CN102504612A - Novel modified nano silicon dioxide and composite coating prepared from same - Google Patents

Novel modified nano silicon dioxide and composite coating prepared from same Download PDF

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CN102504612A
CN102504612A CN201110348076XA CN201110348076A CN102504612A CN 102504612 A CN102504612 A CN 102504612A CN 201110348076X A CN201110348076X A CN 201110348076XA CN 201110348076 A CN201110348076 A CN 201110348076A CN 102504612 A CN102504612 A CN 102504612A
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pamam
nano silicon
silicon dioxide
powder
generation
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CN201110348076XA
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CN102504612B (en
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靳涛
曾荣昌
刘欣
张芬
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山东科技大学
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Abstract

The invention discloses novel modified nano silicon dioxide and a composite coating prepared from the same. The modified nano silicon dioxide is prepared by mixing G4.0 polyamide-polyamidoaminedendrimer with nano SiO2 powder according to a weight proportion of 25: 12, carrying out magnetic agitation and ultrasonic oscillation under the protection of inert gas, and then modifying. The composite coating is prepared by adding various addition agents into fillers including the modified nano silicon dioxide, titanium dioxide, calcium carbonate and the like and grinding, and then adding emulsion. According to the invention, PAMAM (Polyamidoamine) is used as a template to carry out dry-method modification on nano silicon dioxide to cover one layer of carbon-nitrogen molecules on the surface of the nano silicon dioxide, so that the compatibility between the nano silicon dioxide and a film-forming base material is increased and the dispersity is better; and compared with wet-method modification, certain cost is saved, the process is simple and the modification effect is obvious.

Description

New modified nano silicon and by the composite coating of its preparation

Technical field

The present invention relates to nano powder modified and application, relate in particular to the preparation of water nano functional paint.

Background technology

In recent years, external " high-grade paint " product pours in China market, makes Coating Industry in Our Country receive serious impact.I scientific and technical personnel pass through this type of import " high-grade paint " is detected; Find wherein all to have added different types of nano material; Nanoparticle is in " high-grade paint " system; With its unique physics, chemical property and the not available small-size effect of conventional material, quantum size effect and surface interface effect, the scratch resistance wound of coating products, anti-aging, water-fast scrubbing property, antistatic, smooth finish, contrast ratio and performances such as surface hardness of filming and self-cleaning ability have been increased substantially.For example: successfully developed the transparent automobile finish hybrid resin base coating (the hydridization phase size is a nano level) of scratch resistance wound, ultraviolet resistance and resistance to chemical attack abroad, and be applied to the automobile of multiple models such as Ford Taurus.In addition, U.S. Du Pont company also releases the antibiotic paint that is added with nano silver particles.Germany Nano Chem System company; Developed coating surfaces materials such as can be used for concrete, stone material, pottery, timber, glass; The nanotechnology that it is said this coatings applications; Can reduce, thereby reach anti-soil, antifog, easy purpose of cleaning by the surface tension of coating surface (hydrophobic, oleophobic); The said firm has also released the acrylate paint of self-cleaning type exterior coating silicon nanostructure modification, discovers: in resin, mix nano level TiO 2(white), Cr 2O 3(green), Fe 2O 3(brown), ZnO etc. have the powder of semiconductor property; Can produce good electrostatic shielding performance; Institute of Japanese Matsushita Electric Industrial company has successfully developed the resin-base nano oxide compound compound electrostatic shielding coating that is applicable to electric appliance casing in view of the above; Compare with prior resin base carbon black compound coating, resin-base nano oxide compound composite coating has more excellent electrostatic shielding performance, and the latter is also more flexible aspect the color selection; The invisible coating that is militarily utilized; Also at present forms of adding Nano filling that adopt more, its stealthy principle is: the nanoparticle size also is that nanoparticle material is higher than conventional material to the transmitance of infrared and radar wave much smaller than infrared and radar wave wavelength; The specific surface area of nanoparticle is much larger than conventional powder; Cause it also high to the absorption of electromagnetic wave rate; Thereby cause nanoparticle material that the reflectivity of infrared and radar wave is descended; The signal that makes infrared eye and radar receive becomes faint, thereby plays stealthy effect, for example: just scribble the stealth material with wideband electromagnetic ripple receptivity that is made up of multiple ultramicron on the U.S. F117A type aircraft.

