CN105837840A - Preparation method of polymer/ZnO/SiO2 nano-composite microspheres - Google Patents
Preparation method of polymer/ZnO/SiO2 nano-composite microspheres Download PDFInfo
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Abstract
The invention belongs to the field of preparation of organic/inorganic nano-composite microspheres, and particularly relates to a preparation method of polymer/ZnO/SiO2 nano-composite microspheres. The preparation method includes the steps that firstly, vinyl monomers and organic siloxane are copolymerized through a miniemulsion polymerization method to prepare polymer microspheres carrying active silicon hydroxyl on the surfaces; then, an organic amine alkali source acts with active silicon hydroxyl on the surfaces of the polymer microspheres to generate nano-ZnO on the surfaces of the polymer microspheres in situ, and polymer/ZnO nano-composite microspheres are prepared; finally, the polymer/ZnO/SiO2 nano-composite microspheres are prepared in situ with a sol-gel method under the induced nucleation effect of nano-ZnO particles on the surfaces of the polymer microspheres. The obtained polymer/ZnO/SiO2 nano-composite microspheres are controllable in particle size and morphology, and solve the problems that nano-ZnO particles are prone to agglomeration and poor in dispersity; the nano-composite microspheres can be applied to the fields of paint, adhesives, ink, plastic, rubber, fibers and the like as multifunctional filler, and can bring excellent mechanical performance, ultraviolet resistance, antistatic performance, durability and the like to the materials.
Description
Technical field
The present invention relates to the preparation of organic-inorganic nano composite microsphere, particularly to polymer/ZnO/SiO2Nano combined
The preparation method of microballoon, belongs to composite nano-microsphere preparation field.
Background technology
Nano zine oxide (ZnO) is common inorganic, metal oxide, has chemical inertness, Heat stability is good, absorption purple
The advantages such as outside line ability is strong, fluorescence, introduce nano-ZnO in the polymeric material and can give the preferable mechanical property of material, resist
UV protection, heat resistance etc..But due to nano-ZnO the most easily reunite, poor compatibility and easily make to connect with its surface
Touch polymer light degraded and affect materials ' durability, thus limit nano-ZnO extensive application in the polymeric material.How
Reduce the photocatalytic activity of nano-ZnO, keep simultaneously the UV absorbing properties of its excellence be nano-ZnO in the polymeric material
Extensively apply the key issue that need to solve.Nano-ZnO is carried out surface modification or Surface coating is the effective way solving this problem
Footpath, generally can effectively reduce its photocatalytic activity in nano-ZnO Surface coating layer of silicon dioxide or pellumina, but its
Difficult dispersion and the problem such as organic polymer compatibility is bad in organic polymer, polymer overmold can effectively solve its dispersiveness
And consistency problem, but the problem such as cladding process is complicated, coating efficiency is undesirable.Chinese patent CN 101955613 A is by second
Alkenyl siloxane and vinyl monomer carry out miniemulsion copolymerization, carry out polyvinyl surface-functionalized making polymer microballoon
Surface, with activated silica hydroxyl, is interacted by the alkali source (aminated compounds) of silicone hydroxyl with nano-ZnO presoma, in polymerization
Thing microsphere surface in-situ preparation nano-ZnO, prepares polymer/ZnO nano complex microsphere.For suppressing polymer/ZnO to receive further
The photocatalytic activity of rice complex microsphere, expands its application in organic polymer, and improves organic polymer further
Performance, the present invention is on the basis of polymer/ZnO nano complex microsphere research work, by sol-gel process at 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 suppress the photocatalytic activity of ZnO, again can organic enhancing polymer.Additionally, should " grass
Certain kind of berries type " polymer/ZnO/SiO2Composite nano-microsphere has amphiphilic, is i.e. dispersed in water, ethanol polar solvent, it is possible to
It is dispersed in the non-polar solvens such as toluene, therefore should be combined micro-by " strawberry type " amphiphilic polymers/zinc oxide/silica nanometer
Ball can be applicable to various organic polymer systems.
