CN102676028A - Long-acting waterborne nanometer attapulgite clay/epoxy anticorrosive coating material and preparing method thereof - Google Patents
Long-acting waterborne nanometer attapulgite clay/epoxy anticorrosive coating material and preparing method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical engineering materials and relates to a long-acting waterborne nanometer attapulgite clay/epoxy anticorrosive coating material and a preparing method thereof. Organic modified nanometer attapulgite clay particles and waterborne epoxy resin are adopted to obtain waterborne nanometer attapulgite clay/epoxy composite resin in an in situ polymerization method or blending method, then are blended with non-essential waterborne blend resin, non-essential waterborne epoxy hardeners, non-essential water, non-essential pigments and fillers and non-essential coating auxiliaries, then are cured to form a film at temperature of 5-300 DEG C, and accordingly the waterborne nanometer attapulgite clay/epoxy anticorrosive coating material is obtained. The waterborne anticorrosive coating material is good in corrosion resistance, high in mechanical strength, good in transparency and weather resistance and excellent in construction performance. Compared with the waterborne epoxy anticorrosive coating not added with the organic modified nanometer attapulgite clay particles, service life of the long-acting waterborne nanometer attapulgite clay/epoxy anticorrosive coating material is improved by 20-40%, has a long-acting corrosion resistance, and can be used in the fields including metal corrosion resistance and architectural decoration.
Description
Technical field
The invention belongs to chemical industry, material technology field, be specifically related to the recessed soil of a kind of long-acting water nano/epoxy anticorrosion coated material and preparation method thereof.
Background technology
Attapulgite is claimed polygorskite or Palygorskite again, because attapulgite (recessed soil) has unique rhabdolith structure, can be used as functional additive and weighting agent large-scale application aspect matrix material.Like (Zhongjie Du etc. such as Du; Journal of Materials Science; 2003:4863-4868) adopt situ aggregation method to prepare Vilaterm/attapulgite clay nano composite material with linear comb shape, through the poly shock strength of attapulgite enhanced and tensile strength respectively with do not have the attapulgite enhanced to compare to have increased by 63.5% and 21.3%.(Chao Yang etc. such as Yang; Synthetic Metals; 2009,159:2056-2062) earlier attapulgite modified with KH570, in-situ chemical oxypolymerization has prepared attapulgite/Pt/Polypyrrole composite material then; The consistency of both materials improves, and the thermostability of matrix material is improved.
Attapulgite is widely used at coatings industry, as is used for auxiliary agents such as thickening rheology, also can be used for improving the mechanical strength of coating.But after attapulgite is made into ultrafine powder, be easy to generate surface effects, cause the surface-area of material to increase; Surface energy raises, and particle is in unsteady state, is prone to produce agglomeration between each particle; So the dispersiveness of recessed soil in coating is the problem that at first need solve.The consistency of attapulgite and coating is good more, and their interface bond strength is good more, and the coating mechanical property after attapulgite strengthens is better, and other performance such as optical property, wetting ability or hydrophobicity are also better, otherwise cause two to be separated easily.The method that overcomes the above problems is that attapulgite is carried out modification, and the surface grafting functional type functional group at recessed soil introduces the function that natural recessed soil does not possess.Conventional method of modifying is through properties-correcting agent and concavo-convex blend, and the functional group reactions on properties-correcting agent and recessed soil surface is grafted to recessed soil surface with functional segment.Like (Sun Hongxiu etc. such as Sun Hongxiu; Speciality Petrochemicals; 2011; 28:36) attapulgite is carried out earlier organically-modifiedly, prepared attapulgite enhanced polymethyl methacrylate materials with emulsifier-free emulsion polymerization then, find that the temperature and the second-order transition temperature of its decomposition 10% exceeds 4.78 and 20.94 degrees centigrade respectively than pure polymethylmethacrylate with γ-methacryloxypropyl trimethoxy silane (KH-570).(An Li etc., Journal of Applied Polymer Science, 2004 such as Li; 92:1596-1603) use N; The N-methylene-bisacrylamide prepares the acid of attapulgite enhanced polypropylene as linking agent through grafting copolymerization process, has significantly improved the calorifics stability of mixture.Zhang etc. (Junping Zhang etc.,
Carbohydrate Polymers, 2007,68:367-374.) in the aqueous solution, to carry out graft polymerization and prepare attapulgite enhancing chitosan-ROHM emulsion, the calorifics stability of composite emulsion is improved.Chinese patent CN201110291789.7 has introduced the preparation method of a kind of epoxy resin and attapulgite clay nano composite material; Earlier with attapulgite and coupling agent coupling; Then the link coupled attapulgite is joined epoxy resin, solidifying agent, get epoxy resin/Attapulgite nano composite material after the curing, compare with pure epoxy resin; The tensile strength of nano composite material and extension at break intensity all increase, and show toughness preferably.Chinese patent 201110325279.7 has been introduced a kind of preparation method of attapulgite/compound polyurethane material; At first the nano-attapulgite stone powder is carried out organic surperficial hybrid modification with the organic surface modifying agent; Again the organic nano attapulgite powder behind organic surperficial hybrid modification is joined in the isocyanate-monomer; In-situ polymerization prepares attapulgite/compound polyurethane material, and it is good to have mechanical property, hardness advantages of higher after the film forming.Chinese patent CN 201010589078.3 has introduced a kind of polyaniline corrosion-resistant epoxy paint and preparation method thereof; With epoxy resin and polyaniline/palygorskite nano composite material, amine curing agent blend; The preparation protective system, the mechanical property of coating, ageing-resistant performance, corrosion resistance nature obviously improve, and make metal surface passivation; Form fine and close, the stable oxide film of one deck, stoped the further oxidation of metal.But present coating does not relate to compound at nanoscale of organism and attapulgite with recessed land reform property.