And also developed the nano paint that hydrophobic antifouling dyes trade sales coating, antibacterial inner wall paint and rubber-emulsion paint uvioresistant anti-aging nano paint and has certain photocatalytic activity (but in the catalyzed oxidation air obnoxious flavour) and disinfection function in research institution of the many companies of China; These nano-level coatings are except that the film forming base-material is carried out the improvement on the technical recipe; Also mostly is to adopt the prepare nano composite dope that adds nanometer grade powder; For example: in design aqueous architectural coating prescription process, the interpolation massfraction is about 3% nanometer SiO 2, through disperseing to obtain the coating of modification fully, its each item technical performance index all has significant improvement: shortened to less than 1h by original 2h time of drying; Wash-resistant property is brought up to more than 10000 times by 1000 times (exterior coating) and 100 times (interior wall coating); Artificial accelerated aging test by the one-level variable color of 240h, 450h is brought up in the secondary efflorescence does not have any variation, still because nanometer SiO 2For unformed white powder (referring to its soft aggregate), through the transmission electron microscope test analysis, this material obviously demonstrates cotton-shaped and netted accurate grain pattern, and particle size is little, and (3~15nm), specific surface area is (640 ± 50m greatly 2/ g), there is the hydroxyl of a large amount of unsaturated residual bonds and different bonding states in the surface, very easily causes the influence of reuniting to disperse, and it is more outstanding to reunite when especially content is higher.Because the practical application of nano material depends primarily on the surface molecular design conditions (promptly how solving the compatibility problem with the body material system) and the dispersity in body material thereof of nano-powder material; Therefore; When the preparation nano paint; The dispersion of nano-powder becomes the key of the good coating of processability, and improve nano-powder dispersiveness, guarantee the consistency of filler with the film forming base-material, the nano powder surface modification is become the key of preparation functional paint again; This is that consistency missionary society influences the dispersing uniformity of inorganic nanometer powder at film process because the character of inorganic powder surface character and film forming organic substrate differs bigger.

At present, in preparation nano paint process.Physics dispersive mode is adopted in the dispersion of filler more; As: grind dispersion, sand milling dispersion, Ball milling, high-speed stirring (more than the 1500r/min) etc.; In addition, when nano-powder disperses, also can adopt dispersion modes such as ultra-sonic dispersion, colloidal mill dispersion, high energy particle processing in liquid.But the mode of above-mentioned mechanical dispersion all is difficult for " overheated " disperses, and because of in dispersion process, powder particle will receive intensive shearing force or impact force, and nano-powder is cracking probably, produces more active body (as: ≡ Si-O-Si ≡ → ≡ Si ++ ≡ SiO -Or ≡ Si-O-Si ≡ → ≡ Si + ≡ SiO , ≡ Si representative connects the siliconoxygen bond in the powder surface), so the easier chemical reaction that takes place of powder surface, along with the increase of heat energy and mechanical energy, the probability of particle collision also increases, and causes further reunion on the contrary simultaneously.This secondary " reunion " makes and the stability in storage variation of slurry is difficult to the suspension property and the workability that keep stable.Therefore can reduce the surface energy of powder on the one hand to powder surface modification, the opposing party can improve the consistency with matrix, and powder-modified mode is mainly contained at present: 1. coupling agent method.Through coupling agent modified powder, strengthened the solubility of nanoparticle in organic medium, it can be dispersed in the organic matrix preferably, increase powder filled amount, thereby improved the over-all properties of goods.2. surfactant-modified method.This method is to the nano powder surface modification through negatively charged ion, neutral surface active agent or cationic surfactant.3. surface graft modification method.Utilize the surface group of nanoparticle, and can react organic compound deposits yields chemical bonding, form the organic graft compound of nanometer,, strengthen the dispersion of nanoparticle in organic medium through the solubility of organic branched compound in organic medium.For example: utilize nanometer SiO 2Lip-deep active site is prone to produce the character of living radical; Thmoas and Espiard have studied the vinyl-acetic ester graft polymerization reaction in its surface and the graft polymerization reaction of ethyl propenoate respectively; People such as Tsubokawa N and Kaneko Y utilize the Michael addition reaction, have studied respectively at nanometer SiO 2The process of surface grafting daiamid (PAMAM).No matter adopt coupling agent modified still surface graft modification; This modified effect that forms chemisorption (chemical bond) at powder surface depends primarily on the factors such as concentration and molecular weight of quantity, the properties-correcting agent of powder surface active site; And getting quantity, the powder surface active site is difficult to quantitative measurement; And be closely related with size, powder crystal formation, condition of surface etc., therefore the control to diameter of particle size and distribution seems even more important.

