CN101235251A - Obdurability protection coating material for thermal shielding vehicle and preparation method thereof - Google Patents
Obdurability protection coating material for thermal shielding vehicle and preparation method thereof Download PDFInfo
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- CN101235251A CN101235251A CNA2008100593478A CN200810059347A CN101235251A CN 101235251 A CN101235251 A CN 101235251A CN A2008100593478 A CNA2008100593478 A CN A2008100593478A CN 200810059347 A CN200810059347 A CN 200810059347A CN 101235251 A CN101235251 A CN 101235251A
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Abstract
Intensified protective film material for a thermal shield car and a preparation process are disclosed. The preparation process mainly comprises conducting reflux hydrolysis cocondensation for terminated silicon imine I (SiO1-1.5)2 or terminated silicon oxazolidinone OX (SiO1-1.5)2 or terminated silicon polyisocyanates- oxazolidinone PIOX (SiO1-1.5)3, carbon nano tube and metallic alcoholate, transient metal coordinated complex compound in absolute alcoholic solution under the acid condition, or conducting hydrolysis cocondensation with inorganic metal salt, or producing sol through the reflux hydrolysis cocondensation with functional sol under the above-mentioned conditions to prepare the product through adding a certain amount of stabilizer. The product which is prepared through the process of the invention has self-cleaning, thermal shield, natural temperature regulating and high intensified function, which is suitable to intelligent protective material of various cars.
Description
Technical field:
The invention belongs to automobile-used protection class coating material.
Background technology:
Generally use along with China's family-sized car, automobile-used performance requirement of filming is also being improved constantly, existing in the market automobile-used protection class coating material can't satisfy the requirement of following automobile-used coating, and some high-quality automobile-used films more and more are subjected to pursuing of market.Especially require to comprise functions such as heat insulation, impact resistance, high rigidity be anti-scratch.Existing nano-film coating and intelligent building dimming glass its preparation method adopt (1) chemical vapor deposition (CVD) method; (2) physical vapor deposition (PVD) method; (3) so-gel high-temperature sintering process; (4) technology such as interlayer composite algorithm exist preparation costly, and the large-area treatment difficulty is big; Also there are many performance deficiencies simultaneously, do not reach expected effect as A, photocatalysis; B, the fluorine carbon control self-cleaning poor durability of filming, erosion resistant not is difficult on the car body as stated above and practices.
With the present invention be coated with method that the more approaching traditional preparation process metal oxide of membrane technique films be its technical process of sol-gel method craft as shown in Figure 1
One, this conventional metals oxide coating film preparation technology's weak point is:
1, technology of preparing aspect: 1) complicated process of preparation; 2) structure is formed simple; 3) energy consumption height; 4) investment cost height; 5) products production cost height; 6) pure metal oxides hardness of film high-wearing feature is good, but snappiness and crash-worthiness are poor.
2, film forming and construction
Because the restriction of high temperature film-forming process is difficult to overlay film on car body, (comprising part or integral construction), cause on car body as protection film use limited.
3, proterties: the colloidal sol performed polymer of above-mentioned preparation technology's system is the gel state of network molecule structure, and particle size distribution is wide, and mobile difference is difficult for spraying.
Two, form simple in structure and weak point on the product performance that causes has:
1, function singleness; 2, functional performance does not reach expected effect; 3, can not realize integrated and energy-conservation effect of temperature adjustment of function etc.
Summary of the invention
The present invention be according to car with the problem that protection development trend of class coating material and prior art exist, provide a kind of collection automatically cleaning, the automobile-used protective coating of characteristic such as thermoshield and natural temp regulating be in one, and have impact resistance, and be anti-scratch.
For achieving the above object, automobile-used filming of the present invention is that CNT (carbon nano-tube) and many components metal oxide are that alcohol solube metallic salt and co-ordination complex (co-ordination complex that comprises metal alkoxide M (OR) n, nitrate, muriate, methyl ethyl diketone) thereof are made for basic raw material as precursor by end silicon imide or Duan Gui oxazolidone.It forms with weight content wt% as follows:
I (SiO
1-1.5)
2Or OX (SiO
1-1.5)
2Contain 10-30; SiO
2Contain 20-50; Al
2O
3Contain 2-20; TiO
2Contain 1-20; CeO
2Contain 0.2-20; WO
3Contain 1-5; ZrO
2Contain 1-10; ZnO contains 1-10; NiO contains 1-10; Y
2O
3Contain 0.1-5; FCOSiO
1-1.5Contain 0.1-5; VO
2Contain 0.5-10; CNTS contains 0.1-10; In
2O
3Contain 0.02-5.
