CN102504612B - 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 PDFInfo
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- CN102504612B CN102504612B CN 201110348076 CN201110348076A CN102504612B CN 102504612 B CN102504612 B CN 102504612B CN 201110348076 CN201110348076 CN 201110348076 CN 201110348076 A CN201110348076 A CN 201110348076A CN 102504612 B CN102504612 B CN 102504612B
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Abstract
The invention discloses 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
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 be subject to 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, the unique not available small-size effect of physics, chemical property and conventional material, quantum size effect and the surface-interface effect with it, increased substantially the scratch resistant of coating products, anti-aging, water-fast scrubbing property, antistatic, smooth finish, contrast ratio and the performances such as the surface hardness of filming and self-cleaning ability.For example: external develop the transparent automobile finish hybrid resin base coating (the hydridization phase size is nano level) of scratch resistant, ultraviolet resistance and resistance to chemical attack, and be applied to the automobile of the Multiple Type 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 the coated material on surfaces such as can be used for concrete, stone material, pottery, timber, glass, the nanotechnology that it is said this coatings applications, can reduce by the surface tension of coating surface (hydrophobic, oleophobic), thereby reach the purpose of anti-soil, antifog, easy cleaning, the said firm has also released the acrylate paint of self-cleaning type exterior coating silicon nanostructure modification, and research is found: mix nano level TiO in resin
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 accordingly develop be applicable to the compound electrostatic shielding coating of resin-base nano oxide compound of electric appliance casing, with the coating that traditional resin base carbon black is compound, compare, 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 militarily utilized, the forms that also Nano filling is added in many employings at present, its stealthy principle is: the nanoparticle size is much smaller than infrared and radar wave wavelength, be also that nanoparticle material is higher than conventional material to the transmitance of infrared and radar wave, the specific surface area of nanoparticle is much larger than conventional powder, cause it also high to electromagnetic specific absorption, thereby cause nanoparticle material to descend to the reflectivity of infrared and radar wave, it is faint that the signal that makes infrared eye and radar receive becomes, thereby play stealthy effect, for example: on U.S. F117A type aircraft, just scribble the stealth material with wideband electromagnetic ripple receptivity formed by multiple ultramicron.
And also developed in research institution of the many companies of China the nano paint that hydrophobic antifouling dyes building coating, antibacterial inner wall paint and emulsion paint uvioresistant anti-aging nano paint and has certain photocatalytic activity (but in the catalyzed oxidation air obnoxious flavour) and disinfection function, these nano-level coatings are except the film forming base-material is carried out the improvement on technical recipe, also mostly be and adopt the form of adding nanometer grade powder to prepare nano composite dope, for example: in design aqueous architectural coating formula process, the nanometer SiO that the interpolation massfraction is 3% left and right
2, through disperseing to obtain fully the coating of modification, its every technical performance index all has significant improvement: shortened to and be less than 1h time of drying by original 2h; 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 is brought up to 450h and is not any change by one-level variable color, the secondary efflorescence of 240h, still, and due to nanometer SiO
2for unformed white powder (referring to its soft aggregate), through the transmission electron microscope test analysis, this material obviously presents cotton-shaped and netted accurate grain pattern, particle size little (3～15nm), the large (640 ± 50m of specific surface area
2/ g), there is the hydroxyl of a large amount of unsaturated residual bonds and different bond styles in surface, very easily causes the impact of reuniting to disperse, and when especially content is higher, reunites more outstanding.Because the practical application of nano material depends primarily on surface molecular design conditions (how solving the compatibility problem with the body material system) and the dispersity in body material thereof of nano-powder material, therefore, when preparing nano paint, the dispersion of nano-powder becomes the key of the good coating of processability, and the dispersiveness of raising nano-powder, guarantee the consistency of filler with the film forming base-material, the nano powder surface modification is become again to the key for preparing functional paint, this is because the character of inorganic powder surface character and film forming organic substrate differs larger, consistency missionary society affects inorganic nanometer powder being uniformly dispersed at film process
The property.