Summary of the invention
The present invention is directed to nano-ZnO easily reunite in organic polymer material, poor compatibility and easily make 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 functionalisation of surfaces, then by sol-gel process at polymer microballoon table
Face in-situ preparation nano-ZnO and Nano-meter SiO_22, prepare polymer/ZnO/SiO2Composite nano-microsphere, concrete preparation method is as follows:
(1) prepare surface silanol group functionalized polymeric microballoon with fine emulsion polymerization, consist of: vinyl monomer, have
Organic siloxane, emulsifying agent, co-stabilizer, initiator, pH adjusting agent and deionized water, quality consumption is as follows:
Vinyl monomer 0-90,
Organosiloxane 10-100
Other component (percentage amount accounting for vinyl monomer and organosiloxane quality sum is:
Preparation process is as follows:
By proportioning, emulsifying agent, pH adjusting agent are dissolved in deionized water and mix (component A)；By proportioning by vinyl
Monomer, organosiloxane, co-stabilizer and initiator mix (B component)；At ambient temperature B component is slowly dropped to
In component A, dropping limit, limit stirring and emulsifying；Continue stirring 0.5h after dripping slightly to emulsify；Use ultrasonic wave fine crankshaft again
10min, keeps emulsion temperature to be room temperature with water-bath in the process；Under the conditions of 70 DEG C, it is polymerized 4h after fine crankshaft, prepares silicon hydroxyl
The polymer microballoon of primary surface functionalization；
Described vinyl monomer is styrene, methyl methacrylate, vinyl acetate, acrylonitrile, acrylamide；
Described organosiloxane is 3-methacryloxypropyl trimethoxy silane, methacryloxypropyl
Triethoxysilane, methacryloxymethyl dimethoxysilane, VTES, vinyl trimethoxy
Silane, vinyl three ('beta '-methoxy ethyoxyl) silane；
Described emulsifying agent is dodecyl sodium sulfate, lauryl sodium sulfate, DTAB；Described
Co-stabilizer be hexadecanol, lauryl mercaptan, Stearyl mercaptan, hexadecane；
Described initiator is: potassium peroxydisulfate (KPS), ammonium persulfate (APS), azodiisobutyronitrile (AIBN), azo two
Different heptonitrile (ABVN), dibenzoyl peroxide (BPO)；
Described pH adjusting agent be NaOH, sodium acid carbonate, sodium carbonate, sodium phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate it
A kind of or two kinds；
(2) preparation of polymer/ZnO nano complex microsphere, adds organic amine in a certain amount of above-mentioned polymer emulsion,
Add the alcoholic solution of zinc compound, prepare polymer/ZnO nano complex microsphere by sol-gel process；
Quality consumption is as follows:
Preparation process is as follows:
Take out the above-mentioned polymer emulsion of part, dilute ultrasonic disperse by deionized water and temperature is raised to 45 DEG C-60 DEG C, slow
Slowly drip organic amine compound, after dripping off, react 0.5h (C component)；By zinc compound ultrasonic dissolution (D component) in ethanol, will
D component is slowly added dropwise in C component, reacts 0.5h and prepare polymer/ZnO nano complex emulsions after dripping off, emulsion is centrifuged,
Washing purifying obtains polymer/ZnO nano complex microsphere powder；
Described organic amine compound is triethanolamine, diethanol amine, MEA, triisopropanolamine；
Described zinc compound is Zinc diacetate dihydrate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride；
(3) polymer/ZnO/SiO2The preparation of composite nano-microsphere, is combined above-mentioned a certain amount of polymer/ZnO nano
Microsphere powder is dispersed in alcohol solvent, adds ammoniacal liquor, then dropping ethyl orthosilicate ethanol solution, prepares polymer/ZnO/
SiO2Composite nano-microsphere；
Quality consumption is as follows:
Preparation process is as follows:
Polymer after above-mentioned centrifugal purification/ZnO nano composite powder is scattered in absolute ethyl alcohol, the most slowly
Dropping ammonia spirit, reacts 0.5h after dripping off；Then it is slowly added dropwise ethyl orthosilicate ethanol solution, continues reaction 4h.Will dispersion
Liquid is centrifuged washing, isolated and purified i.e. prepares polymer/ZnO/SiO2Composite nano-microsphere.