Wherein: 1) CNTS is a CNT (carbon nano-tube).
2) end siloxy imide I (SiO
1-1.5)
2Structural formula be:
3) end silicon _ oxazolidone OX (SiO
1-1.5)
2Structural formula be:
Annotate: R=propyl group, phenyl, hexichol ether, S=-SiMe (OR)
2,-Si (OR)
3R=methyl, ethyl in the formula.
4) end silicon PFPE FcoSiO
1-1.5, three kinds of general structures are arranged:
(1) the poly-propyl ether of end silicon perfluor
(2) end silicon perfluor second third copolyether
(3) end perfluor oxyethyl group ether
Annotate: W=(RO)
3SiP-, (RO)
3SiPO-P-, P=propylidene (CH
2)
3, PO=propoxy-, FE=perfluor ethylidene, iFPO=perfluor isopropoxy, FEO=perfluor oxyethyl group, X=-SO
2F.
The preparation method of above-mentioned intelligent film coating material:
1, automobile-used filming of the present invention is to be that (metal alkoxide compound) CNT (carbon nano-tube) CNTS is in absolute alcohol (ethanol, Virahol, butanols etc.) solvent by end silicon acid amides or Duan Gui oxazolidone with many components alcohol solube metallic salt M (OR) n, back hydrolysis condensation under the acidic catalyst effect, because the active high hydrolysis rate of transition metal alkoxide is fast in hydrolysis-condensation reaction, for balanced reaction speed obtains the colloidal sol body of the relative homogeneous transparent of structure distribution, adopt the hydrolysis rate of transition metal alkoxide such as inhibition such as methyl ethyl diketone (AcAc) sequestrant of etc.ing.Chelatropic reaction and structure are as shown in the formula M (OR) n+xAcAc=M (OR)
N-x(AcAc) to be advisable be that M (OR) n/AcAc=1-3 is advisable to x X=1-3.In advance the transition metal alkoxide is dissolved in anhydrous solvent, the methyl ethyl diketone (ACAC) that under agitation adds aequum, the complex solution for preparing mixes with integral parts such as other nontransition metal alkoxide, with the storng-acid cation exchange resin is catalyzer, logical nitrogen is in 60-150 ℃ of backflow 1-5h under stirring under PH2-5, and the consumption of water is to be advisable in ratio≤3 of water/metal oxide precursor in the system.Reaction finishes the solution behind the separating catalyst, steams solvent (taking remaining moisture content out of), and its solvent can use repeatedly.Remove anhydrous sol behind the solvent and add anhydrous alcohols equal solvent and be diluted to 10-50%, and add and store after solidifying catalyzer, stablizer, compound solubilizing agent.But redilution as required during use.But this colloidal sol body prolonged storage under sealed state does not produce gel and precipitation.
2, on the basis of above-mentioned technology 1, consider to adopt metal alkoxide and an amount of inorganic metal salt the part that is the metal alkoxide described in the aforesaid method under acidic conditions (PH2-5) from factors such as raw material sources and raw materials cost, the mixed hydrolysis condensation method in alcoholic solution.Used inorganic metal salt is preferably selected nitrate, hydrochloride (muriate) and ammonium salt.The preparation dissolving water of inorganic salt, preparation urges agent and the contained crystal water of inorganic salt all to include the hydrolysis water consumption as calculated in.(being in the scope of ratio≤3 of water/metal oxide).
In the reaction because of by product HNO that nitrate generated
2And NO
2Available ammonia or
Decompose:
The Cl that in reaction system, has the muriate precursor to be generated
-Or HCl absorbs by tail gas or generates insoluble hypostasis and separates.
Back flow reaction (1-5h) end back operation steps is identical with aforesaid method 1.
Illustrate: the colloidal sol of present method preparation is that solubility is low viscous organic---the inorganic hybridization interpolymer, forming structure is the linear cocondensation zoarium of molecular level, simultaneously, owing to pass through the control preparation condition in the product preparation process, can not form gel state and precipitation.Its water consumption is one of key factor in this preparation method, and the product dehydration also is one of key factor that influences the product storage-stable.Simultaneously at decomposing H NO
2Shi Suoyong NH
3Or urea must should not be excessive in More's number of nitroxyl content otherwise also can cause precipitation to form.