Summary of the invention
The objective of the invention is to propose the recessed soil of a kind of long-acting water nano/epoxy anticorrosion coated material; But recessed grogs of water-repellent preservation coated material of the present invention organic modified nano in film process is crosslinked with the aqueous epoxy resins in-situ chemical; Good corrosion resistance, mechanical strength height, transparent good have splendid workability.
Another object of the present invention is to propose the preparation method of the recessed soil of above-mentioned long-acting water nano/epoxy anticorrosion coated material; The recessed soil of the water nano/epoxy anticorrosion coated material of the present invention's preparation is compared with the water-base epoxy anticorrosion coating material that does not add recessed grogs of organic modified nano; The anticorrosion life-span of the recessed soil of water nano/epoxy anticorrosion coated material is improved 20-40%, has the long-effective corrosion effect.
A further object of the present invention is to propose the range of application and the application method thereof of the recessed soil of above-mentioned long-acting water nano/epoxy anticorrosion coated material.The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Be with recessed grogs of organic modified nano and the method for aqueous epoxy resins through in-situ polymerization or blend; Obtain the recessed soil/composite epoxy resin of water nano; Again with nonessential water-based blending resin, nonessential aqueous epoxy curing agent, nonessential water, nonessential color stuffing, nonessential coatings additive(s) blend; At 5-300 ℃ of film-forming, but recessed grogs of organic modified nano is crosslinked with the aqueous epoxy resins in-situ chemical in film process, can obtain the recessed soil of long-acting water nano/epoxy anticorrosion coated material.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; The sub-consumption of the recessed grogs of organic modified nano accounts for the 1-70wt% of starting material total amount; Aqueous epoxy resins accounts for the 30-99wt% of starting material total amount; Nonessential water-based blending resin consumption accounts for the 0-30wt% of starting material total amount, and nonessential aqueous epoxy curing agent consumption accounts for the 0-20wt% of starting material total amount, and nonessential water consumption accounts for the 0-50wt% of starting material total amount; Nonessential color stuffing consumption accounts for the 0-50wt% of starting material total amount, and nonessential coatings additive(s) consumption accounts for the 0-30wt% of starting material total amount.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes is with recessed grogs of organic modified nano and the method for aqueous epoxy resins through in-situ polymerization or blend, the recessed soil/composite epoxy resin of preparation water nano.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Be with the recessed soil/composite epoxy resin of water nano; With nonessential water-based blending resin, nonessential aqueous epoxy curing agent, nonessential water, nonessential color stuffing, nonessential coatings additive(s) blend; At 5-300 ℃ of film-forming, but recessed grogs of organic modified nano is crosslinked with the aqueous epoxy resins in-situ chemical in film process, can obtain the recessed soil of long-acting water nano/epoxy anticorrosion coated material.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Wherein recessed grogs of organic modified nano is to utilize to have molecular recognition and the inducing action of the acid larger molecular organics of functional group to attapulgite (recessed soil); It is that 10-500 nanometer spherical particle or elliposoidal particle obtain that organic-inorganic nano self-assembly, the club shaped structure of recessed soil change particle diameter into.Recessed grogs of the organic modified nano that invention proposes; Be to be raw material with attapulgite, the organic macromolecule that has functional group, pH regulator agent, solvent and nonessential auxiliary agent; Under heating condition, utilize molecular recognition and the inducing action of organic macromolecule, the organic-inorganic nano self-assembly to attapulgite; Change the club shaped structure of attapulgite into spheroidal particle or elliposoidal particle, obtaining particle diameter is recessed grogs of organic modified nano of 10-500 nanometer.