At present, in preparing the nano paint process.The dispersion of filler is adopted more to the mode of physical dispersion, as: grinding distribution, sand milling dispersion, Ball milling, high-speed stirring (more than 1500r/min) etc., in addition, when nano-powder disperses in liquid, also can adopt the dispersion modes such as ultrasonic dispersion, colloidal mill dispersion, high energy particle processing.But the mode of above-mentioned mechanical dispersion all is difficult for " overheated " disperses, and because of in dispersion process, powder particle will be subject to strong 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 siloxane bond in powder surface), so chemical reaction more easily occurs in powder surface, along with the increase of heat energy and mechanical energy, the probability of particle collision also increases, and causes on the contrary further reunion simultaneously.This secondary " reunite,, make the stability in storage variation of slurry, be difficult to the suspension property and the workability that keep stable.Therefore to powder surface modification can reduce on the one hand powder surface can, the opposing party can improve the consistency of same matrix, and powder-modified mode is mainly contained at present: 1. coupling agent method.By coupling agent modified powder, strengthened the solubility of nanoparticle in organic medium, can be dispersed in preferably in organic matrix, 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 by 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, the solubility by organic branched compound in organic medium, strengthen the dispersion of nanoparticle in organic medium.For example: utilize nanometer SiO
2lip-deep active site easily produces the character of living radical, Thmoas and Espiard have studied respectively vinyl-acetic ester graft polymerization reaction in its surface and the graft polymerization reaction of ethyl propenoate, the 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 or surface graft modification, this modified effect that forms chemisorption (chemical bond) at powder surface depends primarily on the factors such as the concentration of quantity, properties-correcting agent of powder surface active site and molecular weight, and obtaining 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 of diameter of particle size and distribution seemed to 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 at cavity and molecular chain characteristics such as having controllability accurately, in recent years, the research work of relevant PAMAM is very active.The investigator is that template has prepared Cu by PAMAM both at home and abroad, Ag, and Pd, Pt, Au, ZnO, CdS, the nano-substances such as ZnS, obtain size even, the nanoparticle that distribution range is narrower.And take at present the document that PAMAM is template preparation modified inorganic nano silicon, have not been reported, find that according to research PAMAM surpasses more than 4 generations, almost become globosity, the cavity that comparatively large vol is contained in inside, in addition because the PAMAM intramolecule contains more functional group, as carbonyl (C=O), inferior acylamino hydrogen (NH), these active function groups are prerequisites of adsorption of modification nano-powder silicon-dioxide.
Summary of the invention
The purpose of this invention is to provide a kind of preparation size distribution controlled, the uniform modified manometer silicon dioxide powder of size, rely 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 prepared by this modified manometer silicon dioxide powder simultaneously.
Modified manometer silicon dioxide powder of the present invention is by 4.0 PAMAM type dendrimers (following replace with PAMAM) and nanometer SiO
2powder mixes according to 50: 12 part by weight, under protection of inert gas, through magnetic agitation and sonic oscillation post-modification, comes.
Can be prepared by following methods by modified manometer silicon dioxide powder of the present invention:
First synthesize PAMAM, then realize dry method modification nanometer SiO as template
2the purpose of powder, manufacture craft is as follows in detail:
The first step: preparation PAMAM
At first, take the second diamino as the core primitive, in methyl alcohol, with methyl acrylate, carry out Michael addition reaction thoroughly, obtain the adduct of three methyl acrylates.Then carry out the aminolysis reaction of ester with excessive quadrol, obtain amidation triamino product, then the addition reaction of repetition and methyl acrylate, prepare the PAMAM in 4.0 generations.
Second step: prepare modified manometer silicon dioxide
By 4.0 generation PAMAM50g of preparation, add nano silicon (particle diameter 10nm left and right) 12g to mix, at the uniform velocity stir 2h at the protection of inert gas lower magnetic force, then sonic oscillation 30min, obtain needing the modified manometer silicon dioxide powder prepared.