3, the functional unit colloidal sol by adopting above-mentioned 1,2 prepared is compounded in as the codoped that is hydrolyzed under the above-mentioned condition with relevant precursor during its structure is formed and can obtains the required function composite sol.
Basic structure is formed:
The colloidal sol of preparation has following functional performance:
1) high-strong toughness:
Form the organic-inorganic metal oxide copolymer height obdurability that contains polyamide structure with multiple metal oxide precursor cocondensation and the strength and toughness of protection class coating material is fully strengthened by the basic link units of polyimide (PI) is made high temperature resistant and obdurability polymkeric substance chain link unit such as end siloxanes imide or end siloxy oxazolidone with the siloxane blocking with hydrolysis reaction activity, and because CNT (carbon nano-tube) is assembled interstitital texture body class coating material with metal oxide formation has with the easy look characteristics in angle by adding CNT (carbon nano-tube) simultaneously.
2) thermoshield and selective regulation functional performance:
This class coating material from energy-conservation temperature adjustment need, but the nano-metal-oxide of reflective infrared light wave that in the material compositional system, mixes, as ZnO
2, Ln
2O
3, Y
2O
2, Al
2O
3With WO
3, V
2O
4Deng the coupling body of metal oxide, form the thermoshield ergasia.Doping thermo-sensitivity metal oxide such as vanadium oxide form and can reduce phase transition temperature between semi-conductor and conductor in system, reach with temperature Change and selectivity absorbs the function that reaches the selectivity attemperation with the shielding infrared waves in season.
3) photocatalysis characteristic:
Adopt with TiO in the coated material
2, CeO
2, ZnO, NiO, In
2O
3Deng consisting of the composite photocatalyst system, its objective is abundant raising photocatalysis and self-cleaning effect, form structure with other function simultaneously and form unified collaborative body mutually, play mutual enhancement each other.
Principle:
4), super two thin self-cleaning function:
Employing is mixed in essentially consist and is held siloxy perfluor ether or end silicon perfluor alkane and formation cocondensation zoarium, except that above-mentioned functions, also have the two thin characteristics of excellent benefit, especially air is had very strong affinity is attraction function to perfluor ether, therefore be coated with membrane interface and form little air film and isolate dirt, the automatic frontier of water droplet is fallen.
Preparation technology's flow process of the present invention as shown in Figure 2.
This automobile-used protection class coating material adopts raw material as follows:
One, basic raw material:
(1) basic raw material adopts following several:
1), end siloxy imide I (SiO
1-1.5)
2
2), Duan Gui oxazolidone OX (SiO
1-1.5)
2Or end silicon polymeric polyisocyanate-oxazolidone PIOX (SIO
1-1.5)
3
3), according to the co-ordination complex M (AcAc) of metal alkoxide compound M (OR) the n transition metal methyl ethyl diketone of the required Si of structure, Al, Ti, Ce, W, V, Ni, Zr, Zn, In, La, Y
nOr MO (AcAc)
N-2In the inorganic metal salt as nitrate or metal chloride (hydrochloride), ammonium salt and colloidal sol body
Annotate: among M (OR) n, M=metal, OR=alcoxyl oxygen base, n=metal valence state
4), end silicon perfluor ether comprises the poly-propyl ether of end silicon perfluor, end silicon perfluor second third copolyether, end silicon perfluor oxyethyl group ether
5), CNT (carbon nano-tube) CNTS;
Two, the selection for preparing required cooperation composition:
1) hydrolysis-condensation reaction catalyzer:
Storng-acid cation exchange resin, perfluorinated sulfonic acid or carboxylic acid and fluorine-containing Zeo-karb, acidic molecular sieve, nitric acid, hydrochloric acid and structure are formed needed metal nitrate, hydrochloride etc.
2) solvent: dehydrated alcohol, anhydrous isopropyl alcohol, methyl ethyl diketone, butanone or tetrahydrofuran (THF) etc.
3) stablizer: water-removal agent solidifies or gelation in the performed polymer storage process in order to prevent, can add stablizer and improve storage stability as siloxanes, silazane, ketoxime base organoalkoxysilane (being preferably the acetoxime radical siloxane), consumption 0.1-5% such as isocyanic ester and tripolymer, isocyanic ester radical siloxane tripolymer, hydrogen-containing siloxane.
