CN101684386B - Corrosion resistance nanometer composite coating and preparation method thereof - Google Patents
Corrosion resistance nanometer composite coating and preparation method thereof Download PDFInfo
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- CN101684386B CN101684386B CN2008101685477A CN200810168547A CN101684386B CN 101684386 B CN101684386 B CN 101684386B CN 2008101685477 A CN2008101685477 A CN 2008101685477A CN 200810168547 A CN200810168547 A CN 200810168547A CN 101684386 B CN101684386 B CN 101684386B
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Abstract
The invention discloses corrosion resistance nanometer composite coating which uses polyurea, organic modified layered clay and proper additive to prepare Polyurea/ClayNanocomposites; the nanometer composite coating is coated on the base material to greatly reduce the corrosion rate of the base material, wherein the polyurea series is prepared through the combination of amino terminated compound and isocyanate compound. The invention also provides a preparation method of the nanometer composite coating and the method comprises the following steps: firstly mixing the amino terminated compound and organic modified layered clay evenly, then mixing the mixture with isocyanate compound and proper additive evenly according to a proper proportion and reacting to obtain the corrosion resistance nanometer composite coating, wherein organic modified layered clay can reach nanoscale dispersion degree after polymerization reaction.
Description
Technical field
The present invention relates to a kind of how rice composite coating and preparation method thereof, be meant a kind of erosion-resisting how rice composite coating and preparation method thereof especially.
Background technology
Coating is claimed paint or lacquer again, forms film on the base material through being coated on, mainly as the usefulness of substrate surface decoration or protection.On the whole existing traditional coating comprises general commercially available cement paint, rubber-emulsion paint etc., mainly all is to be made up of the organic chemistry synthetics; So; Contain many volatile organic matters and heavy metal, organic solvent also has corrodibility or toxicity except that the irritating smell of tool, and is very acute for the respiratory system influence; More very big to human health damage, very the person has more carcinogenic risk.Traditional coating has the restriction of its application, can not cover the surface of all organic or inorganic materials fully like traditional coating, and after traditional coating contacts with air or expose to the sun and rain; Because its structure is not tightr, make it be easy to oxidation, corrode or peel off, work-ing life that all can the loss base material; Very the person causes base material exposed; Cause serious corrosion, rotten or distortion, cause that serious public safety is unexpected, so that this traditional coating obviously can not meet is required at present.
In many etch-proof utilisation technologies; There have the passive metal of use to electroplate with coating to be isolated with two kinds of main method such as coating, and the former utilizes passive metal to be difficult for the characteristic of oxidation, and it is electroplated on the metal object surface; And this metal object is under passivity layer protection, and its oxidation behavior will significantly reduce; The latter coats on the metal object surface with coating, contacts with the direct of oxygen in order to isolated this metal object, and further reaches etch-proof effect.Commonly used with polymkeric substance (polymer), urethane (polyurethane) is as coating, the wide and low price of its purposes, like tackiness agent, sealer, lagging material, engineering plastics, rubber item etc., the buildings waterproof industry often with urethane as waterproof paint.Developed recently goes out polyureas (polyurea; Be called for short PUA) waterproof paint; And effects such as protection against corrosion are better than conventional urethane, and polyureas is strong in the flexibility of various construction environments and object, sticking power is good, and especially easy construction property outclass traditional urethane under wet environment.So, with the coating on base material of highly purified polyureas, the anticorrosion ability that tool is preferable.Yet the high purity polyureas costs an arm and a leg, and the cost value drop of cost and conventional urethane that is used for anti-corrosive treatment is too big, is difficult to popularize.So engineering among the people still more adopts more cheap conventional urethane, or mixed type polyurea/polyurethane coating, but its life expectancy and pure polyureas differ 5 ~ 10 times.
Polyureas mainly comprises two kinds of compositions: isocyanate ester compound (Isocyanate compounds) and end amino compound (Amine terminated compounds).
Wherein isocyanate ester compound can be divided into two big types of the compound of aromatic isocyanate class (Aromatic Isocyanates) and the compounds of aliphatic isocyanates class (Aliphatic isocyanates) etc. again; It can monomer (Monomer), polymer (Polymer), verivate, prepolymer (Prepolymer) and semi prepolymer forms such as (Quasi-prepolymer) exist, and makes to go up different needs and uses for executing.
(terminal functional group is that amine (compound NH2)) is mainly by Amino Terminated polyether(ATPE) (Amine terminated polyether or Polyetheramine to the compound that its middle-end is amino type; Terminal functional group is amine (polyethers NH2)) and the amino type chain extension agent (Amine terminated chain extender) of end; Terminal functional group by amine (chain extension agent NH2)) formed; This chain extension agent regular meeting adds different ratios because of the demand in the construction, and it has comprised two big types of amino chain extension agent (Aliphatic amineterminated chain extender) of fatty family end and the amino chain extension agent of fragrant family end (Aromatic amineterminated chain extender) etc.