Recessed grogs of organic modified nano of the present invention; Good with the organic polymer consistency, both can be dispersed in the aqueous phase system, also can be dispersed in the oil phase system; Be difficult for reuniting, and can be according to different demands at the different functional groups of the recessed grogs sub-surface of synthetic organic modified nano grafting.
Recessed grogs of organic modified nano of the present invention is the spheroidal particle or the elliposoidal particle of 10-500 nanometer for particle diameter.
The recessed grogs of organic modified nano of the present invention is sub, is preferably the spheroidal particle or the elliposoidal particle of particle diameter 10-300 nanometer.
Recessed grogs of organic modified nano of the present invention; The attapulgite consumption occupies the 2-50wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano; The organic macromolecule consumption occupies the 0.5-60wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano; Solvent load occupies the 38-97wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano; PH regulator agent consumption occupies the 0.01-10wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano, and nonessential auxiliary dosage occupies the 0-30wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
Attapulgite of the present invention can be attapulgite powder body or attapulgite hydrogel, and consumption occupies the 2-50wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
Organic macromolecule of the present invention is organism or the polymkeric substance of 300-500000 for molecular weight.
Organic macromolecule of the present invention is preferably organism or the polymkeric substance of molecular weight 300-100000.
Organic macromolecule of the present invention; The surface has or chemically modified have can with attapulgite bonded hydrophilic functional group; Like hydroxyl, carboxyl, sulfonic group, phosphonate group, sulfydryl, amido, carboxamido-group, imido grpup, consumption occupies the 0.5-60wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
Organic macromolecule of the present invention; Surface hydrophilic functional group such as wetting ability hydroxyl organic macromolecule, wetting ability contain carboxyl organic macromolecule, wetting ability and contain sulfonic group organic macromolecule, wetting ability and contain phosphonate group organic macromolecule, wetting ability amino-contained organic macromolecule, wetting ability and contain imido grpup organic macromolecule, wetting ability amide-containing organic macromolecule, wetting ability and contain the sulfydryl organic macromolecule; Select 1-3 kind wherein for use, contain a kind of acid organic macromolecule at least.
Organic macromolecule described in the present invention; Non-limiting example is polyoxyethylene glycol, W 166, Z 150PH, Walocel MT 20.000PV, Natvosol, CMC 99.5, the TKK 021 that contracts, gather hydroxy acrylate, ROHM, polymethyl acrylic acid, polybutylenes acid, polybutylenes diacid, polyvinylsulfonic acid, polypropylene-base sulfonic acid, polyvinylbenzenesulfonic acid, polyvinyl phosphonic acids, polyphosphonic acid, hydroxyl Tripyrophosphoric acid, 2-phosphonic acids butane-1; 2; The 4-tricarboxylic acid, gather propadiene base phosphonic acids, gather 2; 2-dimethylol propionic acid, tannic acid, phytic acid, chitosan, nucleic acid, POLYACTIC ACID, hydroxy octadecadienoic acid, gather 2,4-resorcylic acid, polydiene propyl group amine, gather thanomin, SEPIGEL 305, gather NMA, gather hydroxyl second USAF RH-1, octacosyl dihydroxy ethyl ammonio methacrylate, diethylolamine titanic acid ester, trolamine titanic acid ester, polyene propylmercaptan, polythiol, N, N-diallyl be amino--triazine--mercaptan etc.
Solvent of the present invention, the mixing solutions for water or water and hydrophilic organic solvent contains water at least.
Solvent of the present invention like water, alcohol, ketone, pyrrolidone, alcohol ether, pure ether-ether, THF, N, contains water at least, selects 1-3 kind wherein for use, and consumption occupies the 38-97wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
Solvent described in the present invention; Non-limiting example such as water, methyl alcohol, ethanol, Virahol, 1, ammediol, terepthaloyl moietie, USP Kosher, tetramethylolmethane, acetone, butanone, Methyl amyl ketone, methyl heptyl ketone, N-Methyl pyrrolidone, Vinylpyrrolidone polymer, butyl glycol ether, propylene glycol monomethyl ether, Ucar 35 butyl ether, propylene-glycol ethyl ether acetic ester, Ucar 35 monobutyl ether acetate, 2-Butoxyethyl acetate, THF, N etc.
PH regulator agent described in the present invention is water-soluble inorganic alkaline compound or organic basic compound, selects 1-3 kind wherein for use, and consumption occupies the 0.01-10wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
PH regulator agent described in the present invention, non-limiting example such as sodium hydroxide, Pottasium Hydroxide, ammoniacal liquor, urea, yellow soda ash, salt of wormwood, sodium-acetate, Potassium ethanoate, potassium oxalate, sodium oxalate, diethylamine, triethylamine, diethylolamine, trolamine, 1-amino-2-propyl alcohol, triethylene tetramine, TEPA, methyl-amino-ethyl imidazoles, tetramethyl-imidazoles, pyridine, Phenylpropanolamine etc.