Above-mentioned rare gas element is preferentially selected helium.
Composite coating of the present invention is by fillers such as above-mentioned modified manometer silicon dioxide, titanium dioxide, calcium carbonate, add various auxiliary agents to be ground, then add the emulsion allotment to form, above-mentioned auxiliary agent comprises film coalescence aid, dispersion agent, wetting agent, mould inhibitor and defoamer, is the commercially available prod for preparing coating;
In order greatly to reduce VOC content in coating, film coalescence aid is selected: high boiling point film coalescence aid DBE-IB (ester content >=99%, acid number≤1.0mgKOH/g, moisture content≤0.2%, 253-283 ℃) and Kening Co.,Ltd's VOC free film coalescence aid LOXANOL EFC300 (density (20 ℃): 0.85～0.95 of producing boiling point:, viscosity: 20～30mPas, acidity: 0～5, VOC is 0).
With modified manometer silicon dioxide of the present invention, can also add 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 the wet-process modified certain cost of having saved, technique is simple, and modified effect is outstanding.The dispersed raising after modification, can form finer and close coating during prepared coating film forming as can be seen from Figure 3, and in coating, filler distribution is even as can be seen from Figure 4, has improved the over-all properties of coating.
2, this method adopts high boiling point film coalescence aid DBE-IB and LOXANOL EFC300, 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.
The accompanying drawing explanation
Fig. 1 is nano silicon dry method modification schematic diagram of the present invention;
Fig. 2 is nano-silicon dioxide modified front SEM picture;
Fig. 3 is the SEM picture of the present invention after nano-silicon dioxide modified;
Fig. 4 is the SEM picture of the composite coating coating of utilizing nano silicon of the present invention to prepare.
In Fig. 1: 91-Siliciumatom, 76-nitrogen-atoms (with silicon with singly bound).
Embodiment
Describe technical scheme of the present invention in detail below by concrete implementation step.
Modified manometer silicon dioxide preparation method of the present invention is as follows:
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 in to the 400mL volumetric flask, and 5 ℃ of lower magnetic forces stir, after logical He protection 1h; drip the mixture of quadrol 10.5g and methyl alcohol 27.5g with dropping funnel; drip 1h logical He, after dropwising, under room temperature, react 36h.With Rotary Evaporators underpressure distillation (about 140Pa, 40 ℃), remove unreacted methyl acrylate and methyl alcohol, obtain micro-yellow slightly thick liquid.
The preparation of (2) 1.0 generation PAMAM: quadrol 84g and methyl alcohol 11g are placed in to the 500mL volumetric flask, and 5 ℃ of lower magnetic forces stir, after logical He protects after 1h; drip the mixture of 0.5 generation PAMAM20g and methyl alcohol 64g with dropping funnel; drip 2h logical He, after dropwising, under room temperature, react 36h.With Rotary Evaporators underpressure distillation (about 140Pa, 60 ℃), remove unreacted quadrol and methyl alcohol, obtain micro-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 by the Michael addition reaction, are called for 0.5 generation; (b): ammonolysis reaction occurs and generates a quaternary amide compound in quaternary ester and excessive EDA, is called for 1.0 generations.Repeat the reactions steps of (a), (b) Michael addition and ammonia solution, 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 PAMAM50g that the first step is prepared; add nano silicon (particle diameter 10nm left and right) 12g; insert in the 500ml there-necked flask simultaneously; under rare gas element helium (He) protection; with 3000r/min magnetic agitation 2h; take out modified powder, with sonic oscillation, disperse 30min standby again under 10 ℃.