Polyureas system is that (compound NCO) and terminal functional group are amido (NH to isocyanic ester by terminal functional group
2) compound can form through existing polyreaction (as shown in Figure 5) and have the urea key that (macromolecular material of characteristic repeating unit NH-CO-NH-) is so all have the urea key (macromolecular material of characteristic repeating unit NH-CO-NH-) all belongs to polyureas; This polyreaction need not catalyzer, also must not heat and can react with film-forming rapidly.Existing polyureas polyreaction is as shown in Figure 5, and wherein n is a molecule number, is to represent that (NCO) compound and terminal functional group were amido (NH to isocyanic ester at 1 o'clock like n
2) compound is with the molecular ratio of 1:1, carry out polyreaction and have a urea key (molecular material of feature unit NH-CO-NH-) with formation; Wherein R1, R2 convention can be different types of molecules such as aliphatics or aromatic series.
Clay (Clay) is the material of a stratiform structure; Since the characteristic of its laminate structure, airtight, fluid-tight rerum natura possessed, through the obstruction that this characteristic provided; Path and time that moisture, oxygen permeate be can effectively increase in clay, water-absorbent and gas penetration property reduced.The present more by Application Research widely in all respects, like matrix material, biochemical field, electronics assembling and environmental protection aspect.Clay (Clay) is mainly by aluminium sesquioxide (Al
2O
3) and silicon-dioxide (SiO
2) the silicate stratiform structure formed; Its size is about 1 μ m; Each granular layer heap by hundreds of to thousands of synusia institute storehouse; Average granular layer heap has 850 silicate layers (Silicate sheets) approximately, and the interfloor distance (d-spacing) between each synusia and another synusia is nearly
Between, main crowd is then to be distributed in
Interlamellar spacing person in the majority.Moreover its layer can be divided into cationic exchange type clay, anionresin type clay and neutral ion crossover clay three major types again with the folded ion of interlayer, and mainly be in the great majority with cationic exchange type clay, and mostly its positively charged ion is Li
+, Na
+, K
+, Ca
+, Mg
2+, Ba
2+, La
3+, Ce
2+Deng, contain crystal water partly.These positively charged ions provide the excellent path that clay is organised, and are ion exchange reaction.
The excellent specific property that book clay had is from its special laminate structure.After book clay and macromolecular material blending, produce the interaction of interlayer cation exchange and ionic linkage.How under the metrical scale, many characteristics that are difficult for obtaining in the micron order structure manifest one by one especially, and those characteristics comprise gas barrier property, Ginkgo Biloba Leaf Extract, water preventing ability, thermotolerance, obdurability, wear-resisting, scratch resistance, corrosion protection, chemicals-resistant etc.For the material of coating class, book clay is excellent thickening material, makes construction or coating operation be more prone to, the coating planarization, and the advantage that significantly shortens man-hour and material usage is extremely showing.
Book clay has its restriction on using, and is a kind of inorganic materials and tool wetting ability with book clay, and lacks affinity between the oil loving polymer, and when mixing with organic materials as if desire, it is quite difficult reaching even compatibility.Therefore wish to get homodisperse material, just must carry out upgrading book clay.
In today that traditional coating has been widely used, the rerum natura that it represented is applied and is reached its intended purposes, thus with known material improve be one than fast way; When two kinds of material different all have its advantage separately, as the two is mixed, to obtain a kind of two novel materials that advantage all possesses, this promptly is the basic concepts of matrix material.The degree of blending together of good matrix material its two must be considerably even; The desired gain character of this matrix material can promote, and nanocomposite (Nanocomposites) is meant that especially the degree that blendes together of two kinds of differing materials has reached quite uniform 10
-9The size of m (referring to disperse phase) is more than the degree that blendes together 10 of conventional composite materials
-6M, high.The basic definition of nanocomposite is as follows: 1. when the dispersion of materials size how meter ruler cun (Nanometer, the scope of 1nm～100nm).2. solid-state greater than for the moment as Gibbsian, having a phase in its any one dimension (Dimension) at least is in the scope of the meter ruler cun how, particularly between 1～20nm, promptly can be described as nanocomposite.
How its character of rice composite coating along with size, physical properties, chemical property is different and different; And how the rice composite coating is by how the meter level material is composited; So the blending of different how meter level materials has different application directions; Comprise scrubbing, self-cleaning, antibiotic, wear-resisting, scratch resistant, novel application such as waterproof, ultraviolet light.Wherein this how the meter level material is common is: rice clay how is to be a stratiform structure, is coated on subject surface and can forms scratch resistant, abrasion-resistant coating, also can be used on the packing of food, promotes its water preventing ability and gas barrier property.Yet how meter level particle distribution state has a crucial factor for the characteristic of coating, and therefore how the meter level particle is kept homodisperse technology and how to be the gordian technique of rice composite coating in coating, also is the door of how rice composite coating production and application.
