CN102181175A - Preparation method of surface modified nano particles and application of product thereof - Google Patents
Preparation method of surface modified nano particles and application of product thereof Download PDFInfo
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- CN102181175A CN102181175A CN201110069495XA CN201110069495A CN102181175A CN 102181175 A CN102181175 A CN 102181175A CN 201110069495X A CN201110069495X A CN 201110069495XA CN 201110069495 A CN201110069495 A CN 201110069495A CN 102181175 A CN102181175 A CN 102181175A
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Abstract
The invention discloses a preparation method of surface modified nano particles and application of a product thereof. The method comprises the following steps of: reacting the surfaces of nano particles, atom transfer radical polymerization (ATRP) surface initiator and 2-bromoisobutyryl with silicon chlorine bond to anchor the ATRP surface initiator on the surfaces of the nano particles, and then performing ATRP with methacrylate monomer, catalyst, coordination agent and the like to prepare acrylate polymer modified inorganic nano particles. Therefore, the ATRP method for modifying the nano particles has controllability on the nano particle surface grafted acrylate polymer, the advantages of the nano particles are fully exerted, and the effects of enhancing and toughening the nano particles and the like are achieved under the condition of low adding amount; meanwhile, the chain length distribution of the acrylate polymer is uniform, so the dispersibility and the stability of the modified nano particles in an acrylate coating are improved; and the abrasion resistance of the coating is improved, and high transparency of the coating is kept at the same time.
Description
Technical field
The present invention relates to a kind of novel method of nano particle surface modifying and the application of product thereof, specifically, relate to a kind of atom transfer radical polymerization that adopts nanoparticle surface is carried out controllable modified method, belong to the nanometer surface modification technical field, simultaneously, the surface-modified nanoparticles of aforementioned acquisition is applied in the acrylate paint, belongs to the coating preparation field.
Background technology
Nanoparticle is meant that diameter at several particles (nanoparticle claims ultrafine particulate again) between hundreds of nanometers, belongs to the category of colloidal particle size.Nanoparticle itself has quantum size effect, small-size effect, surface effects and macro quanta tunnel effect, therefore show many distinctive character, have broad application prospects at aspects such as catalysis, optical filtering, photoabsorption, medicine, magneticmedium and novel materials.Because inorganic nano-particle has favorable rigidity, dimensional stability and excellent thermostability and wear resistance, be development polymkeric substance novel material new approach is provided.Yet the specific surface energy that nanoparticle is huge has influenced its dispersion in polymeric matrix, has caused the boundary defect between matrix and the filler, causes performance of composites to descend.Be necessary nanoparticle surface is modified for this reason, improve the cementability of itself and polymer interface.
The method of modifying of nanoparticle surface has multiple, normally uses various coupling agents, comprises silane coupling agent and titante coupling agent etc., and nanoparticle is carried out surface treatment.Though utilize this method can improve the effective dispersion of nanoparticle in polymeric matrix, can not realize the single dispersion of nanoparticle.Patent CN101177470 has described a kind of method with reverse atom transfer radical polymerization reaction synthetic nano-complex particle, prepared good Organic by surface initiated polymerization, successfully realize the surface modification of nanoparticle, improved the dispersed and stable of nanoparticle.But reverse atom transfer radical polymerization is to institute's polymers grafted segmental poor controllability.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of surface-modified nanoparticles is provided, it adopts atom transfer radical polymerization (Atom Transfer Radical Polymerization, ATRP) method is carried out modification to the inorganic nano-particle sub-surface, make nanoparticle surface institute polymers grafted have controllability, give full play to the advantage of nanoparticle.Make it under the situation of few additive, reach the enhancing of nanoparticle, effect such as toughness reinforcing.
For realizing above technical purpose, the present invention will take following technical scheme:
A kind of preparation method of surface-modified nanoparticles, may further comprise the steps: under (1) room temperature, earlier nanoparticle is dissolved in the mixed solvent of being made up of toluene and Virahol, the 2-bromine isobutyryl that then adds triethylamine and silanization, with surperficial initiator at the surface anchoring ATRP of nanoparticle, prepare the nanoparticle that has ATRP surface initiator, the 2-bromine isobutyryl of described silanization contains silicon chlorine key; (2) the prepared nanoparticle that has ATRP surface initiator that goes out of step (1) is scattered in the Virahol, with the methyl acrylic ester monomer ATRP reaction takes place under the effect of catalyzer, coordination agent, to prepare the inorganic nano-particle of polymethacrylate monomer graft modification under oxygen free condition.