Nonessential auxiliary agent described in the present invention is coprecipitator, dispersion agent, viscosity modifier, skimmer, small molecules mineral acid or organic acid etc., can select wherein one or more for use, and consumption occupies the 0-30wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
Coprecipitator described in the present invention; Be the reagent that in liquid phase, adds; With had weak interaction (like electrostatic interaction, hydrogen bond action, positive and negative charge effect etc.) by throw out, can deposition be produced with precipitation agent synergy, this reagent just is called coprecipitator.Non-limiting example that coprecipitator described in the present invention adopts such as oxine, oxalic acid tetraacethyl disodium, sodium ascorbate, Trisodium Citrate, SEPIGEL 305, Poly aluminum Chloride (PAC) etc.
Dispersion agent described in the present invention is the interfacial agent that has oleophilicity and two kinds of opposite nature of wetting ability at intramolecularly simultaneously, adopts conventional pigment dispersing agent in water-borne coatings, the production of water-based sizing agent.
Viscosity modifier described in the present invention adopts conventional thickening material, anti-settling agent, viscosity-depression agent etc. in water-borne coatings, the production of water-based sizing agent.
Skimmer described in the present invention adopts conventional water-based skimmer in water-borne coatings, the production of water-based sizing agent.
Small molecules mineral acid or organic acid described in the present invention, the non-limiting example example hydrochloric acid of employing, sulfuric acid, phosphoric acid, acetic acid, oxalic acid etc.
The preparation method of recessed grogs of organic modified nano of the present invention; Be first, add pH regulator agent and nonessential auxiliary agent, pH regulator to 1 ~ 14 of mixed system with attapulgite, the larger molecular organics that has functional group, solvent blend; Under 50 ℃ of-300 ℃ of conditions; Reacted 1-1000 hour, and, realized the nanometer and the organic-inorganic nano self-assembly of attapulgite through attapulgite and organic macromolecule interfacial interaction; Change the club shaped structure of attapulgite into microsphere particles, obtaining particle diameter is recessed grogs of organic modified nano of 10-500 nanometer.
The preparation method of recessed grogs of organic modified nano of the present invention; Preferred earlier with attapulgite, the larger molecular organics that has functional group, solvent blend, add pH regulator agent and nonessential auxiliary agent, with pH regulator to 3 ~ 14 of mixed system; Under 70 ℃ of-250 ℃ of conditions; Reacted 1-600 hour, and, realized the nanometer and the organic-inorganic nano self-assembly of attapulgite through attapulgite and organic macromolecule interfacial interaction; Change the club shaped structure of attapulgite into microsphere particles, obtaining particle diameter is recessed grogs of organic modified nano of 10-500 nanometer.
The preparation method of recessed grogs of organic modified nano of the present invention; The attapulgite consumption occupies the 2-50wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano; The organic macromolecule consumption occupies the 0.5-60wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano; Solvent load occupies the 38-97wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano; PH regulator agent consumption occupies the 0.01-10wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano, and nonessential auxiliary dosage occupies the 0-30wt% of the sub-starting material total amount of the recessed grogs of machine modified Nano.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Aqueous epoxy resins is selected from one or more the combination in water-based bisphenol A epoxide resin, water-based hydrogenated bisphenol A epoxy resin, water-based cycloaliphatic epoxy resin, the water-based bisphenol F epoxy resin, and aqueous epoxy resins accounts for the 30-99wt% of starting material total amount.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Nonessential water-based blending resin is selected from one or more combination of conventional water-and acrylate resin in the coating, aqueous polyester resin, aqueous alkide resin, waterborne organic silicon resin, waterborne polyurethane resin, water-compatible amino resin, water-based fluorocarbon resin, and nonessential water-based blending resin consumption accounts for the 0-30wt% of starting material total amount.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Nonessential aqueous epoxy curing agent is selected from one or more combination of conventional aqueous epoxy resins use epoxy hardener in the coating material production, and nonessential aqueous epoxy curing agent consumption accounts for the 0-20wt% of starting material total amount.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes, nonessential color stuffing be selected from water-based anticorrosive paint produce in one or more combination of conventional color stuffing, nonessential color stuffing consumption accounts for the 0-50wt% of starting material total amount.