Because book clay is hydrophilic material, and polymkeric substance (Polymer) coating belongs to oleophilicity, so both intermiscibilities are not good; Even if book clay is ground with increase mixing contact area between the two, but its disperse phase is still uneven, so usually can cause being separated of two phases (Two Phase); And the key knot that mixes has not mutually between the two almost existed; The book clay that is added can't be evenly and is scattered in effectively in the polymkeric substance, so increasing both compatible modifying method is committed step.Wherein be used as by modification person book clay more or less freely with chemical method again; As previously mentioned, owing to accompany positively charged ion in the silicate layer of book clay, it promptly is to modify work optimum utilization thing; So with cation exchange reaction; Cation replacement in the silicate layer is come out, and to exchange the positively charged ion that the another kind of entering has machine property, then organic property of its book clay promptly can increase.The modification agent of this modification usefulness can be described as interfacial agents such as intercalator or swelling agent again.Because modification agent possesses oleophilicity and wetting ability two characteristics simultaneously, thus can with wetting ability stratiform clay with the oleophilicity polymkeric substance link in.
Summary of the invention
The object of the invention promptly is to provide a kind of corrosion resistance nanometer composite coating, in order to be covered on the base material, can make base material significantly reduce its erosion rate.
Secondary objective of the present invention is to provide a kind of preparation method of corrosion resistance nanometer composite coating; This method is to hold amino compound to mix with the upgrading book clay earlier; Again with isocyanate ester compound mixing in the proper ratio, with must this corrosion resistance nanometer composite coating.
For realizing above purpose; Technical scheme below the present invention has taked: a kind of corrosion resistance nanometer composite coating; Upgrading book clay and suitable additive that its composition comprises polyureas, organises, wherein this how a rice composite coating be covered on the base material, can make base material significantly slow down corrosion speed; Wherein this polyureas is by the compound of amino type of end and the compound of isocyanates, through polyreaction and synthetic.
A kind of preparation method of corrosion resistance nanometer composite coating comprises the following steps:
Step 1: get the compound of amino type of an amount of end and an amount of upgrading book clay that organises, stir with machine mixer earlier, get mixture;
Step 2: get the mixture of step 1,, get homogenous mass again with three groups of roller blending three times;
Step 3: the homogenous mass of getting step 2; With the isocyanate ester compound of suitable proportion and suitable additive with reaction injection moulding method (Reaction Injection Molding; Abbreviation RIM) BCD hybrid technology carries out the blending program; After treating that polyreaction is accomplished, can get corrosion resistance nanometer composite coating.
Wherein in the reaction injection moulding method of step 3; Earlier different material is placed different bins; Through high pressure different material is injected mixing device fast, quick mixing, again with the high pressure fast spraying to base material; Different material promptly carries out chemical reaction at once through mixing in this process, so need mix apace and spray material in substrate surface.
Wherein in the homogenous mass blending process of step 3 with the isocyanate ester compound of suitable proportion and step 2, the compound that end is amino type contains urea key (polyureas NHCONH-) with the rapid chemical combination formation of isocyanate ester compound.
A kind of corrosion resistance nanometer composite coating provided by the present invention, its preparation method and application when comparing each other with aforementioned prior art, have more following advantage:
A kind of corrosion resistance nanometer composite coating provided by the invention, the purer polyureas of the anti-corrosion effects of this coating is better, prolongs the work-ing life of base material.
A kind of corrosion resistance nanometer composite coating provided by the invention, the usage quantity of the purer polyureas of usage quantity of this coating still less, so the required cost of coating of the present invention is more cheap.
Description of drawings
Fig. 1 reaches the not XRD analysis collection of illustrative plates of upgrading polynite for the upgrading polynite;
Fig. 2 is the XRD analysis collection of illustrative plates of rice composite coating how;
Fig. 3 is the TEM kenel figure () of rice composite coating how;
Fig. 4 is the TEM kenel figure (two) of rice composite coating how;
Fig. 5 is existing polyureas polyreaction formula, and wherein n is a molecule number; Wherein R1, R2 can be different types of molecules such as aliphatics or aromatic series.
Embodiment
Below in conjunction with accompanying drawing and embodiment content of the present invention is explained further details.
The present invention provides a kind of preparation method of corrosion resistance nanometer composite coating, comprises the following steps:
Step 1:
Get the compound and the upgrading book clay of amino type of end, stir with machine mixer earlier, get mixture.