Described nanoparticle is bifluoride magnesium, silicon-dioxide or titanium dioxide.
The molecular structural formula of the 2-bromine isobutyryl of described silanization is as follows:
Wherein: the R substituting group is Cl, CH
3-O-or C
2H
5-O-; N=6 ~ 11.
Described polymethacrylate monomer is methyl methacrylate, N, N-dimethylaminomethyl ethyl propenoate, poly ethyldiol modified methacrylic ester, butyl methacrylate or hydroxyethyl methylacrylate.
Described catalyzer is a cuprous bromide, cuprous chloride.
Described coordination agent is bipyridine or pentamethyl-diethylenetriamine.
In addition, the application of the inorganic nano-particle of the prepared polymethacrylate monomer graft modification that goes out of the preparation method that another technical purpose of the present invention provides a kind of above-mentioned surface-modified nanoparticles, its inorganic nano-particle with the polymethacrylate monomer graft modification is applied in the acrylate paint.
According to above technical scheme, can realize following beneficial effect:
The present invention adopts the method for atom transfer radical polymerization to nanometer particle-modified, the grafted acrylic polymer has controllability in nanoparticle surface institute, give full play to the advantage of nanoparticle, make it under the situation of few additive, reach the enhancing of nanoparticle, effect such as toughness reinforcing; Simultaneously, the present invention is chain length distribution evenly at nanoparticle surface grafted acrylic polymer, has improved this modified Nano particle dispersed and stable in acrylate paint.In addition, ATRP of the present invention reaction is at room temperature carried out, and the low energy environmental protection meets the demand of national Green Chemistry.In addition, the nanoparticle of institute's modification has good dispersiveness in acrylate paint, improved the wear resistance of coating, has kept the high transparent of coating simultaneously.
Embodiment
Explain technical scheme of the present invention below with reference to embodiment.
Reaction principle:
The first step: the surperficial initiator of introducing ATRP in nanoparticle surface.Concrete grammar is: (its chemical formula is SiO with the silicon-dioxide of 20-150nm
2), (its chemical formula is TiO to titanium dioxide
2) or bifluoride magnesium (its chemical formula is MgF
2) be dispersed in the reactor that has toluene and isopropyl alcohol mixed solvent, system maintains room temperature, adds an amount of triethylamine and the 2-bromine isobutyryl with silanization of following structure (molecular formula 1).
R:?Cl,?CH
3-O-，C
2H
5-O-;?n=6~11
Molecular formula 1
Press reaction formula 1 reaction after 18 hours, to product wash, centrifugal, the nanoparticle of the surperficial initiator that has ATRP of gained is carried out vacuum-drying.
Reaction formula 1
Hence one can see that, and the surperficial initiator of ATRP of the present invention is for containing the 2-bromine isobutyryl ester of silicon chlorine key (Cl-Si).
Second step was that the nanoparticle that will have the surperficial initiator of ATRP is dispersed in the isopropanol solvent, feeds nitrogen oxygen is discharged, and added appropriate amount of catalysts, coordination agent and grafted monomer and carried out graft polymerization according to reaction formula 2 under the condition of room temperature, anaerobic.Feed isopropanol behind the reaction 2-8 h, reaction product is carried out centrifugal, washing, drying, promptly get the inorganic nano-particle of polymethacrylate polymer graft modification.
Reaction formula 2
Inorganic nano-particle involvement aspect of the present invention is very wide, comprise tin indium oxide, aluminium sesquioxide, ferric oxide, bifluoride magnesium, silicon-dioxide, titanium dioxide etc., be meant bifluoride magnesium especially, silicon-dioxide and titanium dioxide, nanoparticle is of a size of 1-500nm, and specifically 10-250nm more particularly is meant 20-150 nm.
ATRP of the present invention surface initiator mainly is the 2-bromine isobutyryl of silanization, shown in molecular formula 1, and the number n from 6 to 11 of alkyl; Silane coverlet chlorination at least also can be by two chlorinations, tri-chlorination, methyl alkoxide or ethyl alkoxide.