From Tomalia first since synthesizing polyamides-amine type dendrimer (hereinafter to be referred as PAMAM); Because PAMAM has the geometrical symmetry of height, molecular structure, a large amount of functional group, molecular memories increase characteristics such as having controllability at cavity and molecular chain accurately; In recent years, the research work of relevant PAMAM is very active.The investigator is that template has prepared Cu through PAMAM both at home and abroad, Ag, and Pd, Pt, Au, ZnO, CdS, nano-substances such as ZnS, it is even to obtain size, the nanoparticle that distribution range is narrower.And be that template prepares and the document of modified inorganic nano silicon does not also appear in the newspapers at present with PAMAM; According to discovering that PAMAM surpassed more than 4 generations; Almost become globosity, the cavity of comparatively large vol is contained in inside, in addition because the PAMAM intramolecule contains more functional group; (NH), these active function groups are prerequisites of adsorption of modification nano-powder silicon-dioxide like carbonyl (C=O), inferior acylamino hydrogen.

Summary of the invention

It is controlled to the purpose of this invention is to provide a kind of preparation size distribution, and the uniform modified manometer silicon dioxide powder of size relies on the functional group on the PAMAM molecular chain to realize the modification to nano-powder silicon-dioxide.

The present invention provides the composite coating by this modified manometer silicon dioxide powder preparing simultaneously.

Modified manometer silicon dioxide powder of the present invention is by 4.0 generation polyamide-amide type dendrimers (following replace with PAMAM) and nanometer SiO 2Powder mixes according to 25: 12 part by weight, under protection of inert gas, through magnetic agitation and sonic oscillation post-modification and.

Modified manometer silicon dioxide powder of the present invention can be prepared by following method:

Earlier synthetic PAMAM realizes dry method modification nanometer SiO as template again 2The purpose of powder, manufacture craft is following in detail:

The first step: preparation PAMAM

At first, serve as the nuclear primitive with the second diamino, in methyl alcohol, carry out Michael addition reaction completely with methyl acrylate, obtain the adduct of three methyl acrylates.Carry out the aminolysis reaction of ester then with excessive quadrol, obtain amidation triamino product, the addition reaction of repetition and methyl acrylate prepares the PAMAM in 4.0 generations again.

Second step: preparation modified manometer silicon dioxide

With 4.0 generation PAMAM 50g of preparation, add nano silicon (about particle diameter 10nm) 12g and mix, at the uniform velocity stir 2h at the protection of inert gas lower magnetic force, sonic oscillation 30min promptly obtains the modified manometer silicon dioxide powder that need prepare then.

Above-mentioned rare gas element is preferentially selected helium for use.