Wherein the compound of the amino class of this end is that terminal functional group is amido (NH
2) compound, preferably's principal constituent is a polyetheramine (Polyetheramine) and the mixture of chain extension agent (Chain extender), wherein this chain extension agent has terminal functional group and is amido.(The mixture may be purchased from Huntsman's
D -2000,
T-5000,
4200 and
100 terminal amino such class of compounds);
Wherein the compound of the amino class of this end can be by chemosynthesis or commercially available obtaining, like U.S. Huntsman company, American UOP company, BASF Corp, U.S. Albemarle Corporation company;
The weight percent of the upgrading book clay that wherein organises accounts for the 2-14wt% of mixture gross weight;
Wherein this upgrading book clay that organises can carry out upgrading with commercially available book clay through modification agent, obtains the upgrading book clay that this organises in commercially available, like U.S. Nanocor company, hundred Kang Naimi Science and Technology Co., Ltd.;
Wherein this book clay can comprise silicon aluminite class clay (smectite clay), vermiculite (vermiculite), tubulose kaolin (halloysite), sericite (sericite) or mica (mica); Wherein this silicon aluminite class clay (smectite clay) can comprise polynite (montmorillonite), bentonite (saponite), rich aluminium polynite (beidellite), canbyite (nontronite) or lithium soap soil (hectorite), and the preferably is polynite;
Wherein this modification agent can comprise ammonium salt class modification agent, microcosmic salt class modification agent, and it can make inorganic laminated clay tool oleophilicity and be prone to be scattered in the composition of how rice composite coating of the present invention; Wherein this ammonium salt class modification agent preferably is four decyl brometo de amonios (Tetrakis (decyl) ammoniumbromide, [CH
3(CH
2)
9]
4N (Br), CAS.No.14937-42-9), or methyl trialkyl (heptane-decane) brometo de amonio (Methyltrialkyl (C
8-C
10) ammonium chloride, CAS.No.72749-59-8), or bromination dodecyl dimethyl 2-phenoxy ethylamine (Dodecyldimethyl-2-phenoxyethyl) ammonium bromide, CAS.No.538-71-6); Wherein this microcosmic salt class modification agent preferably is dodecyl tri-phenyl-phosphorus bromide (Dodecyltriphenylphosphonium bromide (CH
3(CH
2)
11N (CH
3)
2(CH
2CH
2OC
6H
5) Br, CAS.No.15510-55-1); Above-mentioned modification agent can be buied in friend and Trading Co., Ltd;
Step 2:
Get the mixture of step 1,, get homogenous mass again with three groups of roller blending three times; Wherein this is respectively organized roller gap and is respectively 25～30 μ m, 12～13 μ m, 3～5 μ m; Wherein this rotating speed of respectively organizing roller is respectively 150rpm, 250rpm, 550rpm.
Wherein will hold amino type compound to mix, and impel the compound of holding amino type to be squeezed into the interlayer of this upgrading book clay that organises further with the upgrading book clay that organises in step 2.
Step 3:
Get the homogenous mass of step 2; Carry out the blending program with the compound of the isocyanates of suitable proportion and suitable additive with the BCD hybrid technology of reaction injection moulding method (Reaction Injection Molding); After treating that polyreaction is accomplished, get final product corrosion resistance nanometer composite coating.
Wherein in the reaction injection moulding method of step 3; Prior art places different bins with different material earlier; Through high pressure different material is injected mixing device fast, quick mixing, again with the high pressure fast spraying to base material; Different material promptly carries out chemical reaction at once through mixing in this process, so need mix apace and spray material in substrate surface.
Wherein in step 3 blending process; The compound of the compound of isocyanates and amino type of the end that is uniformly distributed in upgrading book clay interlayer; Produce rapid violent polyreaction (as shown in Figure 5) and form polyureas; And the polyureas of this formation is because the increase rapidly of its molecular chain; Its molecular chain promptly can strut the silicate synusia of its upgrading clay further, makes the interfloor distance of its upgrading book clay strutted greatly more, becomes the polyureas/upgrading clay mixture of the how meter level that evenly blendes together eventually.
