CN111574949A - Elastic anti-corrosion adhesive and preparation method thereof - Google Patents

Elastic anti-corrosion adhesive and preparation method thereof Download PDF

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CN111574949A
CN111574949A CN202010488935.4A CN202010488935A CN111574949A CN 111574949 A CN111574949 A CN 111574949A CN 202010488935 A CN202010488935 A CN 202010488935A CN 111574949 A CN111574949 A CN 111574949A
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polyether
corrosion
rpm
speed
stirring motor
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杨小刚
王向阳
李斌
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Qingdao Haifulai Safety Technology Co ltd
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Qingdao Haifulai Safety Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses an elastic anticorrosion adhesive and a preparation method thereof, belonging to the technical field of anticorrosion materials, wherein an amino polyether is adopted in the formula of a component A, a self-synthesized polyurea modified silyl polyether resin is adopted in a component B, and the polyurea modified silyl polyether resin contains trace residual isocyanate group for reaction, so that the stock of free amino polyether in the elastic anticorrosion adhesive is greatly reduced; meanwhile, the amino polyether reacts with the epoxy resin in the component B and part of epoxy groups in the gamma-glycidyl ether oxypropyltrimethoxysilane, so that the mechanical property of the elastic anticorrosive adhesive is improved, and the introduction of the epoxy groups is favorable for improving the chemical resistance of the elastic anticorrosive adhesive and can adapt to the erosion of acid rain and the like in industrial atmospheric environment; most of free amine-terminated polyether is reacted through the reaction, so that the phenomenon that the free amine-terminated polyether is excessive to be migrated and separated out is avoided, the method can be widely applied to acidic or alkaline environments, and has remarkable economic benefit.

Description

Elastic anti-corrosion adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of anticorrosive materials, in particular to an elastic anticorrosive adhesive and a preparation method thereof.
Background
The boiler steel frame is a common facility and component in the industries of petrifaction, electric power, gas and the like, and plays a vital role in the daily production process. The top of the boiler steel frame is a structure that an overhead color steel plate and an I-shaped steel purline penetrate and are fixed through self-tapping screws at the drill tail. Due to the fact that the steel plate is in a severe marine atmosphere corrosion environment and a severe industrial atmosphere corrosion environment, rainwater, corrosive gas, accumulated water, acidic slurry, microorganisms and the like all corrode the steel plate, and dust and the like deposited at gaps accelerate electrochemical corrosion, and threaten the construction safety. At present, the phenomena that the joint and the fixing part of the color steel plate and the purline and the nearby part are rusted and perforated, and even the head part of a self-tapping screw for partially fixing the color steel plate is rusted and broken are common.
In engineering practice, the connection part of the color steel plate and the steel purline directly leads to the fixation failure of the self-tapping screw at the drill tail due to corrosion. Moreover, the color steel plate is positioned at high altitude, and once the fixation fails, if strong wind force is met, the high altitude falls, and nearly fatal threats can be formed on the safety of personnel, equipment and the like. The corrosion reason analysis of the connecting part of the color steel plate and the steel purline is as follows: (1) the overhead (corrugated) color steel plate is in salt spray corrosion and industrial atmospheric corrosion environment all the year round due to being located at a higher position above the ground. (2) Because the color steel plates and the steel purlins are penetrated and fixed together through the self-tapping screws at the drill tails, and a large number of gaps exist at the joints, the corrosion of the gaps at the positions generally exists, and the damage to the color steel plates, the self-tapping screws and the steel purlins is aggravated. (3) Fretting corrosion caused by vibration generated during the operation of the boiler unit also aggravates the damage to the connecting part of the color steel plate and the steel purline. (4) The junction between various steel sheet and steel purlin forms stress corrosion, and the great wind-force of year leads to various steel sheet to produce frequent fluctuation by a relatively large margin to the pressure of the joint portion of steel purlin simultaneously in the high altitude, has further aggravated the stress of stress point position and has fluctuated by a wide margin, leads to corroding further aggravation. (5) Because the highest end and the lowest end of the color steel plate ceiling are easy to have a small amount of accumulated water, the electrochemical corrosion condition is common, and the damage to the two parts is aggravated.
Due to the reasons, the color steel plate is corroded and damaged, and the corrosion part of the color steel plate ceiling is mainly at the steel purlines, and the color steel plates at the highest point and the lowest point are corroded most seriously.