Nonessential color stuffing described in the present invention, non-limiting example such as white titanium pigment, permanent white, kaolin, coarse whiting, zn phosphate, phosphagel phosphaljel, iron oxide red, mica iron, silicon powder etc.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes; Nonessential auxiliary agent is selected from the conventional auxiliary agent of water-borne coatings kind; Like one or more combination of flow agent, thickening material, film coalescence aid, skimmer, anti-settling agent, dispersion agent, nonessential auxiliary dosage accounts for the 0-30wt% of starting material total amount.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes, the preparation method comprises following steps:
(1) under agitation condition, recessed grogs of organic modified nano is mixed the recessed soil/composite epoxy resin of preparation water nano with aqueous epoxy resins;
(2) under agitation condition; In the recessed soil/composite epoxy resin of water nano, add nonessential water-based blending resin, nonessential aqueous epoxy curing agent, nonessential water, nonessential color stuffing, the mixing of nonessential auxiliary agent, the recessed soil/corrosion-resistant epoxy paint of preparation water nano;
(3) at 5-300 ℃ of film-forming.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes, the preparation method comprises following steps:
(1) under agitation condition, with recessed grogs of organic modified nano and epoxy blend;
(2) adopt in-situ polymerization, carboxyl and epoxy resin ring-opening reaction on recessed grogs of organic modified nano, preparation nano concave earth/composite epoxy resin;
(3) under agitation condition, adopt conventional back emulsification method in the water-borne coatings production of resins, the recessed soil/composite epoxy resin of preparation water nano;
(4) under agitation condition; In the recessed soil/composite epoxy resin of water nano, add nonessential water-based blending resin, nonessential water, nonessential aqueous epoxy curing agent, nonessential color stuffing, the mixing of nonessential auxiliary agent, the recessed soil/corrosion-resistant epoxy paint of preparation water nano;
(5) at 5-300 ℃ of film-forming.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes can be used for the corrosionproof protection in anti-corrosion of metal, building decoration field.
The recessed soil of long-acting water nano/epoxy anticorrosion coated material that the present invention proposes and preparation method thereof; Its advantage is: the present invention adopts in-situ polymerization or blend method; The recessed soil of preparation water nano/epoxy composite coated material; The recessed grogs of organic modified nano is good with the organic polymer consistency, stability high being difficult for reunites, but it is crosslinked with the aqueous epoxy resins in-situ chemical in film process, to have recessed grogs of organic modified nano of acidic-group, thereby significantly improves corrosion resistance of coating.Water-repellent preservation coated material good corrosion resistance, the mechanical strength of the present invention's preparation is high, the transparency is good; Has splendid workability; Compare with the water-base epoxy anticorrosion coating material that does not add recessed grogs of organic modified nano; The recessed soil of water nano/anticorrosion life-span of epoxy anticorrosion coated material can be improved 20-40%, has the long-effective corrosion effect, can be used for fields such as anti-corrosion of metal, building decoration.
Unless otherwise, all per-cents that use among this paper and ratio are all by weight.
ESEM (SEM) is taken pictures by Philips XL 30 field emission microscope,s, and all samples all carry out metal spraying before observation.Chemistry exchanges the three-electrode system of resistance reactance spectrum (Electrochemical Impedance Spectroscopy) test employing standard; Equipment is the electrochemical workstation CHl604B that Shanghai occasion China equipment company produces; Reference electrode is SCE (SCE), and supporting electrode is to be about lcm over against area
2Platinized platinum.The measurement temperature is a room temperature, and working fluid is selected 5% NaCl solution for use.The cathodic polarization curve scan rate is at 0.5mV/s, and frequency range is 10
-2Hz to 10
5Hz, sinusoidal wave amplitude is ± 10mv.
The test of adhesive force of coatings test employing standard " GB/T 9286-1998 " cross-hatching.Coating hardness adopts the test of standard " GB/T 6739-2006 " pencil method or tests according to standard " GB/T 1730-1993 " fork method.The viscosity of coating is tested according to standard " GB/T 1723-1993 ".The impact resistance test of coating is tested according to standard " GB/T 1732-1993 ".The snappiness test of coating is tested according to standard " GB/T 1731-1993 ".The salt spray resistance test of coating is tested according to standard " GB/T 1771-1991 ".
Description of drawings
Fig. 1 is ESEM (SEM) photo on primary attapulgite (left side), shows among the figure that the basic structural unit of attapulgite is bar-shaped or fibrous single crystal.
Fig. 2 is ESEM (SEM) photo of recessed grogs of the organic modified nano of the inventive method, demonstrates recessed grogs of organic modified nano among the figure and is sphere or elliposoidal nanostructure.
Fig. 3 is that recessed grogs of the organic modified nano of the inventive method is dispersed in ESEM (SEM) photo in the aqueous epoxy resins, demonstrates recessed grogs of organic modified nano good dispersivity in aqueous epoxy resins among the figure.
Fig. 4 is that the electrochemical AC impedance spectrum that water-base epoxy corrosion protection coating (1) and the recessed soil of water nano/epoxy anticorrosion coating (2) are soaked in 5% NaCl solution after 30 compares.As can be seen from the figure, compare with the water-base epoxy anticorrosion coating material that does not add recessed grogs of organic modified nano, the recessed soil of water nano/epoxy anticorrosion coated material has the long-effective corrosion effect.