Beneficial effects of the present invention:
(1) polymer/ZnO/SiO prepared by the present invention2Composite nano-microsphere form is " strawberry type ", and its particle diameter with
And the ZnO Nanoparticles on polymer microballoon surface and SiO2Particle shape is controlled；
(2) should " strawberry type " polymer/ZnO/SiO2Composite nano-microsphere has amphiphilic, is i.e. dispersed in water, ethanol
In polar solvent, it is possible to be dispersed in the non-polar solvens such as toluene,
Therefore should " strawberry type " polymer/ZnO/SiO2Composite nano-microsphere can be applicable to various organic polymer systems.
(3) should " strawberry type " polymer/ZnO/SiO2The Nano-meter SiO_2 on composite nano-microsphere surface2Can effectively suppress nanometer
The photocatalytic activity of ZnO
Accompanying drawing explanation
The TEM figure of the polymer microballoon of Fig. 1 silicone hydroxyl functionalization
The TEM figure of Fig. 2 polymer/ZnO nano complex microsphere
Fig. 3 polymer/ZnO/SiO2The TEM figure of composite nano-microsphere
Detailed description of the invention:
Below in conjunction with example, the present invention will be described:
Embodiment 1
Weigh 0.1g SDS, 0.1g sodium acid carbonate, 0.1g sodium dihydrogen phosphate, dilute by 90g deionized water, move into stirring
Mix in the 250ml four-hole bottle of device, thermometer and reflux condensate device (component A)；Weigh 7.5g styrene monomer, 2.5g 3-
Methacrylic acid propyl trimethoxy silicane (MEMO), 0.5g HD, 0.1g AIBN (B component), move into dropping liquid after stirring
In funnel.Under room temperature condition, B component is slowly dropped in component A, continues stirring 0.5h after adding and emulsify.Take out above-mentioned
Mixed composition, ultrasonic wave fine crankshaft 10min.Continue to transfer 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 microballoon of surface silanol group, its microballoon pattern such as Fig. 1
Shown in.
Take out 5g above-mentioned PS emulsion, dilute by 40g deionized water, transfer to agitating device, thermometer and returned cold
In the 250ml four-hole bottle of solidifying device, temperature is slowly raised to 55 DEG C；Being slowly added dropwise 8g triethanolamine in four-hole bottle, limit drips
Limit is stirred, and continues stirring 0.5h (C component) after adding；Weigh 0.2g bis-water and zinc acetate, use 30g anhydrous alcohol solution, completely
Transfer to after dissolving (D component) in dropping funel；D component is slowly dropped in C component, after adding, continues reaction 0.5h, will
Emulsion is centrifuged isolated and purified (rotating speed is 8000-10000 rev/min, and the time is 0.5h), prepares PS/ZnO nano combined micro-
Ball, PS microsphere surface shown in Fig. 2 transmission electron microscope (TEM) figure has been coated with one layer of ZnO Nanoparticles uniformly.
Take out the PS/ZnO nano particle after 0.5g is centrifuged, 45g absolute ethyl alcohol, transfer to agitating device, thermometer
With in the 250ml four-necked bottle of reflux condensate device；Weigh 2.5g deionized water, 0.2gNH3·H2O, is slowly added dropwise after rocking uniformly
Limit dropping limit stirring in four-necked bottle, continues stirring 0.5h after adding；Weigh 7.5g absolute ethyl alcohol, 0.1gTEOS (0.008mol/
L), be slowly dropped in bottle, after adding continue reaction 4h. emulsion is centrifuged isolated and purified (rotating speed be 8000-10000 turn/
Minute, the time is 0.5h), obtain PS/ZnO/SiO2Composite nano-microsphere, PS/ZnO microballoon table shown in Fig. 3 transmission electron microscope (TEM)
Face is uniformly coated with Nano-meter SiO_22Particle, forms " strawberry " type complex microsphere.