When the color steel plate is installed, the lower concave surface of the steel plate is lapped on the surface of supporting steel (purlin) and is penetrated and fixed through the self-tapping screw at the drill tail, so that gaps exist between the surface of the steel plate and the surface of the purlin, between the surface of the self-tapping screw at the drill tail and the surface of the color steel plate, and between the surface of the self-tapping screw at the drill tail and the surface of the purlin, and the corrosion of the gaps is a big problem facing the corrosion prevention of the color. Moreover, the purlin surface has born weight more than the various steel sheet, and purlin surface bearing pressure is greater than the dead weight more than the various steel sheet under positive wind pressure state, and purlin surface bearing pressure is less than dead weight more than the various steel sheet under the negative wind pressure state, nevertheless bores the self tapping screw head of tail and has received ascending pulling force simultaneously, so various steel sheet, purlin and bore the self tapping screw surface of tail and all have stress corrosion. In addition, fretting corrosion also occurs due to vibration and frequent alternating of wind strength during the operation of the unit.
In the prior art, the color steel plate adopts an anti-corrosion means of brushing acrylic polyurethane anti-corrosion paint at present, the initial anti-corrosion effect is still good, but the boiler color steel plate is in a severe marine atmospheric corrosion environment and a severe industrial atmospheric corrosion environment, and the coating can generate the phenomena of rust return, yellowing and the like after a period of time use, and even generates obvious bubbling, cracking and peeling phenomena; secondly, the coating in the prior art does not have the functions of rust prevention and rust conversion, and can not effectively inhibit the occurrence and growth of rust for a long time; finally, microorganisms are easy to breed in the working condition environment where the color steel plate of the boiler unit is located, metabolites of the microorganisms are directly deposited due to the existence of the microorganisms, and then electrochemical corrosion is caused, and the currently used acrylic polyurethane anticorrosive paint is difficult to effectively kill and inhibit the microorganisms, so that the microbial corrosion is difficult to prevent.
The ceiling is generally composed of a steel purline and a color steel plate, the connection and fixation is realized by screwing a stainless steel drill tail wire into a whole after penetrating through the color steel plate and the steel purline, the connection structure is corroded quickly in a marine atmospheric environment, the corrosion rate of the color steel plate at the part contacted with the drill tail wire is in geometric multiple and rapidly diffuses towards the periphery of the drill tail wire, once the corrosion surface is larger than the diameter of the tail wire at the end part of the drill tail wire, the original fixing mode fails, in addition, coastal typhoon is frequent, the ceiling is very easy to be scraped by strong typhoon to fall to the ground, and the safety of nearby personnel and other facilities is seriously threatened. In the prior art, in order to solve the corrosion problem of the part of the color steel plate, building sealant is adopted to cover the connecting part. In recent years, silicone sealant, polysulfide sealant and the like are adopted successively, but the problems are not solved, firstly, the silicone sealant contains more plasticizers, the plasticizers are easy to precipitate in the long-term high-low temperature exposure process of the outside to cause pollution, and in addition, the precipitation loss of the plasticizers causes the volume loss of the sealant layer, so that the defects of the sealant layer are formed to gradually lose the sealing effect, and water vapor carrying oxygen is easy to permeate the sealant layer to corrode a color steel plate and a steel structure part contacted with the color steel plate; polysulfide sealant has strong odor, is easy to cause discomfort to constructors, and a glue layer is easy to cause polysulfide group to break and form a new cross-linking point with an adjacent chain segment due to heating in the presence of oxygen, so that the material is aged, hardened and loses elasticity, further, the surface of the glue has cracks, the elongation at break is reduced, the part needing to be protected is gradually lost, and the corrosion hazard is further aggravated.
Disclosure of Invention
The invention provides an elastic anti-corrosion adhesive and a preparation method thereof, aiming at solving the defects of short protection life, poor anti-rust and rust conversion effects, poor microbial corrosion protection effects and the like of an acrylic polyurethane anti-corrosion coating, effectively solving the typical corrosion problems of pitting corrosion, crevice corrosion, galvanic corrosion, microbial corrosion and the like of a color steel plate part of a boiler unit, having better waterproof sealing property, not going bad after long-term use, having stronger anti-rust and rust conversion functions, effectively killing microorganisms such as iron bacteria, thiobacillus, sulfate reducing bacteria and the like so as to prevent microbial corrosion, being widely applicable to acidic or alkaline environments and having remarkable economic benefits.
The specific technical scheme provided by the invention is as follows:
in a first aspect, the elastic anti-corrosion adhesive provided by the invention comprises a component A and a component B, wherein the component A and the component B are in a mass fraction ratio of 4:1, and the component A comprises the following raw materials in percentage by mass: 30-48% of amine-terminated polyether, 3-7% of fumed silica, 30-45% of pigment, 0.5-2.5% of catalyst, 0.5-4.5% of accelerator, 7-13% of metal corrosion inhibition additive and 1-8% of deionized water, wherein the component B comprises the following raw materials in percentage by mass: 45-60% of matrix polymer, 1-5% of liquid epoxy resin, 1.5-3.5% of stabilizer, 1-4% of adhesion promoter, 7.1-14% of fumed silica, 13.5-35% of nano reinforcing powder, 1.2-3.5% of antioxidant and 1.2-3.5% of ultraviolet absorbent.