4) curing catalysts:
The used curing catalysts of the present invention is a tin titanium composite catalyst system, and consumption is that 0.2-3% tin/titanium ratio of coated material composition is l-1.5, the perhaps metallic naphthenate of 0-3%.
5) compound solubilizing agent and consumption:
In low viscosity perfluor ether oil, in its ratio of mixture of low viscous alkoxy end-capped silicone oil be 1: 1, consumption is 1-5%.
Beneficial effect of the present invention: the present invention has good technical characterstic and functional performance.
1, prepares organic-inorganic metal divided oxide minor structure codoped by sol method, non-network solubility intelligent nano colloidal sol;
2, structure composition diversification and functional performance are polynary integrated;
3, functional performance: A, have high rigidity (＞7H) and snappiness impact resistance, anti-scratch; B, have purifying air and automatic cleaning action; C, thermoshield and selectivity thermoregulatory effect;
4, preparation technology is simple, energy consumption is low;
5, the normal temperature moisture-curable is easy to use;
6, pollution-free from being prepared into use;
7, solved that automobile-used coating does not have the thermoshield function and surface strength is low, not erosion resistant and bump come off, problems such as poor mechanical property such as scratch resistance, reach compoundization of functional performance, improve overall characteristic and practicality.Strengthened original functional property simultaneously, simplified preparation technology, reduced production costs significantly.From being prepared into the use non-environmental-pollution.
Description of drawings
Fig. 1 is the prior art processes schema;
Fig. 2 is the technology of the present invention process flow sheet.
Embodiment:
With reference to technique scheme embodiment is described:
Embodiment one:
1, presoma is formed and share
| Form (precursor) | Mass fraction | Form (precursor) | Mass fraction |
| Tetraethoxy | 125 | Zirconium iso-propoxide | 32 |
| End silicon imide | 31 | Titanium isopropylate | 57 |
| Multiple-wall carbon nanotube | 1 | The Virahol vanadium | 40.2 |
| Aluminum isopropylate | 21 | Methyl ethyl diketone | 70 |
| The ethanol indium | 3.2 | FCOSiO 1-1.5 | 4 |
| Cerous nitrate | 17 | Deionized water | 20 |
| Yttrium trinitrate | 2.5 | Dehydrated alcohol | 1000ml |
| Ethanol tungsten | 9.5 | Strongly acidic cation-exchange | 25-50 |
| Zinc nitrate | 14.2 | Urea | 18 |
| Nickelous nitrate | 13.8 | Compound solubilizing agent | 7.8 |
2, preparation process:
1) purification of CNT (carbon nano-tube):
(1) multiple-wall carbon nanotube (MWNTS) is scattered under high-speed stirring contains in the 0.5-1% tensio-active agent (as alkyl sodium sulfonate or cats product), or behind the ultra-sonic dispersion, standing sedimentation filters, and boils the vacuum heat filtering again through deionized water.
(2) above-mentioned CNT (carbon nano-tube) being invaded bubble with 1-10% nitric acid and spend the night, is that neutrality is to (PH5-7) with deionized water wash sedimentation vacuum filtration to filtrate more repeatedly, and drying is to anhydrous.
(3) with the MWNTS after the above-mentioned purification process and 0.1-1% end silicon perfluor ether, or fluorocarbon surfactant, be scattered in the absolute alcohol stand-by.
2) operation steps:
(1) the end silicon imide 1 (SiO that in reaction flask, add required following raw material: A in proper order, prepares in advance
1-1.5)
2Or end silicon mouth oxazolidone OX (SiO
1-1.5)
2Or end silicon polymeric polyisocyanate-oxazolidone PIOX (SIO
1-1.5)
3B, activation treatment is crossed CNT (carbon nano-tube) in advance.C, transition metal alkoxide is dissolved in dehydrated alcohol, makes complex solution by being metered into AcAc again.D, Nitrates are dissolved in ethanol or water.E, aluminum isopropylate or aluminium acetylacetonate are dissolved in the dehydrated alcohol.F, add inferior tetraethyl silicate components such as (TEOS) at refluxed under nitrogen 1-5h.
(2) hydrolytic condensation finishes filtration catalizer, filtrate steams solvent, and moisture content, add anhydrous solvent (dehydrated alcohol or Virahol, butanols, butanone, cyclohexanone, tetrahydrochysene are muttered etc.) again and be diluted to 10-50%, and adding stablizer 1-5%, tin titanium composite curing catalyzer (Sn/Ti=1-1.5), 0.2-3%.