Embodiment
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Embodiment 1:
The attapulgite water-sol that takes by weighing 20g10% places beaker, and ultra-sonic dispersion 10min is uniformly dispersed system; Add 2 gram polyoxyethylene glycol, 1 gram CMC 99.5,5 gram ROHM, 62 gram deionized waters, 10 gram Virahols again, dispersed with stirring 30 minutes adds 10% aqueous sodium hydroxide solution; The pH value of system is adjusted to 3, is warming up to 80 ℃, constant temperature stirred 500 hours; Take out reaction product, separating, washing can obtain recessed grogs of organic modified nano.
Embodiment 2:
Take by weighing 10g attapulgite powder, 1 gram Trisodium Citrate, 1 gram sodium ascorbate, add 50 gram water, 10 gram N-Methyl pyrrolidone, 3 gram oxalic acid, place beaker; Dispersed with stirring 1 hour adds 1 gram chitosan, 1 gram polyvinyl phosphonic acids, 20 gram deionized waters, 3 gram Ucar 35 monobutyl ether acetates, dispersed with stirring 1 hour again; The urea and the yellow soda ash that add 1:1 are adjusted to 6 with the pH value of system, and above-mentioned mixed solution is transferred in the encloses container; Be warming up to 120 ℃, reaction product is taken out in isothermal reaction 120 hours; Separating, washing can obtain recessed grogs of organic modified nano.
Embodiment 3:
Take by weighing 20g attapulgite powder, 2 gram BYK-P104 dispersion agents, 1 gram oxine, 20 gram water, 10 gram Ucar 35 butyl ether, 5 gram Vinylpyrrolidone polymers, place beaker, dispersed with stirring 1 hour; Add 10 gram tannic acids, 5 gram diethylolamine titanic acid ester, 20 gram deionized waters, 7 gram Ns again, dispersed with stirring 1 hour adds 10% ammoniacal liquor; The pH value of system is adjusted to 9, above-mentioned dispersion liquid is transferred in the encloses container, be warming up to 180 ℃; Constant temperature stirred 60 hours; Take out reaction product, separating, washing can obtain recessed grogs of organic modified nano.
Embodiment 4:
Take by weighing 40g attapulgite powder, 1 and restrain Sodium hexametaphosphate 99 dispersion agent, 1 gram PE-100 dispersion moisture agent, the 1 gram vitriol oil, 10 gram water, 20 gram Ucar 35, place beaker, stirring, ultra-sonic dispersion 1 hour; Add 17 gram phytic acid, 5 gram polyene propylmercaptans, 5 gram 2-Butoxyethyl acetates again, dispersed with stirring 1 hour adds Phenylpropanolamine; The pH value of system is adjusted to 12, above-mentioned dispersion liquid is transferred in the encloses container, be warming up to 250 ℃; Constant temperature stirred 3 hours; Take out reaction product, separating, washing can obtain recessed grogs of organic modified nano.
Recessed grogs of the organic modified nano of 40 gram embodiment 4 is added in the 40 gram aqueous epoxy resins; Dispersed with stirring 20 minutes; Ultra-sonic dispersion is 5 minutes again; Add 16 gram water-and acrylate resins, 1 gram water-based skimmer, 1 gram water-based flow agent, 2 gram waterborne film-forming auxiliary agents, dispersed with stirring 30 minutes obtains water-based anticorrosive paint.Coating is coated on the iron plate 48 hours film forming of normal temperature.
Nano concave earth/epoxy anticorrosion the layer material of preparation, coating light transmission rate＞80%, hardness 2H, 0 grade of sticking power (cross-hatching), weathering resistance＞600 hour, salt-fog resistant time＞250 hour.
Embodiment 5:
The attapulgite water-sol, 5 that takes by weighing 40g10% restrains sodium malates, 5 gram ethanol, 1 gram acetic acid, 1 gram oxalic acid, places beaker, and dispersed with stirring 30 minutes adds 10 gram Z 150PH, 30 again and restrains polymethyl acrylic acid, 2 gram POLYACTIC ACIDs, 1 gram BYK-420 anti-settling agent, 5 gram deionized waters; Dispersed with stirring 1 hour adds 5% potassium hydroxide aqueous solution, and the pH value of system is adjusted to 8; Above-mentioned dispersion liquid is transferred in the encloses container; Be warming up to 120 ℃, constant temperature 100 hours takes out reaction product; Separating, washing can obtain recessed grogs of organic modified nano.