Composite coating of the present invention is by fillers such as above-mentioned modified manometer silicon dioxide, titanium oxide, lime carbonate; Adding various auxiliary agents grinds; Adding the emulsion allotment then forms; Above-mentioned auxiliary agent comprises film coalescence aid, dispersion agent, wetting agent, mould inhibitor and skimmer, is the commercially available prod of preparation coating;

In order to reduce VOC content in the coating greatly; Film coalescence aid is selected for use: high boiling point film coalescence aid DBE-IB (ester content>=99%, acid number≤1.0mgKOH/g, moisture content≤0.2%; Boiling point: 253-283 ℃) and Kening Co.,Ltd's VOC free film coalescence aid LOXANOL EFC 300 (density (20 ℃): 0.85~0.95 of producing; Viscosity: 20~30mPas, acidity: 0~5, VOC is 0).

Can also add to modified manometer silicon dioxide of the present invention in the polymer composites such as rubber, plastics, to improve the over-all properties of material.

Advantage of the present invention is:

1, adopting PAMAM is that template is carried out dry method modification to nano silicon, makes nano-silica surface parcel one deck carbon nitrogen chain molecule, has increased the consistency with the film forming base-material; Dispersed better; Compare wet-process modified certain cost of having saved, technology is simple, and modified effect is outstanding.Can find out dispersed raising the after the modification from Fig. 3, can form the more coating of densification during prepared coating film forming, can find out that from Fig. 4 filler distribution is even the coating, improve the over-all properties of coating.

2, this method adopts high boiling point film coalescence aid DBE-IB and LOXANOL EFC 300, calculates the consumption of EFC300 and DBE-IB according to minimum film-forming temperature (MFFT), and according to U.S. EPA 24 examination criterias, the VOC of coating is 0.1g/l.The invention enables the weathering resistance of paint coatings, abrasion resistance is improved, and greatly reduces VOC content, and test-results has confirmed the feasibility of such scheme.

Description of drawings

Fig. 1 is a nano silicon dry method modification schematic diagram of the present invention;

Fig. 2 is nano-silicon dioxide modified preceding SEM picture;

Fig. 3 is the SEM picture of the present invention after nano-silicon dioxide modified;

Fig. 4 is the SEM picture that utilizes the composite coating coating of nano silicon preparation of the present invention.

Among Fig. 1: 91-Siliciumatom, 76-nitrogen-atoms (with silicon with singly bound).

Embodiment

Specify technical scheme of the present invention through the practical implementation step below.

Modified manometer silicon dioxide preparation method of the present invention is following:

The first step: the preparation of PAMAM template

The preparation of (1) 0.5 generation PAMAM: methyl acrylate 120g and methyl alcohol 10g are placed the 400mL volumetric flask, and 5 ℃ of lower magnetic forces stir, behind the logical He protection 1h; Drip the mixture of quadrol 10.5g and methyl alcohol 27.5g with tap funnel; Drip 1h and logical He, after dropwising, react 36h under the room temperature.With Rotary Evaporators underpressure distillation (about 140Pa, 40 ℃), remove unreacted methyl acrylate and methyl alcohol, get little yellow slightly thick liquid.

The preparation of (2) 1.0 generation PAMAM: quadrol 84g and methyl alcohol 11g are placed the 500mL volumetric flask, and 5 ℃ of lower magnetic forces stir, after logical He protects behind the 1h; Drip the mixture of 0.5 generation PAMAM 20g and methyl alcohol 64g with tap funnel; Drip 2h and logical He, after dropwising, react 36h under the room temperature.With Rotary Evaporators underpressure distillation (about 140Pa, 60 ℃), remove unreacted quadrol and methyl alcohol, get little yellow thick liquid.

The preparation of half generation, 1.5,2.5 and 3.5 generation PAMAM: with the preparation of 0.5 generation PAMAM.

The preparation of whole generation 2.0,3.0 and 4.0 generation PAMAM: with the preparation of 1.0 generation PAMAM

Its reaction principle is: (a): methyl alcohol and methyl acrylate (MA) generate a quaternary ester through the Michael addition reaction, are called for 0.5 generation; (b): ammonolysis reaction takes place and generates a quaternary amide compound in quaternary ester and excessive EDA, is called for 1.0 generations.Repeat the reactions step that (a) and (b) Michael addition and ammonia are separated, can obtain the PAMAM type macromolecular cpd of different algebraically (being different end groups and relative molecular mass).