Illustrate: prevent to generate in the reaction NOx and escape, tail gas absorbs with urea, and perhaps raw material is selected ammonium salt for use in forming, the More's numbers such as nitro in the ammonium salt in amino and the nitrate.
Can get the automobile-used composition of filming and the weight content per-cent of example one according to above-mentioned presoma composition, share and preparation process:
Sio
2 24％ I(Sio
1-1.5)
2 20％ CNTS 0.6％ AL
2O
3 10％ In
2O
3 2％
CeO
2 6％ Y
2O
3 3.5％ WO
3 3％ ZnO 2.5％ NiO 2.5％
ZrO
2 6.1％ VO
2 7.3％ FCOSiO
1-1.5 2.5％ TiO
2 10％
Embodiment two
| Form (precursor) | Mass fraction | Form (precursor) | Mass fraction |
| Tetraethoxy | 165 | The methyl ethyl diketone zirconium | 34.5 |
| End silicon imide | 24 | Titanium acetylacetone | 70.5 |
| Multiple-wall carbon nanotube | 0.8 | The methyl ethyl diketone vanadyl | 40 |
| Aluminum isopropylate | 35 | FCOSiO 1-1.5 | 3.2 |
| Tetrem acyl acetone cerium | 39.5 | Deionized water | In right amount |
| The methyl ethyl diketone yttrium | 8.1 | Dehydrated alcohol | 1000ml |
| Methyl ethyl diketone tungsten | 13.3 | Strongly acidic cation-exchange | 25-50 |
| The ethanol indium | 2.14 | Urea | 18 |
| Zinc nitrate | 18.4 | Compound solubilizing agent | 7.8 part |
| Nickelous nitrate | 11.6 |
Operation steps is with embodiment one:
The automobile-used composition of filming and the weight content per-cent of example two:
SiO
230% I (SiO
1-1.5)
2Or XO (SiO
1-1.5)
215%
CNTS 0.5％ AL
2O
3 9％ ln
2O
3 1.5％ CeO
2 8％
Y
2O
3 3％ WO
3 2％ ZnO 2％ NiO 3％
ZrO
2 6％ VO
2 9％ TiO
2 9％ FCOSiO
1-1.5 2％
Embodiment three:
| Form (precursor) | Mass fraction | Form (precursor) | Mass fraction |
| Tetraethoxy | 104 | Three ethanol indiums | 5 |
| End silicon imide or end silicon _ oxazolidone | 16 | Zinc nitrate | 9 |
| Nickelous nitrate | 12 | ||
| CNT (carbon nano-tube) (many walls) | 0.5-1 | Zirconium iso-propoxide | 17 |
| Temperature adjusting colloidal sol | 30 | FCOSiO 1-1.5 | 5 |
| Strongly-acid separaant exchange resin | 20 | Dehydrated alcohol | 1000ml |
| Methyl ethyl diketone | 51 | Urea | 7 |
| Tetrabutyl titanate | 16 | Distilled water | In right amount |
Operation steps is with 1:
1, in reaction flask, adds the A of required metering, the end silicon imide I (SiO for preparing in advance in proper order
1-1.5)
2Or end silicon _ oxazolidone OX (SiO
1-1.5)
2Or end silicon polymeric polyisocyanate-oxazolidone PIOX (SIO
1-1.5)
3B, activation treatment is crossed CNT (carbon nano-tube) in advance.C, transition metal alkoxide is dissolved in dehydrated alcohol, makes complex solution by being metered into AcAc again.D, Nitrates are dissolved in ethanol or water.E, aluminum isopropylate or aluminium acetylacetonate are dissolved in the dehydrated alcohol.Components such as F, adding tetraethoxy (TEOS), function colloidal sol are at refluxed under nitrogen 1-5h.
2, it is identical with example one that reaction finishes the back.