Its modification theory is: in whipping process, nano silica powder is subject to the effect of the power such as mechanical shearing force, impact force and frictional force, heterolytic fission or homologisation occur, obtain the active silica powder, its cracking process and the results are shown in formula (1) and (2), the active body skeleton symbol after cracking is shown in structural formula (3);
Then under properties-correcting agent PAMAM effect, the active silica powder reacts with PAMAM, thereby obtains the nano silica powder of modification, and modification theory is shown in Fig. 1; The 1.0 generation PAMAM improved silica cation groups of take in figure are example, so that explanation PAMAM and silicon ion in conjunction with situation, formed chemical bond between silicon ion and PAMAM as can be seen from Figure, dry method modification takes full advantage of the activity of the amide group in the PAMAM molecule, present electronegativity on N atom 76, and silicon positively charged ion 91 presents positive polarity, more easily form the N-Si key.
Finally the nano silicon activation number after modification is measured, the method of measuring activation index is as follows: with the 200mL beaker, add 150mL distilled water, the filler powder 10g got after modification adds wherein, stir 2min also more than standing 1h with glass stick, then will fall to beaker bottom material filtering, dry, weigh, deduct the quality of this sedimentation material by the former quality taken (10g), can obtain the quality of floating part in sample.In activation number=sample, the quality of floating part/sample total mass, can try to achieve activation index.
Through check, the activation number of improved silica of the present invention reaches 0.94, according to another Fig. 2 and Fig. 3, relatively can find out, 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 dioxide, calcium carbonate, add various auxiliary agents and film forming base-material to be ground, then add the emulsion allotment to form, the proportioning of various color stuffings, auxiliary agent and emulsion, concrete proportioning situation is in Table lattice 1, and preparation process is as follows in detail:
The first step: get high boiling point film coalescence aid DBE-IB:1.4g, LOXANOL EFC300:2.8g, dispersion agent FS3204:0.15g, dispersing agent C D50:0.4g, wetting agent H885:0.2g, wetting agent 188A:0.10g, defoamer A10:0.10g, defoamer F111:0.15g, adhesion promoter 0.05:g and deionized water 20g, stirring at low speed 15min evenly mixes, the silicon-dioxide 20g and other color stuffings 11g that add again modification, thickening material HEC:0.4g, thickening material DSX3116:0.5g and supplementary part deionized water carry out high speed dispersion, make white slurry, jitter time is not less than 1.5h.
Second step: ground white slurry is joined at a slow speed in 35g benzene emulsion PA237 in batches to (refer at a slow speed until before batch white slurry added a collection of white slurry after stirring at low speed just can add after evenly) to continue stirring at low speed even again in batches, finally by the first viscosity of coating of thickening material adjustment, adjusting the pH value by pH adjusting agent is 8.5 to be the emulsion paint finished product.
In order to verify the performance of composite coating of the present invention, the nano silicon of getting respectively modification of the present invention is prepared into composite coating with existing unmodified nano silicon and carries out performance comparison, and comparing result is in Table 2, and the method for inspection is according to GB/T9755-2001.
As can be seen from Table 2, the property indices of the composite coating of preparation all is improved significantly.
Table 1 formula rate (unit: g)
The coating traditional performance contrast that the nano-silicon dioxide modified front and back of table 2 are prepared
Claims (7)
1. a modified manometer silicon dioxide, is characterized in that, it is by 4.0 PAMAM type dendrimers and nanometer SiO
2powder mixes according to 50: 12 part by weight, under protection of inert gas, through magnetic agitation and sonic oscillation post-modification, comes; Magnetic agitation speed is 3000r/min, churning time 2h.
2. modified manometer silicon dioxide as claimed in claim 1, is characterized in that, described rare gas element is helium.