Second step: the preparation of modified nano powder silicon-dioxide

The 4.0 generation PAMAM 50g that the first step is prepared; Add nano silicon (about particle diameter 10nm) 12g; Insert simultaneously in the 500ml there-necked flask, under rare gas element helium (He) protection, with 3000r/min magnetic agitation 2h; Take out modified powder, disperse 30min subsequent use with sonic oscillation again under 10 ℃.

Its modification theory is: in whipping process; Nano silica powder receives the isodynamic effect of shearing force, impact force and frictional force of machinery; Heterolytic fission or homologisation take place; Obtain the active silica powder, its cracking process and result see formula (1) and (2), and the active body skeleton symbol after the cracking is seen structural formula (3);

≡Si-O-Si≡→≡Si ++≡SiO - (1)

=Si-O-Si≡→≡Si ·+≡SiO ·(2)

Under properties-correcting agent PAMAM effect, the active silica powder reacts with PAMAM then, thereby obtains the nano silica powder of modification, and modification theory is seen Fig. 1; Be example with 1.0 generation PAMAM improved silica cation groups among the figure; So that the situation that combines of explanation PAMAM and silicon ion can find out between silicon ion and the PAMAM from scheme to have formed chemical bond that dry method modification has made full use of the activity of the amide group in the PAMAM molecule; Present electronegativity on the N atom 76; And silicon positively charged ion 91 presents positive polarity, is prone to form the N-Si key.

At last the nano silicon activation number after the modification is measured; The method of measuring activation index is following: add 150mL zero(ppm) water with the 200mL beaker; The filler powder 10g that gets after the modification adds wherein, stirs 2min and leaves standstill more than the 1h with glass stick, will fall to then beaker bottom material filtering, dry, weigh; Deduct the quality of this sedimentation material with the former quality that takes by weighing (10g), can obtain the quality of floating part in the sample.By the quality/sample total mass of floating part in activation number=sample, can try to achieve activation index.

Through check, the activation number of improved silica of the present invention reaches 0.94, can find out relatively that according to another Fig. 2 and Fig. 3 the dispersiveness of improved silica of the present invention improves greatly.

Coating of the present invention is by fillers such as above-mentioned modified manometer silicon dioxide, titanium oxide, lime carbonate; Add various auxiliary agents and the film forming base-material grinds; Adding the emulsion allotment then forms; The proportioning of various color stuffings, auxiliary agent and emulsion, concrete proportioning situation is seen form 1, preparation process is following in detail:

The first step: get high boiling point film coalescence aid DBE-IB:1.4g, LOXANOL EFC 300:2.8g, dispersion agent FS3204:0.15g, dispersing agent C D50:0.4g, wetting agent H885:0.2g, wetting agent 188A:0.10g, skimmer A10:0.10g, skimmer F111:0.15g, adhesion promoter 0.05:g and deionized water 20g; Stirring at low speed 15min uniform mixing; The silicon-dioxide 20g that adds modification again carries out high speed dispersion with other color stuffings 11g, thickening material HEC:0.4g, thickening material DSX3116:0.5g and additional part deionized water; Process white slurry, jitter time is not less than 1.5h.

Second step: join ground white slurry at a slow speed among the 35g benzene emulsion PA237 (being meant before treating batch white slurry that adds a collection of white slurry after stirring at low speed just can add after evenly at a slow speed) to continue stirring at low speed more even in batches in batches; At last with the first viscosity of coating of thickening material adjustment, using pH regulator agent adjustment pH value is 8.5 to be the rubber-emulsion paint finished product.

In order to verify the performance of composite coating of the present invention, the nano silicon of getting modification of the present invention respectively is prepared into composite coating with existing unmodified nano silicon and carries out performance comparison, and comparing result is seen table 2, and the method for inspection is according to GB/T9755-2001.