Wherein the compound of this isocyanates is that terminal functional group is isocyanic ester (compound NCO); Preferably's principal constituent is a ditan 4; The mixture (this mixture can be purchased in the isocyanate compound of
of Huntsman company series) of 4 '-vulcabond (4,4 '-Methylenebis (phenylisocyanate)) and MDI-substrate prepolymer (MDI-Based Prepolymer);
Wherein the compound of this isocyanates can be synthetic through chemical reaction, also can obtain in commercially available, like U.S. Dow Chemical company, U.S. Du Pont company, U.S. Cytec company, German Bayer company etc.;
Wherein the compound of the amino class of this end and the compound of isocyanates are with suitable part by weight, and to form the polyureas of tool urea key, wherein this suitable part by weight is that 1:1 is preferable demonstration through polyreaction; Wherein this upgrading book clay weight percent accounts for the 1-7wt% of corrosion resistance nanometer composite coating gross weight;
Wherein suitable additive can comprise but be not limited to thickening material, thinner, dispersion agent, fire retardant, static inhibitor, staining agent, releasing agent, mould inhibitor, photostabilizer, inhibitor, antisettling agent, rheological agent, weighting agent, coupling agent, catalyzer, flow agent, skimmer etc.; Visual different construction environments of the additive that it added or client terminal require required character and do suitable interpolation.
The present invention more provides a kind of corrosion resistance nanometer composite coating through above-mentioned preparing method's gained, upgrading book clay and suitable additive that its composition comprises polyureas, organises.
Wherein this polyureas system is synthesized through polyreaction by the compound of amino type of end and the compound of isocyanates.
Wherein the part by weight of the compound of the compound of the amino class of this end and isocyanates is 1:1; Wherein this upgrading book clay weight percent accounts for the 1-7wt% of corrosion resistance nanometer composite coating gross weight;
The present invention demonstrates with following embodiment to illustrating, but the present invention is not limited by following preferred embodiment.
Embodiment one: the polynite of preparation upgrading
Known with the distinctive cationic characteristic of polynite (Montmorillonite) interlayer; Modify with modification agent; This step is a kind of cation exchange reaction, and the modification agent of selecting for use belongs to a kind of cation interfacial active agent, after cation exchange reaction is accomplished; Can make polynite layer with layer between distance more holding of being able to support, this helps organic polymer and inserts wherein more easily.
The upgrading polynite can be carried out upgrading with commercially available polynite through modification agent; Also can obtain this upgrading polynite in commercially available; Like U.S. Nanocor company, hundred Kang Naimi Science and Technology Co., Ltd., present embodiment is with modification agent commercially available polynite upgrading to be explained.
Method for modifying sees also people's documents such as Liu Shizhou (Liu Shizhou, Ye Ruiming, the synthetic and property research of polyaniline/clay nanocomposite; Master's thesis in 1991); Sketch it down, get polynite (to purchase in Nanocor, Inc.USA.) place deionized water; Under room temperature, stirred 24 hours, can get the polynite aqueous solution of swelling.In addition; Get modification agent four decyl brometo de amonios (Tetrakis (decyl) ammonium bromide, CAS.No.14937-42-9), or methyl trialkyl (heptane-decane) brometo de amonio (Methyltrialkyl (C8-C10) ammonium chloride; CAS.No.72749-59-8); Or bromination dodecyl dimethyl 2-phenoxy ethylamine (Dodecyldimethyl-2-phenoxyethyl) ammoniumbromide, CAS.No.538-71-6), or dodecyl tri-phenyl-phosphorus bromide (Dodecyltriphenylphosphonium bromide; CAS.No.15510-55-1) place deionized water, under room temperature, be stirred to dissolving; With 1N HCl titration to pH 3～4 (pH=3～4), (pH meter) monitors it with the pH detector again, in stirring at room 1 hour, can get modification agent solution again.Wherein above-listed four kinds of modification agents all can reach similar upgrading effect, can increase the interfloor distance of the upgrading book clay that organises, and are with modification agent methyl trialkyl (heptane-decane) brometo de amonio (Methyltrialkyl (C in the present embodiment
8-C
10) ammonium chloride, CAS.No.72749-59-8) upgrading being carried out in polynite is exemplary.Again modification agent solution (methyl trialkyl (heptane-decane) brometo de amonio) is added in the polynite aqueous solution of swelling, under room temperature, stirred 24 hours., modification agent solution has with fixed attention silk fabric phenomenon when adding the polynite aqueous solution of swelling, thus must slowly add, and impose powerful stirring.Afterwards, with the whizzer spinning it, centrifugation rate 9000rpm, 30 minutes, again with 30 times of deionized water rinsings more than the volume it, repeat this process 4 ~ 5 times.The sodium cation that this flushing centrifugation step can be removed excessive remaining modification agent and exchanged out.The polynite that obtains through above-mentioned steps, again under room temperature with vacuum-drying 48 hours, again with the pulverizer mill grinding, can obtain powder, be the upgrading polynite that organises.
Embodiment two: the preparation method of rice composite coating how
Step 1:
Get the compound of amino type of end and the upgrading polynite that organises of embodiment one gained, stir with machine mixer earlier, get mixture.
