionalization by mini-emulsion polymerization, then passes through sol-gel method
Nano-ZnO and Nano-meter SiO_2 are generated in polymer microballoon surface in situ2, polymer/ZnO/SiO is made2Composite nano-microsphere, specifically
Preparation method is as follows：
(1) surface silanol group functionalized polymeric microballoon is prepared with fine emulsion polymerization, forms and be：Vinyl monomer, organosilicon
Oxygen alkane, emulsifier, co-stabilizer, initiator, pH adjusting agent and deionized water, quality dosage are as follows：
Vinyl monomer 0-90
Organosiloxane 10-100
The sum of above two material mass is 100, and wherein vinyl monomer quality is not 0；
Other amounts of components are：
Preparation process is as follows：
Emulsifier, pH adjusting agent are dissolved in deionized water by proportioning and are uniformly mixed as component A；By proportioning by vinyl list
Body, organosiloxane, co-stabilizer and initiator are uniformly mixed as B component；B component is slowly dropped to A at ambient temperature
In component, the stirring and emulsifying when being added dropwise；Continue stirring 0.5h after dripping slightly to be emulsified；Ultrasonic wave fine crankshaft 10min is used again,
It is room temperature to keep emulsion temperature with water-bath in the process；It polymerize 4h under the conditions of 70 DEG C after fine crankshaft, silicone hydroxyl surface is made
Functionalized polymer microballoon；
The vinyl monomer is styrene, methyl methacrylate, vinyl acetate, acrylonitrile or acrylamide；
The organosiloxane is 3- methacryloxypropyl trimethoxy silanes, three second of methacryloxypropyl
Oxysilane, methacryloxymethyl dimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane
Or vinyl three ('beta '-methoxy ethyoxyl) silane；
The emulsifier is dodecyl sodium sulfate, lauryl sodium sulfate or dodecyl trimethyl ammonium bromide；
The co-stabilizer is hexadecanol, lauryl mercaptan, Stearyl mercaptan or hexadecane；
The initiator is：Potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile, azobisisoheptonitrile or diphenyl peroxide first
Acyl；
The pH adjusting agent is：One of sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium phosphate, sodium dihydrogen phosphate or potassium hydrogen phosphate
Kind or two kinds；
(2) preparation of polymer/ZnO nano complex microsphere adds in organic amine into a certain amount of above-mentioned polymer emulsion, then adds
Enter the alcoholic solution of zinc compound, polymer/ZnO nano complex microsphere is prepared by sol-gel method；
Quality dosage is as follows：
Preparation process is as follows：
The above-mentioned polymer emulsion in part is taken out, dilute ultrasonic disperse with deionized water and temperature is raised to 45 DEG C -60 DEG C, is slowly dripped
Add organic amine compound, it is C components that 0.5h is reacted after dripping off；It is in ethanol D components by zinc compound ultrasonic dissolution, by D groups
Part is slowly added dropwise in C components, 0.5h is reacted after dripping off, polymer/ZnO nano complex emulsions are made, lotion is centrifuged, water
It washes purifying and obtains polymer/ZnO nano complex microsphere powder；
The organic amine compound is triethanolamine, diethanol amine, monoethanolamine or triisopropanolamine；
The zinc compound is Zinc diacetate dihydrate, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride；
(3) polymer/ZnO/SiO2The preparation of composite nano-microsphere, by above-mentioned a certain amount of polymer/ZnO nano complex microsphere
Powder is dispersed in alcohol solvent, adds in ammonium hydroxide, and ethyl orthosilicate ethanol solution is then added dropwise, and polymer/ZnO/SiO is made2
Composite nano-microsphere；
Quality dosage is as follows：
Preparation process is as follows：
Polymer after above-mentioned centrifugal purification/ZnO nano composite powder is scattered in absolute ethyl alcohol, is slowly added dropwise at room temperature
Ammonia spirit reacts 0.5h after dripping off；Then ethyl orthosilicate ethanol solution is slowly added dropwise, the reaction was continued 4h, by above-mentioned dispersion
Liquid carries out centrifugation washing, isolates and purifies and obtains polymer/ZnO/SiO2Composite nano-microsphere.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955613A (en) * | 2010-10-20 | 2011-01-26 | 江南大学 | Method for preparing polymer-zinc oxide nano composite microspheres |
| CN102993782A (en) * | 2012-12-12 | 2013-03-27 | 江南大学 | Preparation method of polyurethane acrylate oligomer surface modified silica |
| CN103588951A (en) * | 2013-11-12 | 2014-02-19 | 江南大学 | Preparation of high-strength hydrophobic photo-curing waterborne polyurethane nano-composite emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955613A (en) * | 2010-10-20 | 2011-01-26 | 江南大学 | Method for preparing polymer-zinc oxide nano composite microspheres |
| CN102993782A (en) * | 2012-12-12 | 2013-03-27 | 江南大学 | Preparation method of polyurethane acrylate oligomer surface modified silica |
| CN103588951A (en) * | 2013-11-12 | 2014-02-19 | 江南大学 | Preparation of high-strength hydrophobic photo-curing waterborne polyurethane nano-composite emulsion |
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