ATRP grafted monomer of the present invention mainly is the polymethacrylate monomer, and it contains the methacrylate based (CH of group
2=C (CH
3)-CO-O-) simultaneously can be passed through ATRP method polymeric monomer, comprises methyl methacrylate, butyl methacrylate, N, N-dimethylaminomethyl ethyl propenoate, poly ethyldiol modified methacrylic ester, hydroxyethyl methylacrylate etc.
ATRP catalyzer of the present invention mainly is a univalent copper ion salt, comprises cuprous bromide, cuprous chloride.
ATRP coordination agent of the present invention comprises bipyridine (bpy) and pentamethyl-diethylenetriamine (PMDETA).
The preferred embodiment of modified Nano particle preparation method of the present invention below will at length be disclosed.
Embodiment 1
The anchoring of the first step ATRP surface initiator: with 20 gram particles directly is that the silicon-dioxide of 50 ± 5 nanometers joins in the mixed solvent that 200ml toluene/20ml Virahol is housed, in this mixed solvent, the volume ratio of toluene and Virahol generally is no more than 20:1, at room temperature stir, add the 2-bromine isobutyryl and the 1.4g triethylamine of the trichlorosilicane hexane of 5g.At room temperature slowly stirred 18 hours, and filtered solvent, use Virahol repetitive scrubbing filter cake, filter cake is placed at room temperature is dried to constant weight in the vacuum drying oven.With the energy spectrum analysis of X ray photoelectric sub-surface, nanoparticle surface has the absorption peak of bromine at the 73eV place, shows that ATRP surface initiator has been grafted on silica sphere.
The second step graft polymerization reaction: the silicon-dioxide that the 10g surface is had the surperficial initiator of ATRP is dispersed in the 200ml Virahol, feed nitrogen 30min, add 23mg monobromination copper, poly ethyldiol modified methacrylic ester (the m=4.5 of 50mg bipyridine (bpy) and 2.4g anaerobic, molecular weight 300), reaction solution is a Vandyke brown, at room temperature reacts 2 hours.Use isopropanol, reaction product is carried out centrifugal, washing, drying, promptly obtain poly ethyldiol modified methacrylate polymers grafted silicon-dioxide inorganic nano-particle.The diameter that records the silicon-dioxide of graft modification with little angle dynamic laser light scattering experimental method is 65 ± 5 nanometers, shows that silica sphere has polymkeric substance.
Embodiment 2
The first step directly is that the bifluoride magnesium of 100 ± 5 nanometers joins in the mixed solvent that 400ml toluene/20ml Virahol is housed with 50 gram particles, at room temperature stirs, and adds the 2-bromine isobutyryl and the 4.5g triethylamine of the trichlorosilicane certain herbaceous plants with big flowers alkane of 12.5g.At room temperature slowly stirred 18 hours, and filtered solvent, use Virahol repetitive scrubbing filter cake, filter cake is placed at room temperature is dried to constant weight in the vacuum drying oven.With the energy spectrum analysis of X ray photoelectric sub-surface, nanoparticle surface has the absorption peak of bromine at the 73eV place, shows that ATRP surface initiator has been grafted on the bifluoride magnesium surface.
Second step was dispersed in the silicon-dioxide that the 20g surface has the surperficial initiator of ATRP in the 200ml Virahol, feed nitrogen 30min, add 46mg monobromination copper, the N of 100mg pentamethyl-diethylenetriamine (PMDETA) and 10g anaerobic, N-dimethylaminomethyl ethyl propenoate, reaction solution is a Vandyke brown, reaction at room temperature, 5 hours.Use isopropanol, reaction product is carried out centrifugal, washing, drying, promptly gathered (N, N-dimethylaminomethyl ethyl propenoate) grafted bifluoride magnesium inorganic nano-particle.The diameter that records the silicon-dioxide of graft modification with little angle dynamic laser light scattering experimental method is 113 ± 5 nanometers, shows that the bifluoride magnesium surface has polymkeric substance.