The automobile-used composition of filming and the weight content per-cent of example three are as follows:
SiO
240% I (SiO
1-1.5)
2Or XO (SiO
1-1.5)
210% CNTS O.3%
AL
2O
3 5％ TiO
2 12％ CeO
2 8％ Ln
2O
3 0.7％
WO
3 2％ Y
2O
3 1.5％ ZnO 3％ NiO 3％
ZrO
2 5％ VO
2 8％ FCOSiO
1-1.5 1.5％
The example of preparation function colloidal sol:
The preparation of temperature adjusting function colloidal sol
| Form (precursor) | Mass fraction | Form | Mass fraction |
| Tetraethoxy | 329 | Cerous nitrate | 72 |
| The Virahol vanadium | 132 | Methyl ethyl diketone | 200 |
| Ethanol tungsten | 19 | Dehydrated alcohol | 1600 |
| Isopropyl titanate | 236 | Storng-acid cation exchange resin | 20-25 |
| Aluminum isopropylate | 47 | Deionized water | In right amount |
Wherein: 1, transition metal alkoxide is dissolved in dehydrated alcohol, adds AcAc and stir 50min with volume; 2, nitrate is dissolved in the absolute alcohol, adds tetraethyl silicate then, integral parts such as transition metal coordination complexes are at refluxed under nitrogen condensation 3h, and following operation steps is identical with example 1.
The composition and the weight content per-cent of this kind temperature adjusting function colloidal sol:
SiO
2 27.6％ VO
2 11％ TiO 16.5％ WO
3 27.2％
AL
2O
3 6.7％ CeO
2 11％
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to the foregoing description, can also many operative combination.The all scenario that those of ordinary skill in the art can directly derive or associate from disclosure of invention all should be thought protection scope of the present invention.
Claims (8)
1, obdurability protection coating material for thermal shielding vehicle is characterized in that forming with weight content wt% as follows:
L (SiO
1-1-5)
2Or OX (SiO
1-1-5)
2Contain 10-30; SiO
2Contain 20-50; TiO
2Contain 2-20; Al
2O
3Contain 2-20; CNTS contains 0.1-5; CeO
2Contain 0.2-20; ZnO contains 1-10; NiO contains 1-10; Y
2O
3Contain 0.1-5; ZrO
2Contain 1-10; WO
3Contain 1-5; VO
2Contain 0.5-10; FCOSiO
1-1.5Contain 0.1-5; In
2O
3Contain 0.02-5.
2,, it is characterized in that composition and weight content are by the described obdurability protection coating material for thermal shielding vehicle of claim 1:
SiO
2 24％ I(Sio
1-1.5)
220％ CNTS 0.6％ AL
2O
3 10％ In
2O
3 2％
CeO
2 6％ Y
2O
3 3.5％ WO
3 3％ ZnO 2.5％ NiO 2.5％
ZrO
2 6.1％ VO
2 7.3％ FCOSiO
1-1.5 2.5％ TiO
2 10％
3,, it is characterized in that composition and weight content are by the described obdurability protection coating material for thermal shielding vehicle of claim 1:
SiO
230% I (SiO
1-1.5)
2Or XO (SiO
1-1.5)
215%
CNTS 0.5％ AL
2O
3 9％ ln
2O
3 1.5％ CeO
2 8％
Y
2O
3 3％ WO
3 2％ ZnO 2％ NiO 3％
ZrO
2 6％ VO
2 9％ TiO
2 9％ FCOSiO
1-1.5 2％
4,, it is characterized in that composition and weight content are by the described obdurability protection coating material for thermal shielding vehicle of claim 1:
SiO
240% I (SiO
1-1.5)
2Or XO (SiO
1-1.5)
210% CNTS 0.3%
AL
2O
3 5％ TiO
2 12％ CeO
2 8％ Ln
2O
3 0.7％
WO
3 2％ Y
2O
3 1.5％ ZnO 3％ NiO 3％
ZrO
2 5％ VO
2 8％ FCOSiO
1-1.5 1.5％
5,, it is characterized in that composition and weight content are by the described obdurability protection coating material for thermal shielding vehicle of claim 1:
SiO
2 27.6％ VO
2 11％ TiO 16.5％ WO
3 27.2％
AL
2O
3 6.7％ CeO
2 11％
6, by the described obdurability protection coating material for thermal shielding vehicle of claim 1, wherein I (SiO
1-1.5)
2Or OX (SiO
1-1.5)
2Structural formula as follows:
1) end siloxy imide I (SiO
1-1.5)
2] structural formula be following two kinds:
2) end silicon _ oxazolidone OX (SiO
1-1.5)
2] structural formula be following two kinds:
Annotate: R=propyl group, phenyl, hexichol ether, S=-SiMe (OR)
2,-Si (OR)
3R=methyl, ethyl in the formula.