Can find out that from table 2 each item performance index of the composite coating of preparation all are improved significantly.

Table 1 formula rate (unit: g)

The prepared coating traditional performance contrast of the nano-silicon dioxide modified front and back of table 2

Claims (7)

1. a new modified nano silicon is characterized in that, it be by 4.0 generation polyamide-amide type dendrimer and nanometer SiO 2Powder mixes according to 25: 12 part by weight, under protection of inert gas, through magnetic agitation and sonic oscillation post-modification and.
2. silicon-dioxide as claimed in claim 1 is characterized in that, described rare gas element is a helium.
3. a method for preparing nano silicon according to claim 1 or claim 2 is characterized in that, earlier synthetic PAMAM realizes dry method modification nanometer SiO as template again 2The purpose of powder, manufacture craft is following in detail:
The first step: preparation PAMAM
At first, serve as the nuclear primitive with the second diamino, in methyl alcohol, carry out Michael addition reaction completely with methyl acrylate, obtain the adduct of three methyl acrylates; Carry out the aminolysis reaction of ester then with excessive quadrol, obtain amidation triamino product, the addition reaction of repetition and methyl acrylate prepares the PAMAM in 4.0 generations again;
Second step: preparation modified manometer silicon dioxide
With 4.0 generation PAMAM 50g of preparation, the nano silicon 12g that adds particle diameter 10nm mixes, and at the uniform velocity stirs 2h at the protection of inert gas lower magnetic force, and sonic oscillation 30min promptly obtains the modified manometer silicon dioxide powder that need prepare then.
4. the method for preparing nano silicon as claimed in claim 3 is characterized in that detailed step is following:
The first step: the preparation of PAMAM template
The preparation of (1) 0.5 generation PAMAM: methyl acrylate 120g and methyl alcohol 10g are placed the 400mL volumetric flask, and 5 ℃ of lower magnetic forces stir, behind the logical He protection 1h; Drip the mixture of quadrol 10.5g and methyl alcohol 27.5g with tap funnel; Drip 1h and logical He, after dropwising, react 36h under the room temperature.With Rotary Evaporators underpressure distillation (about 140Pa, 40 ℃), remove unreacted methyl acrylate and methyl alcohol, get little yellow slightly thick liquid.
The preparation of (2) 1.0 generation PAMAM: quadrol 84g and methyl alcohol 11g are placed the 500mL volumetric flask, and 5 ℃ of lower magnetic forces stir, after logical He protects behind the 1h; Drip the mixture of 0.5 generation PAMAM 20g and methyl alcohol 64g with tap funnel; Drip 2h and logical He, after dropwising, react 36h under the room temperature.With Rotary Evaporators underpressure distillation (about 140Pa, 60 ℃), remove unreacted quadrol and methyl alcohol, get little yellow thick liquid.
The preparation of half generation, 1.5,2.5 and 3.5 generation PAMAM: with the preparation of 0.5 generation PAMAM.
The preparation of whole generation 2.0,3.0 and 4.0 generation PAMAM: with the preparation of 1.0 generation PAMAM
Second step: the preparation of modified nano powder silicon-dioxide
With the 4.0 generation PAMAM 50g that the first step prepares, add particle diameter 10nm nano silicon 12g, insert simultaneously in the 500ml there-necked flask; Under rare gas element helium He protection; With 3000r/min magnetic agitation 2h, take out modified powder, disperse 30min subsequent use with sonic oscillation again under 10 ℃.
5. composite coating by claim 1 or the preparation of 2 described modified manometer silicon dioxides; It is characterized in that; It is by above-mentioned modified manometer silicon dioxide, titanium oxide and pearl filler; Add various auxiliary agents and grind, add the emulsion allotment then and form, above-mentioned auxiliary agent comprises commercially available film coalescence aid, dispersion agent, wetting agent, mould inhibitor and skimmer.
6. composite coating as claimed in claim 5; It is characterized in that described film coalescence aid selects that high boiling point film coalescence aid and 20 ℃ of density 0.85g/ml~0.95g/ml, viscosity 20~30mPas, pH values of ester content>=99%, acid number≤1.0mKgKOH/Kg, moisture content≤0.2%, boiling point: 253-283 ℃ are 0~5 for use, VOC is that 0 film coalescence aid mixes.
7. according to claim 1 or claim 2 the application of nano silicon in preparation rubber-emulsion paint composite coating, rubber and plastics polymer composite.
CN 201110348076 2011-10-29 2011-10-29 Novel modified nano silicon dioxide and composite coating prepared from same CN102504612B (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN104177655A (en) * 2014-07-10 2014-12-03 池州市英派科技有限公司 Modified nano-titanium dioxide with good dispersity and good uvioresistant effect and preparation method thereof
CN105355879A (en) * 2015-11-11 2016-02-24 兰州理工大学 Composite carbon coated metal oxide and preparation method thereof
CN105602411A (en) * 2016-04-01 2016-05-25 厦门大学 Fluorine-containing hydrophobic coating material and preparation method thereof
CN105733408A (en) * 2016-04-01 2016-07-06 厦门大学 Self-lubricating coating for knuckle bearing and preparation method thereof
CN104130422B (en) * 2014-07-25 2017-08-29 鲁东大学 A kind of silica gel keys carry the preparation method of daiamid type tree shaped numerator adsorbent
CN107446417A (en) * 2017-08-16 2017-12-08 天津市津海特种涂料装饰有限公司 A kind of thick coated type chlorinated rubber antirust paint
US9950307B1 (en) * 2013-08-29 2018-04-24 University Of South Florida Metal chelating composites, methods of using composites, and methods of making composites
CN109486344A (en) * 2018-09-30 2019-03-19 镇江宝海船舶五金有限公司 A kind of antibacterial epoxy coating of anchor chain and preparation method thereof