3. a method for preparing modified manometer silicon dioxide as claimed in claim 1 or 2, is characterized in that, first synthesizes PAMAM, then realize dry method modification nanometer SiO as template
2the purpose of powder, manufacture craft is as follows in detail:
The first step: preparation PAMAM
At first, take quadrol as the core primitive, in methyl alcohol, with methyl acrylate, carry out Michael addition reaction thoroughly, obtain the adduct of tetrapropylene acid methyl esters; Then carry out the aminolysis reaction of ester with excessive quadrol, obtain amidation tetramino product, then the addition reaction of repetition and methyl acrylate, prepare the PAMAM in 4.0 generations;
Second step: prepare modified manometer silicon dioxide
By 4.0 generation PAMAM50g of preparation, add the nano silicon 12g of particle diameter 10nm to mix, at the uniform velocity stir 2h at the protection of inert gas lower magnetic force, then sonic oscillation 30min, obtain needing the modified manometer silicon dioxide powder prepared.
4. the method for preparing modified manometer silicon dioxide as claimed in claim 3, is characterized in that, detailed step is as follows:
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 in to the 400mL volumetric flask, and 5 ℃ of lower magnetic forces stir, after logical He protection 1h, drip the mixture of quadrol 10.5g and methyl alcohol 27.5g with dropping funnel, drip 1h logical He, after dropwising, under room temperature, react 36h; With Rotary Evaporators underpressure distillation under 140Pa, 40 ℃ of conditions, remove unreacted methyl acrylate and methyl alcohol, obtain micro-yellow slightly thick liquid;
The preparation of (2) 1.0 generation PAMAM: quadrol 84g and methyl alcohol 11g are placed in to the 500mL volumetric flask, and 5 ℃ of lower magnetic forces stir, after logical He protects after 1h, drip the mixture of 0.5 generation PAMAM20g and methyl alcohol 64g with dropping funnel, drip 2h logical He, after dropwising, under room temperature, react 36h; With Rotary Evaporators underpressure distillation under 140Pa, 60 ℃ of conditions, remove unreacted quadrol and methyl alcohol, obtain micro-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
The 4.0 generation PAMAM50g that the first step is prepared, add particle diameter 10nm nano silicon 12g, inserts in the 500ml there-necked flask simultaneously; under rare gas element helium He protection; with 3000r/min magnetic agitation 2h, take out modified powder, with sonic oscillation, disperse 30min standby again under 10 ℃.
5. the composite coating prepared by the described modified manometer silicon dioxide of claim 1 or 2, it is characterized in that, it is by above-mentioned modified manometer silicon dioxide, titanium dioxide and pearl filler, add various auxiliary agents to be ground, then add the emulsion allotment to form, above-mentioned auxiliary agent comprises commercially available film coalescence aid, dispersion agent, wetting agent, mould inhibitor and defoamer.
6. composite coating as claimed in claim 5, it is characterized in that, described film coalescence aid selects the film coalescence aid that the high boiling point film coalescence aid of ester content >=99%, acid number≤1.0mKgKOH/Kg, moisture content≤0.2%, boiling point: 253-283 ℃ and 20 ℃ of density 0.85g/ml～0.95g/ml, viscosity 20～30mPas, pH values are 0～5, VOC is 0 to mix.
7. the application of modified manometer silicon dioxide as claimed in claim 1 or 2 in preparing emulsion paint composite coating, rubber and plastics polymer composite.
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| CN110713604B (en) * | 2019-10-14 | 2021-07-13 | 浙江海洋大学 | Preparation method of PAMAM composite antifouling material |
| CN111151230A (en) * | 2019-11-04 | 2020-05-15 | 鲁东大学 | Magnetic Fe3O4Preparation method of supported dendrimer adsorbent |
| CN111589428B (en) * | 2020-05-18 | 2023-01-31 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Composite material for purifying air and preparation method thereof |
| CN111825480B (en) * | 2020-08-13 | 2022-11-04 | 西藏大学 | Ultraviolet-resistant super-hydrophobic anti-freezing material and preparation method thereof |
| CN113583452B (en) * | 2021-08-11 | 2022-08-16 | 深圳市鑫俊通科技有限公司 | Anti-slip silica gel applied to keyboard keys |
| CN115626805B (en) * | 2022-10-31 | 2023-09-15 | 山东高速工程建设集团有限公司 | Slag gypsum-based cementing material and preparation method thereof |
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