Claims (1)
1. 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 functionalisation of surfaces by mini-emulsion polymerization, then passes through sol-gel process
Nano-ZnO and Nano-meter SiO_2 is generated at polymer microballoon surface in situ2, prepare polymer/ZnO/SiO2Composite nano-microsphere, specifically
Preparation method is as follows:
(1) prepare surface silanol group functionalized polymeric microballoon with fine emulsion polymerization, consist of: vinyl monomer, organosilicon
Oxygen alkane, emulsifying agent, co-stabilizer, initiator, pH adjusting agent and deionized water, quality consumption is as follows:
Vinyl monomer 0-90,
Organosiloxane 10-100
Other component (percentage amount accounting for vinyl monomer and organosiloxane quality sum is:
Preparation process is as follows:
By proportioning, emulsifying agent, pH adjusting agent are dissolved in deionized water and mix (component A)；By proportioning by vinyl list
Body, organosiloxane, co-stabilizer and initiator mix (B component)；At ambient temperature B component is slowly dropped to A
In component, dropping limit, limit stirring and emulsifying；Continue stirring 0.5h after dripping slightly to emulsify；Again with ultrasonic wave fine crankshaft 10min,
Emulsion temperature is kept to be room temperature with water-bath in the process；Under the conditions of 70 DEG C, it is polymerized 4h after fine crankshaft, prepares silicone hydroxyl surface
The polymer microballoon of functionalization；
Described vinyl monomer is styrene, methyl methacrylate, vinyl acetate, acrylonitrile, acrylamide；
Described organosiloxane is 3-methacryloxypropyl trimethoxy silane, methacryloxypropyl three second
TMOS, methacryloxymethyl dimethoxysilane, VTES, vinyl trimethoxy silicon
Alkane, vinyl three ('beta '-methoxy ethyoxyl) silane；
Described emulsifying agent is dodecyl sodium sulfate, lauryl sodium sulfate, DTAB；
Described co-stabilizer is hexadecanol, lauryl mercaptan, Stearyl mercaptan, hexadecane；
Described initiator is: potassium peroxydisulfate (KPS), ammonium persulfate (APS), azodiisobutyronitrile (AIBN), azo two different heptan
Nitrile (ABVN), dibenzoyl peroxide (BPO)；
Described pH adjusting agent is the one of NaOH, sodium acid carbonate, sodium carbonate, sodium phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate
Or two kinds；
(2) preparation of polymer/ZnO nano complex microsphere, adds organic amine in a certain amount of above-mentioned polymer emulsion, then adds
Enter the alcoholic solution of zinc compound, prepare polymer/ZnO nano complex microsphere by sol-gel process；
Quality consumption is as follows:
Preparation process is as follows:
Take out the above-mentioned polymer emulsion of part, dilute ultrasonic disperse by deionized water and temperature is raised to 45 DEG C-60 DEG C, slowly dripping
Add organic amine compound, after dripping off, react 0.5h (C component)；By zinc compound ultrasonic dissolution (D component) in ethanol, by D group
Part it is slowly added dropwise in C component, reacts 0.5h after dripping off and prepare polymer/ZnO nano complex emulsions, emulsion is centrifuged, water
Wash purifying and obtain polymer/ZnO nano complex microsphere powder；
Described organic amine compound is triethanolamine, diethanol amine, MEA, triisopropanolamine；
Described zinc compound is Zinc diacetate dihydrate, zinc acetate, zinc nitrate, zinc sulfate, 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 ammoniacal liquor, then dropping ethyl orthosilicate ethanol solution, prepares polymer/ZnO/SiO2
Composite nano-microsphere；
Quality consumption 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 at room temperature slowly added dropwise
Ammonia spirit, reacts 0.5h after dripping off；Then it is slowly added dropwise ethyl orthosilicate ethanol solution, continues reaction 4h, by above-mentioned dispersion
Liquid is centrifuged washing, isolated and purified i.e. prepares polymer/ZnO/SiO2Composite nano-microsphere.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823017A (en) * | 2016-12-12 | 2017-06-13 | 湖北大学 | A kind of preparation method of the hydridization biological function coating based on halogen ammoniate and zinc oxide nano-particle |
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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2016
- 2016-05-11 CN CN201610308631.9A patent/CN105837840B/en not_active Expired - Fee Related
Patent 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823017A (en) * | 2016-12-12 | 2017-06-13 | 湖北大学 | A kind of preparation method of the hydridization biological function coating based on halogen ammoniate and zinc oxide nano-particle |
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