Recessed grogs of 15 gram organic modified nanos is added in the 40 gram aqueous epoxy resins; Dispersed with stirring 10 minutes; Add 10 gram aqueous epoxy curing agents, 3 gram permanent white, 3 gram white titanium pigments, 2 gram silicon powders, 3 grammes per square metre calcium, 20 gram water, 1 gram aqueous dispersant, 1 gram water-based skimmer, dispersed with stirring 1 hour adds 1 gram water-based skimmer, 1 gram water-based flow agent again; Dispersed with stirring 10 minutes obtains water-based anticorrosive paint.Coating is coated on the iron plate 80 ℃ of 3 hours drying and forming-films.
Nano concave earth/epoxy anticorrosion the layer material of preparation, hardness 3H, 1 grade of sticking power (cross-hatching), weathering resistance＞800 hour, salt-fog resistant time＞600 hour.
Embodiment 6:
Take by weighing 5g attapulgite, 0.5 gram phosphoric acid, 30 gram water, 5 gram Virahols, place beaker, dispersed with stirring 30 minutes adds 30 gram polyvinyl phosphonic acids, 25 gram tannic acids, 4.5 gram deionized waters again; Dispersed with stirring 1 hour adds the 5% potassium oxalate aqueous solution, and the pH value of system is adjusted to 5; Above-mentioned dispersion liquid is transferred in the encloses container, is warming up to 80 ℃, constant temperature stirred 1000 hours; Take out reaction product, separating, washing can obtain recessed grogs of organic modified nano.
The recessed grogs of 30 gram organic modified nanos is added in the 15 gram epoxy resin, with this mixture heating up to 100 ℃, home position polymerization reaction 4 hours; Make the epoxy resin ring-opening reaction; Add 7.5 gram epoxy resin, 35 gram water, 1 gram anionic emulsifier, 0.5 donaxine neutralizing agent again, adopt the back emulsification method, 5000 rev/mins of high-speed stirring were disperseed 1 hour; Recessed soil/the composite epoxy resin of preparation water nano; Add 5 gram aqueous epoxy curing agents, 2 gram aqueous dispersants, 1 gram rust-preventive agent, 1 gram water-based skimmer, 2 gram water-based flow agents again, dispersed with stirring 10 minutes obtains water-based anticorrosive paint.Coating is coated on the iron plate, and 100 ℃ solidified drying and forming-film 2 hours.
Nano concave earth/epoxy anticorrosion the layer material of preparation, hardness 2H, 0 grade of sticking power (cross-hatching), weathering resistance＞600 hour, salt-fog resistant time＞500 hour.
Embodiment 7:
The recessed grogs of 5 gram organic modified nanos is added in the 20 gram epoxy resin, with this mixture heating up to 100 ℃, home position polymerization reaction 4 hours; Make the epoxy resin ring-opening reaction; Add 40 gram water, 2 gram anionic emulsifiers, 1 donaxine neutralizing agent again, adopt the back emulsification method, 5000 rev/mins of high-speed stirring were disperseed 2 hours; Recessed soil/the composite epoxy resin of preparation water nano; Add 10 gram aqueous epoxy curing agents, 5 gram white titanium pigments, 2 gram permanent white, 5 gram iron micas, 1 gram silica powder, 2 gram aqueous dispersants, 2 gram water-based skimmers again, dispersed with stirring 1 hour obtains water-based anticorrosive paint.Coating is coated on the iron plate, and 200 ℃ solidified drying and forming-film 5 minutes.
Nano concave earth/epoxy anticorrosion the layer material of preparation, hardness 4H, 1 grade of sticking power (cross-hatching), weathering resistance＞800 hour, salt-fog resistant time＞600 hour.
Claims (10)
1. the recessed soil of long-acting water nano/epoxy anticorrosion coated material; It is characterized in that recessed grogs of organic modified nano and the method for aqueous epoxy resins through in-situ polymerization or blend; Obtain the recessed soil/composite epoxy resin of water nano; With nonessential water-based blending resin, nonessential aqueous epoxy curing agent, nonessential water, nonessential color stuffing, nonessential coatings additive(s) blend, at 5-300 ℃ of film-forming, but recessed grogs of organic modified nano is crosslinked with the aqueous epoxy resins in-situ chemical in film process again; Can obtain the recessed soil of long-acting water nano/epoxy anticorrosion coated material
Wherein, Recessed grogs of organic modified nano is that to utilize the acid larger molecular organics have functional group be the molecular recognition and the inducing action of recessed soil to attapulgite; The organic-inorganic nano self-assembly; It is that 10-500 nanometer spherical particle or elliposoidal particle obtain that the club shaped structure of recessed soil changes particle diameter into
The sub-consumption of the recessed grogs of organic modified nano accounts for the 1-70wt% of starting material total amount,
Aqueous epoxy resins accounts for the 30-99wt% of starting material total amount,
Nonessential water-based blending resin consumption accounts for the 0-30wt% of starting material total amount,
Nonessential aqueous epoxy curing agent consumption accounts for the 0-20wt% of starting material total amount,
Nonessential water consumption accounts for the 0-50wt% of starting material total amount,
Nonessential color stuffing consumption accounts for the 0-50wt% of starting material total amount,
Nonessential coatings additive(s) consumption accounts for the 0-30wt% of starting material total amount.