Wherein the compound of the amino class of this end is that terminal functional group is amido (NH
2) compound, preferably's principal constituent is a polyetheramine (Polyetheramine) and the mixture of chain extension agent (Chain extender), wherein this chain extension agent also has terminal functional group and is amido.(The mixture may be purchased from Huntsman's
D -2000,
T-5000,
4200 and
100 terminal amino such class of compounds);
The weight percent of the upgrading book clay that wherein organises accounts for the 2-14wt% of mixture gross weight;
Step 2:
Get the mixture of step 1; Be that 150rpm, roller gap are that 25～30 μ m carry out blending with the rotating speed with first roller set earlier; Be that 250rpm, roller gap are that 12～13 μ m carry out blending with the rotating speed with second roller set again; Be that 550rpm, roller gap are that 3～5 μ m carry out blending with the rotating speed finally, can get homogenous mass with the 3rd roller set.
Step 3:
Get the homogenous mass of step 2; Carry out the blending program with the compound of the isocyanates of suitable proportion and suitable additive with the BCD hybrid technology of reaction injection moulding method (Reaction Injection Molding); After treating that polyreaction is accomplished, can the De Naimi composite coating.
Wherein the compound of this isocyanates is that terminal functional group is isocyanic ester (compound NCO); Preferably's principal constituent is a ditan 4; The mixture (this mixture can be purchased in the isocyanate compound of
of Huntsman company series) of 4 '-vulcabond (4,4 '-Methylenebis (phenylisocyanate)) and MDI-substrate prepolymer (MDI-Based Prepolymer);
The compound of amino type of the end between the compound of this isocyanates and uniform distribution upgrading cheating engaging layer wherein; Carry out violent polyreaction rapidly in interlayer; As shown in Figure 5, with the polyureas of formation tool urea key, so; The macromolecular chain of polyureas is grown up in the interlayer of upgrading polynite, and then can support big upgrading polynite interfloor distance.
Wherein the compound of amino type of the used end of the compound of the isocyanates of this suitable proportion and step 1 is the part by weight of 1:1.
Wherein suitable additive can comprise but be not limited to thickening material, thinner, dispersion agent, fire retardant, static inhibitor, staining agent, releasing agent, mould inhibitor, photostabilizer, inhibitor, antisettling agent, rheological agent, weighting agent, coupling agent, catalyzer, flow agent, skimmer etc.; Visual different construction environments of the additive that it added or client terminal require required character and do suitable interpolation.
Through above-mentioned steps and how rice composite coating, its composition comprises polyureas, upgrading polynite and suitable additive.Wherein how the weight percent of this upgrading polynite accounts for that the 1-7wt% of rice composite coating gross weight is preferred embodiment, down with the upgrading polynite that comprises 3wt% how a rice composite coating is an exemplary.
Embodiment three: the how evaluation of rice composite coating
How rice composite coating like above-mentioned embodiment two gained; At first; In this enforcement profit with the X-ray diffractometer (X-ray Diffraction instrument, XRD) identify this upgrading polynite and how the rice composite coating for how meter level, again with transmission electron microscope (Transmission Electron Microscopy; TEM) identify this how the rice composite coating for how meter level, and its contained upgrading polynite is dispersed in the polyureas.Following XRD and TEM authentication method see also people's documents such as Liu Shizhou (Liu Shizhou, Ye Ruiming, the synthetic and property research of polyaniline/clay nanocomposite, Master's thesis in 1991), sketch it down:
1, upgrading polynite and how X-ray diffractometer (XRD) identification and analysis of rice composite coating
At first, pulverous sample fully is ground to thinner micro mist shape with agate mortar, this step will be beneficial to pulverous sample and more be prone to invest and carry on the ware and smooth.Again the ware that carries of having sample is inserted in the X-ray diffractometer (XRD, Rigaku D/Max-3COD-2988N are Wide-angle XRD).Experiment condition during XRD measures is: WV 35KV, working current 25mA; The speed that scans with 2 °/min is done 2 °～10 ° scanning; Get signal point (copper target,
) for per 0.05 °.Through the collection of illustrative plates of Analysis of X-ray diffraction (XRD), calculate the interfloor distance (d-spacing) of testing sample again according to Bragg's equation (Bragg ' s Law).
Bragg's equation: 2dsin θ=n λ, wherein λ is the wavelength (λ=1.54, copper target) of X-ray; Wherein θ is an input angle; Wherein n is round valuess such as 2,3,4; Wherein d is interfloor distance (d-spacing).
The XRD qualification result of upgrading polynite:
See also Fig. 1; Testing sample is upgrading polynite and not upgrading polynite; Wherein 2 θ of upgrading polynite are not 7; Its interfloor distance (d) is
, promptly about 1.26 rice how; Wherein 2 θ of upgrading polynite are 3.8; Its interfloor distance (d) is
, promptly about 2.32 rice how.Confirmation is through modification agent methyl trialkyl (heptane-decane) brometo de amonio (Methyltrialkyl (C
8-C
10) ammonium chloride; CAS.No.72749-59-8) interfloor distance of the polynite of upgrading is really because of modification agent increases, among the interfloor distance of its increase can make that the compound of the isocyanates that step 3 is added more is prone to get between this upgrading cheating engaging layer.