Embodiment 3
The first step directly is that the titanium dioxide of 25 ± 5 nanometers joins in the mixed solvent that 200ml toluene/10ml Virahol is housed with 20 gram particles, at room temperature stirs, and adds the 2-bromine isobutyryl and the 1.54g triethylamine of the trichlorosilicane last of the twelve Earthly Branches alkane of 5.5g.At room temperature slowly stirred 18 hours, and filtered solvent, use Virahol repetitive scrubbing filter cake, filter cake is placed at room temperature is dried to constant weight in the vacuum drying oven.With the energy spectrum analysis of X ray photoelectric sub-surface, nanoparticle surface has the absorption peak of bromine at the 73eV place, shows that ATRP surface initiator has been grafted on titanium dioxide surface.
Second step was dispersed in the titanium dioxide that the 10g surface has the surperficial initiator of ATRP in the 200ml Virahol, feed nitrogen 30min, add 23mg monobromination copper, the hydroxyethyl methylacrylate of 50mg bipyridine (bpy) and 1.2g anaerobic, reaction solution is a Vandyke brown, at room temperature reacts 5 hours.Use isopropanol, reaction product is carried out centrifugal, washing, drying, promptly gathered (hydroxyethyl methylacrylate) grafted titanium oxide inorganic nanoparticle.The diameter that records the silicon-dioxide of graft modification with little angle dynamic laser light scattering experimental method is 25 ± 5 nanometers, shows that titanium dioxide surface has polymkeric substance.
The Application Example of modified Nano particle of the present invention below will be disclosed
Embodiment 4
The Nano particles of silicon dioxide of 3g example 1 modification is joined the l of 45g, in the 6-hexanediyl ester, stir after adding 2g UV initiator (1104) simultaneously, liquid-transparent does not have cohesion.Transparent liquid is coated on the polyester film, and with the UVA energy-curable of 300mJ, the mist degree of gained hardening film (ASTM D-1003) is 0.3%, and wear resistance (100 change the CS-10F emery wheel for ASTM D-1044,500 gram load) is 5%.
The simultaneous test of embodiment 4
3g is not carried out silicon-dioxide that surface modification is of a size of 50 ± 5 nanometers join in the same prescription of embodiment 3, gained liquid is sent out mist after stirring, opaque.Be coated on the polyester film solidify with similarity condition UV after, the mist degree of gained hardening film (ASTM D-1003) is 1.3%, wear resistance (100 change the CS-10F emery wheel for ASTM D-1044,500 gram load) is 8%.
Although the present invention has been done detailed explanation and quoted some specific exampless as proof, for a person skilled in the art, only otherwise leave the spirit and scope of the present invention, it is obvious doing various variations or correction.
Claims (7)
1. the preparation method of a surface-modified nanoparticles, it is characterized in that, may further comprise the steps: under (1) room temperature, earlier nanoparticle is dissolved in the mixed solvent of being made up of toluene and Virahol, the 2-bromine isobutyryl that then adds triethylamine and silanization, with surperficial initiator at the surface anchoring ATRP of nanoparticle, prepare the nanoparticle that has ATRP surface initiator, the 2-bromine isobutyryl of described silanization contains silicon chlorine key; (2) the prepared nanoparticle that has ATRP surface initiator that goes out of step (1) is scattered in the Virahol, with the methyl acrylic ester monomer ATRP reaction takes place under the effect of catalyzer, coordination agent, to prepare the inorganic nano-particle of polymethacrylate monomer graft modification under oxygen free condition.
2. according to the preparation method of the described surface-modified nanoparticles of claim 1, it is characterized in that described nanoparticle is bifluoride magnesium, silicon-dioxide or titanium dioxide.
3. according to the preparation method of the described surface-modified nanoparticles of claim 1, it is characterized in that the molecular structural formula of the 2-bromine isobutyryl of described silanization is as follows:
Wherein: the R substituting group is Cl, CH
3-O-or C
2H
5-O-; N=6 ~ 11.
4. according to the preparation method of the described surface-modified nanoparticles of claim 1, it is characterized in that, described polymethacrylate monomer is methyl methacrylate, N, N-dimethylaminomethyl ethyl propenoate, poly ethyldiol modified methacrylic ester, butyl methacrylate or hydroxyethyl methylacrylate.
5. according to the preparation method of the described surface-modified nanoparticles of claim 1, it is characterized in that described catalyzer is cuprous bromide or cuprous chloride.
6. according to the preparation method of the described surface-modified nanoparticles of claim 1, it is characterized in that described coordination agent is bipyridine or pentamethyl-diethylenetriamine.