7, by the described obdurability protection coating material for thermal shielding vehicle of claim 1, its middle-end silicon PFPE FcoSiO
1-1.5, three kinds of general structures are arranged:
(1) the poly-propyl ether of end silicon perfluor
(2) end silicon perfluor second third copolyether
(3) end perfluor oxyethyl group ether
Annotate: W=(RO)
3Si P-, (RO)
3SiPO-P-, P=propylidene (CH
2)
3, PO=propoxy-, FE=perfluor ethylidene, iFPO=perfluor isopropoxy, FEO=perfluor oxyethyl group, X=-SO
2F.
8, the preparation method of the described obdurability protection coating material for thermal shielding vehicle of claim 1 comprises following content:
One, material choice
(1) basic raw material adopts following several:
1), end siloxy imide I (SiO
1-1.5)
2
2), Duan Gui oxazolidone OX (SiO
1-1.5)
2Or end silicon polymeric polyisocyanate-oxazolidone PIOX (SIO
1-1.5)
3
3), according to the co-ordination complex M (AcAc) of metal alkoxide compound M (OR) the n transition metal methyl ethyl diketone of the required Si of structure, Al, Ti, Ce, W, V, Ni, Zr, Zn, In, La, Y
nOr MO (AcAc)
N-2In the inorganic metal salt as nitrate or metal chloride (hydrochloride), ammonium salt and colloidal sol body
Annotate: among M (OR) n, M=metal, OR=alcoxyl oxygen base, n=metal valence state
4), end silicon perfluor ether comprises the poly-propyl ether of end silicon perfluor, end silicon perfluor second third copolyether, end silicon perfluor oxyethyl group ether
5), CNT (carbon nano-tube) CNTS;
(2) required batching is:
1) hydrolysis-condensation reaction catalyzer:
Adopt storng-acid cation exchange resin, perfluorinated sulfonic acid or carboxylic acid and fluorine-containing Zeo-karb, acidic molecular sieve, nitric acid, hydrochloric acid and structure to form needed metal nitrate, hydrochloride
2) solvent: adopt dehydrated alcohol, anhydrous isopropyl alcohol, methyl ethyl diketone, butanone or tetrahydrofuran (THF)
3) stablizer: in order to prevent to solidify or gelation in the performed polymer storage process, can add stablizer improve storage stability as: adopt siloxanes, silazane, ketoxime base organoalkoxysilane, consumption 0.1-5% such as the tripolymer of isocyanic ester and tripolymer, isocyanic ester radical siloxane, hydrogen-containing siloxane
4) curing catalysts:
Adopt tin titanium composite catalyst system, consumption is the 0.2-3% that coating is formed total amount, and its tin/titanium is than being 1-1.5, the perhaps metallic naphthenate of 0-3%
5) compound solubilizing agent and consumption:
In low viscosity perfluor ether oil, in low viscous alkoxy end-capped its ratio of silicone oil mixture be 1: 1, consumption is 1-5%;
Two, operation steps
(1) get in end siloxy imide A, the B formula a kind of or two kinds, perhaps hold in A in the silica oxazolidinone, the B formula any one, the co-ordination complex of metal alkoxide compound M (OR) n, methyl ethyl diketone, or a kind of in a kind of and end silicon PFPE in the inorganic metal salt or two kinds, three species complexs, CNT (carbon nano-tube), with the absolute alcohol is solvent, in hydrolysis-condensation reaction with an acidic catalyst, at PH2-5, stir logical nitrogen in 60-150 ℃ of backflow 1-5h, reaction finishes:
(2) will react the solution that finishes behind the separating catalyst, and steam solvent bank and go out moisture content;
(3) will remove anhydrous sol behind the solvent adds the absolute alcohol kind solvent and is diluted to 10-50%;
(4) colloidal sol after will diluting adds and stores after solidifying catalyzer, stablizer, compound solubilizing agent, redilution on demand during use.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747670B (en) * | 2008-11-28 | 2012-03-07 | 富港电子（东莞）有限公司 | Preparation method of composite paint and product thereof |
| CN104559725A (en) * | 2015-01-26 | 2015-04-29 | 青岛理工大学 | Polyisocyanate oxazolidinone/polyurethane/epoxy material and preparation method thereof |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747670B (en) * | 2008-11-28 | 2012-03-07 | 富港电子（东莞）有限公司 | Preparation method of composite paint and product thereof |
| CN104559725A (en) * | 2015-01-26 | 2015-04-29 | 青岛理工大学 | Polyisocyanate oxazolidinone/polyurethane/epoxy material and preparation method thereof |
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