How the XRD qualification result of rice composite coating:
See also Fig. 2, testing sample is polyureas/upgrading polynite how rice composite coating, the pure polyureas of embodiment two gained.Through the XRD identification and analysis, these two groups of testing samples all do not have signal in 1～10 degree at 2 θ angles, because pure polyureas does not contain the upgrading polynite, can not produce so have signal; And polyureas/upgrading polynite how 1～10 degree of rice composite coating in 2 θ angles all do not have signal and produce; Show that between its clay layer 20 jiaos are smaller or equal to 1; And; When n was 1, its interfloor distance (d) was about
, promptly about 8.8 rice how; So when this 20 smaller or equal to 1 the time, this minimum interfloor distance of two groups is all more than or equal to 8.8 rice how, confirms that how these two groups of coating all belong to the rice level.
2, transmission electron microscope (TEM) identification and analysis of rice composite coating how
Before TEM identifies, must be earlier with testing sample, carry out embedding with commercially available special-purpose embedding medium or commercial epoxy resin (Epoxyresin) or PMMA, get final product work piece, cut into slices in order to slicing machine (Microtome).In when section, with gage controller slice thickness is controlled at the scope of 60～90nm, after doing cutting repeatedly, can be the thin slice of platinum look or gold coloured light elongated reflector, with copper mesh it is picked up again, can carry out the TEM test.TEM (TEM, JEOL JEM1200EX II) operational condition is: the penetrating electrons bundle of 120KV, 50000 times of enlargement ratios are obtained suitable image and are adjusted focal length again, can absorb its reflection.
How the TEM qualification result of rice composite coating
See also the TEM kenel figure of Fig. 3 for 50000 times of amplifications; Testing sample system is the polyureas/upgrading polynite of embodiment two gained rice composite coating how; Wherein Fig. 3 and Fig. 4 are the how TEM kenel of rice composite coating (containing the upgrading polynite 3wt% that organises) of different positions; Wherein black lines is partly for the light areas of upgrading polynite, other non-black bar is polyureas, so, like Fig. 3 and shown in Figure 4; The upgrading polynite has been dispersed in the polyureas, and its upgrading polynite is scattered in the polyureas with delamination type discrete form (Exfoliation) and two kinds of degrees of scatter of intercal type discrete form (Intercalation) simultaneously; Wherein still there is not the person in the crystalline form of the silicate layer of the clay pile structure that changes, is called the intercal type discrete form; And the silicate layer of its clay has not been had the crystalline form pile structure person that changes, belongs to the chaotic person of existence of distribution, claims delamination type discrete form.
Embodiment four: the how anti-corrosion effects assessment of rice composite coating
Because the polyureas cording has erosion-resisting excellent specific property; So in present embodiment; Be with cyclic voltammetric appearance (Cyclic Voltammetry/CV; Label is Radiometer Copenhagen, and model is Voltalab21 and VoltaLab40) test in the how rice composite coating of embodiment two gained whether anticorrosion properties are arranged.
The corrosion test method sees also people's documents such as Liu Shizhou (Liu Shizhou, Ye Ruiming, the synthetic and property research of polyaniline/clay nanocomposite, Master's thesis in 1991), sketches it down, is that (Cold-rolled steel CRS) is testing substrates with cold rolling steel disc; Get an amount of coating to be measured, apply cold rolling steel disc, get final product the CRS diaphragm of painting of coating.A side that again the CRS diaphragm is not coated (Coating) attaches on the working electrode with conductive silver glue; Seal its outer rim with commercially available epoxy resin (Epoxy resin) again; After treating that epoxy resin (Epoxy resin) is stiff; It being inserted in the NaCl solution (electrolytic solution) of 5wt%, is that canonical reference electrode, carbon-point are supporting electrode with the mercurous chloride electrode again, carries out 30 minutes corrosion test; Current potential after getting corrosion test and finish with cyclic voltammetric appearance program again is Free Potential; The corrosion current that carries out scope ± 250mV with 500mV/min scans; Obtain Cyclic Voltammetry Curve; Can obtain corrosion potential (the corrosionpotent ial of tower volt graphic representation (Tafel Curve), measurement sample through data computation; Ecorr), corrosion current (corrosion current, i corr), polarization resistance (polarization resistance Rp), erosion rate (Rcorr, data MPY); Wherein MPY representes each year corrosion one milli inch (milli-inch/year).