7. the application of the inorganic nano-particle of the prepared polymethacrylate monomer graft modification that goes out of the preparation method of the described surface-modified nanoparticles of claim 1 is characterized in that: the inorganic nano-particle of polymethacrylate monomer graft modification is applied in the acrylate paint.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702798A (en) * | 2012-06-18 | 2012-10-03 | 中国船舶重工集团公司第七二五研究所 | Modified silica filler and preparation method thereof |
| CN103336098A (en) * | 2013-07-15 | 2013-10-02 | 四川大学 | Method for forecasting effective action range of functional particles on polymer matrix |
| CN104497641A (en) * | 2014-12-24 | 2015-04-08 | 清华大学 | Preparation method of nano-silica with surface grafted with polystearylmethacrylate |
| CN106810651A (en) * | 2017-01-23 | 2017-06-09 | 中国皮革和制鞋工业研究院 | Surface modification has nano titanium oxide of fluorocarbon polymer and preparation method thereof, finishing agent, film and painting membrane product |
| CN109554088A (en) * | 2017-09-27 | 2019-04-02 | 洛阳尖端技术研究院 | A kind of infrared stealth coating and preparation method thereof |
| CN110284750A (en) * | 2019-03-21 | 2019-09-27 | 国家电网有限公司 | A kind of pole guy barrier cover |
| CN114834112A (en) * | 2022-05-19 | 2022-08-02 | 青岛炯晟新材料科技有限公司 | Puncture-resistant high-heat-insulation vacuum heat-insulation plate and preparation method thereof |
| CN115010972A (en) * | 2022-07-15 | 2022-09-06 | 南京先进生物材料与过程装备研究院有限公司 | Ceramic/chitosan nano high-strength composite film and preparation method thereof |
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| CN101580570A (en) * | 2009-06-17 | 2009-11-18 | 厦门大学 | Siloxane-acrylate copolymer/nano-silicon dioxide organic/inorganic hybrid nano-material and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702798A (en) * | 2012-06-18 | 2012-10-03 | 中国船舶重工集团公司第七二五研究所 | Modified silica filler and preparation method thereof |
| CN102702798B (en) * | 2012-06-18 | 2014-04-02 | 中国船舶重工集团公司第七二五研究所 | Modified silica filler and preparation method thereof |
| CN103336098A (en) * | 2013-07-15 | 2013-10-02 | 四川大学 | Method for forecasting effective action range of functional particles on polymer matrix |
| CN103336098B (en) * | 2013-07-15 | 2016-03-30 | 四川大学 | A kind of forecast function particle is to the method for polymeric matrix effective range |
| CN104497641A (en) * | 2014-12-24 | 2015-04-08 | 清华大学 | Preparation method of nano-silica with surface grafted with polystearylmethacrylate |
| CN106810651A (en) * | 2017-01-23 | 2017-06-09 | 中国皮革和制鞋工业研究院 | Surface modification has nano titanium oxide of fluorocarbon polymer and preparation method thereof, finishing agent, film and painting membrane product |
| CN109554088A (en) * | 2017-09-27 | 2019-04-02 | 洛阳尖端技术研究院 | A kind of infrared stealth coating and preparation method thereof |
| CN110284750A (en) * | 2019-03-21 | 2019-09-27 | 国家电网有限公司 | A kind of pole guy barrier cover |
| CN114834112A (en) * | 2022-05-19 | 2022-08-02 | 青岛炯晟新材料科技有限公司 | Puncture-resistant high-heat-insulation vacuum heat-insulation plate and preparation method thereof |
| CN114834112B (en) * | 2022-05-19 | 2024-03-29 | 青岛新材料科技工业园发展有限公司 | Puncture-resistant high-heat-insulation vacuum insulation panel and preparation method thereof |
| CN115010972A (en) * | 2022-07-15 | 2022-09-06 | 南京先进生物材料与过程装备研究院有限公司 | Ceramic/chitosan nano high-strength composite film and preparation method thereof |
| CN115010972B (en) * | 2022-07-15 | 2024-05-28 | 南京先进生物材料与过程装备研究院有限公司 | Ceramic/chitosan nano high-strength composite film and preparation method thereof |
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Application publication date: 20110914 |