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CN102058891A (en) * 2009-11-11 2011-05-18 首都医科大学 Fluorescent magnetic silicon nano carrier modified with polyethylene glycol and preparation method and application

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US20030012942A1 (en) * 2001-05-03 2003-01-16 The Board Of Regents Of The University Of Nebraska Sol-gel preparation of porous solids using dendrimers
CN102058891A (en) * 2009-11-11 2011-05-18 首都医科大学 Fluorescent magnetic silicon nano carrier modified with polyethylene glycol and preparation method and application

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9950307B1 (en) * 2013-08-29 2018-04-24 University Of South Florida Metal chelating composites, methods of using composites, and methods of making composites
CN104177655A (en) * 2014-07-10 2014-12-03 池州市英派科技有限公司 Modified nano-titanium dioxide with good dispersity and good uvioresistant effect and preparation method thereof
CN104177655B (en) * 2014-07-10 2016-01-20 池州市英派科技有限公司 Modified nano-titanium dioxide that a kind of scattered uvioresistant is effective and preparation method thereof
CN104130422B (en) * 2014-07-25 2017-08-29 鲁东大学 A kind of silica gel keys carry the preparation method of daiamid type tree shaped numerator adsorbent
CN105355879A (en) * 2015-11-11 2016-02-24 兰州理工大学 Composite carbon coated metal oxide and preparation method thereof
CN105355879B (en) * 2015-11-11 2019-07-02 兰州理工大学 Composite carbon coated metal oxide and preparation method thereof
CN105733408A (en) * 2016-04-01 2016-07-06 厦门大学 Self-lubricating coating for knuckle bearing and preparation method thereof
CN105602411A (en) * 2016-04-01 2016-05-25 厦门大学 Fluorine-containing hydrophobic coating material and preparation method thereof
CN107446417A (en) * 2017-08-16 2017-12-08 天津市津海特种涂料装饰有限公司 A kind of thick coated type chlorinated rubber antirust paint
CN109486344A (en) * 2018-09-30 2019-03-19 镇江宝海船舶五金有限公司 A kind of antibacterial epoxy coating of anchor chain and preparation method thereof

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