2. the recessed soil of long-acting water nano according to claim 1/epoxy anticorrosion coated material; It is characterized in that recessed grogs of organic modified nano is to utilize to have molecular recognition and the inducing action of the acid larger molecular organics of functional group to attapulgite (recessed soil); The organic-inorganic nano self-assembly; It is that 10-500 nanometer spherical particle or elliposoidal particle obtain that the club shaped structure of recessed soil changes particle diameter into; Acid larger molecular organics is that molecular weight is organism or the polymkeric substance of 300-500000; The surface has or chemically modified has and can comprise hydroxyl, carboxyl, sulfonic group, sulfydryl, amido, carboxamido-group, imido grpup with attapulgite bonded hydrophilic functional group; Being specially wetting ability hydroxyl organic macromolecule, wetting ability contains carboxyl organic macromolecule, wetting ability and contains sulfonic group organic macromolecule, wetting ability amino-contained organic macromolecule, wetting ability and contain imido grpup organic macromolecule, wetting ability amide-containing organic macromolecule, wetting ability and contain the sulfydryl organic macromolecule; Select 1-3 kind wherein for use, contain a kind of acid organic macromolecule at least.
3. the recessed soil of long-acting water nano according to claim 1/epoxy anticorrosion coated material is characterized in that aqueous epoxy resins is selected from one or more the combination in water-based bisphenol A epoxide resin, water-based hydrogenated bisphenol A epoxy resin, water-based cycloaliphatic epoxy resin, the water-based bisphenol F epoxy resin.
4. the recessed soil of long-acting water nano according to claim 1/epoxy anticorrosion coated material is characterized in that nonessential water-based blending resin is selected from one or more combination of conventional water-and acrylate resin in the coating, aqueous polyester resin, aqueous alkide resin, waterborne organic silicon resin, waterborne polyurethane resin, water-compatible amino resin, water-based fluorocarbon resin.
5. the recessed soil of long-acting water nano according to claim 1/epoxy anticorrosion coated material is characterized in that nonessential aqueous epoxy curing agent is selected from one or more combination of conventional aqueous epoxy resins use epoxy hardener in the coating material production.
6. the recessed soil of long-acting water nano according to claim 1/epoxy anticorrosion coated material, it is characterized in that nonessential color stuffing be selected from water-borne coatings produce in one or more combination of conventional color stuffing.
7. the recessed soil of long-acting water nano according to claim 1/epoxy anticorrosion coated material; It is characterized in that nonessential coatings additive(s) is selected from conventional auxiliary agent in the water-borne coatings; Like one or more combination of flow agent, thickening material, film coalescence aid, skimmer, anti-settling agent, dispersion agent, solubility promoter, nonessential auxiliary dosage accounts for the 0-30wt% of starting material total amount.
8. the preparation method of the recessed soil of long-acting water nano as claimed in claim 1/epoxy anticorrosion coated material, it comprises following steps:
(1) under agitation condition, recessed grogs of organic modified nano is mixed the recessed soil/composite epoxy resin of preparation water nano with aqueous epoxy resins;
(2) under agitation condition; In the recessed soil/composite epoxy resin of water nano, add nonessential water-based blending resin, nonessential aqueous epoxy curing agent, nonessential water, nonessential color stuffing, the mixing of nonessential coatings additive(s), the recessed soil/corrosion-resistant epoxy paint of preparation water nano;
(3) at 5-300 ℃ of film-forming.
9. the preparation method of the recessed soil of long-acting water nano as claimed in claim 1/epoxy anticorrosion coated material, it comprises following steps:
(1) under agitation condition, with recessed grogs of organic modified nano and epoxy blend;
(2) adopt in-situ polymerization, carboxyl and epoxy resin ring-opening reaction on recessed grogs of organic modified nano, preparation nano concave earth/composite epoxy resin;
(3) under agitation condition, adopt conventional back emulsification method in the water-borne coatings production of resins, the recessed soil/composite epoxy resin of preparation water nano;
(4) under agitation condition; In the recessed soil/composite epoxy resin of water nano, add nonessential water-based blending resin, nonessential water, nonessential aqueous epoxy curing agent, nonessential color stuffing, the mixing of nonessential coatings additive(s), the recessed soil/corrosion-resistant epoxy paint of preparation water nano;
(5) at 5-300 ℃ of film-forming.
10. one kind like the application of the recessed soil of each described long-acting water nano of claim 1-9/epoxy anticorrosion coated material in anti-corrosion of metal, building decoration field.
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