How the anticorrosive efficiency analysis result of rice composite coating
Shown in table one, wherein control group for exposed cold rolling steel disc, the testing sample group of no painting of coating be the cold rolling steel disc that applies of polyureas, and the cold rolling steel disc of the how meter composite coating coating of embodiment two gained carry out corrosion test.The erosion rate of wherein control group (the exposed cold rolling steel disc of no painting of coating) is that 0.18MPY, its erosion rate of cold rolling steel disc that applies pure polyureas 12 μ m are 0.1226MPY, how apply that its erosion rate of cold rolling steel disc of rice composite coating 10 μ m is 0.056MPY.So compared to applying thicker pure polyureas, its erosion rate of cold rolling steel disc that applies thin how rice composite coating is slower; Reduce about 2.2 times of erosion rate; Therefore, of the present invention how they anticorrosion properties that possess of rice composite coating not only more are superior to pure polyureas, and required coating thickness also still less.
Table one coating is coated on the anticorrosive efficiency analysis on the base material
Above-listed detailed description is to the specifying of possible embodiments of the present invention, and this embodiment is not in order to limiting claim of the present invention, and the equivalence that all the present invention of disengaging do is implemented or change, all should be contained in the claim of this case.
Claims (12)
1. the preparation method of a corrosion resistance nanometer composite coating is characterized in that, comprises the following steps:
Step 1: with the mixture of polyetheramine and chain extension agent and the book clay through the modification agent upgrading that organises, how the weight percent of this upgrading book clay accounts for the 1-7wt% of rice composite coating gross weight, stir with machine mixer earlier, mixture;
Step 2: the mixture of getting step 1; Be that 150rpm, roller gap are that 25～30 μ m carry out blending with the rotating speed with first roller set earlier; Be that 250rpm, roller gap are that 12～13 μ m carry out blending with the rotating speed with second roller set again; Be that 550rpm, roller gap are that 3～5 μ m carry out blending with the rotating speed finally, can get homogenous mass with the 3rd roller set;
Step 3: the homogenous mass of getting step 2; Add additive and become the ditan 4 of 1: 1 part by weight with the mixture of chain extension agent with the polyetheramine of step 1; The mixture of 4 '-vulcabond and MDI-substrate prepolymer; BCD hybrid technology with the reaction injection moulding method carries out the blending program, get final product corrosion resistance nanometer composite coating.
2. preparation method as claimed in claim 1 is characterized in that: the weight percent of the upgrading book clay that organises of said step 1 accounts for the 2-14wt% of mixture gross weight.
3. preparation method as claimed in claim 1 is characterized in that: said modification agent is four decyl brometo de amonios, or methyl trialkyl (heptane-decane) brometo de amonio, or bromination dodecyl dimethyl 2-phenoxy ethylamine, or the dodecyl tri-phenyl-phosphorus bromide.
4. preparation method as claimed in claim 1 is characterized in that: layered clay is polynite or bentonite.
5. by the described preparation method of claim 1, it is characterized in that: said additive comprises thickening material, thinner, dispersion agent, fire retardant, static inhibitor, staining agent, releasing agent, mould inhibitor, photostabilizer, inhibitor, antisettling agent, rheological agent, weighting agent, coupling agent, catalyzer, flow agent or skimmer.
A preparation method as claimed in claim 1 and corrosion resistance nanometer composite coating, it is characterized in that: the upgrading book clay and the suitable additive that include polyureas, organise.
7. like 6 described corrosion resistance nanometer composite coatings of claim the; It is characterized in that: wherein polyureas is mixture and the ditan 4 by polyetheramine and chain extension agent; The mixture of 4 '-vulcabond and MDI-substrate prepolymer is through polyreaction and synthetic.
8. corrosion resistance nanometer composite coating as claimed in claim 6 is characterized in that: the mixture of said polyetheramine and chain extension agent and ditan 4, the part by weight of the mixture of 4 '-vulcabond and MDI-substrate prepolymer is 1: 1.
9. corrosion resistance nanometer composite coating as claimed in claim 6 is characterized in that: the said upgrading book clay that organises is the upgrading polynite.
10. corrosion resistance nanometer composite coating as claimed in claim 6 is characterized in that: the said upgrading book clay weight percent that organises accounts for the 1-7wt% of corrosion resistance nanometer composite coating gross weight.
11. corrosion resistance nanometer composite coating as claimed in claim 6 is characterized in that: the minimum interfloor distance of said corrosion resistance nanometer composite coating is greater than 8.8 rice how.
12. corrosion resistance nanometer composite coating as claimed in claim 6 is characterized in that: said its degree of scatter of upgrading book clay comprises the dispersion kenel of delamination type discrete form and intercal type discrete form simultaneously.
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