Optionally, the metal corrosion inhibition additive comprises a rust converting agent, polyaniline and a metal corrosion inhibitor in a mass ratio of 2:1:1, wherein the polyaniline is a mixture of intrinsic polyaniline and secondarily doped polyaniline.
Optionally, the rust converting agent is a polyphosphoric acid-tannic acid type rust converting agent, and the polyphosphoric acid-tannic acid type rust converting agent comprises the following raw materials in percentage by mass: 45% of polyphosphoric acid, 1% of tannic acid, 1% of urotropine and 10% of hydroxyl polyether.
Optionally, the metal corrosion inhibitor is a complex metal corrosion inhibitor, and the complex metal corrosion inhibitor comprises sodium tungstate, zinc sulfate, thiourea, calcium gluconate, sodium polyphosphate, polyaspartic acid and sodium silicate in a mass ratio of 1:3:4:3:2.5: 2.
Optionally, the base polymer includes silane-modified polyether resin and polyurea-modified silane-based polyether resin, wherein the silane-modified polyether resin is at least one of methyldimethoxysilane-terminated polyether resin or trimethoxysilane-terminated polyether resin.
Optionally, the polyurea modified silyl polyether resin contains urea bonds and ether bonds, wherein the urea bonds and the ether bonds are introduced into the dehydrated and hydrogenated MDI reacted terminal secondary amino polyether and terminal primary amino polyether, and the terminal secondary amino polyether and the terminal primary amino polyether are reacted with N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyltrimethoxysilane.
Optionally, the polyurea modified silane-based polyether resin comprises the following raw materials in percentage by mass: 17-23% of hydrogenated MDI, 36-67% of terminal secondary amino polyether, 2-39% of terminal primary amino polyether, 0.5-4.5% of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 3.5-8% of N-butylaminopropyltrimethoxysilane.
In another aspect, the present invention also provides a method for preparing the above elastic anti-corrosive adhesive, comprising:
(1) adding amine-terminated polyether into a planetary stirring kettle, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 10-20 rpm and 500-800 rpm, sequentially adding fumed silica, pigment, a catalyst, an accelerant and a metal corrosion inhibition additive, respectively regulating the speed of the planetary stirring motor and the high-speed stirring motor to 30-40 rpm and 1000-1200 rpm after the addition is finished, starting a heating device, heating to 60 ℃, and stirring for 1-1.5 hours at the temperature of 60 +/-5 ℃;
(2) stopping heating, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 10-20 rpm and 500-800 rpm, adding deionized water, continuously stirring for 1-1.5 h, then opening a vacuum valve, defoaming for 10-15 min under the vacuum degree of 0.07MPa, then closing the vacuum valve, and closing the planetary stirring kettle to discharge after the temperature is lower than 50 ℃ to prepare a component A of the elastic anticorrosive adhesive;
(3) metering a matrix polymer, nano reinforcing powder, fumed silica and liquid epoxy resin, adding the metered matrix polymer, nano reinforcing powder, fumed silica and liquid epoxy resin into an empty planetary stirring kettle, starting a planetary stirring motor and a high-speed stirring motor, respectively regulating the speeds to 10-20 rpm and 500-800 rpm, and continuously stirring until the powder material is completely wetted;
(4) regulating the speed of a planetary stirring motor and a high-speed stirring motor to 30-40 rpm and 1000-1200 rpm respectively, stirring at a high speed for 1-1.5 h, starting a heating device, starting a vacuum valve after the temperature is raised to 110 ℃, and dehydrating for 20-30 min under the negative pressure of 0.07 MPa;
(5) stopping heating after dehydration is finished, adding a stabilizer, an adhesion promoter, an antioxidant and an ultraviolet absorbent, continuously stirring for 1-1.5 h, then opening a vacuum valve, keeping the negative pressure at 0.07MPa, continuously degassing for 20-30 min, and then discharging to obtain a component B of the elastic anticorrosive adhesive;
(6) before use, the component A and the component B are mixed with each other according to the volume ratio of 4:1 to obtain the elastic anti-corrosion adhesive.
Optionally, the matrix polymer is prepared by the following method:
metering secondary amine-terminated polyether and primary amine-terminated polyether, adding the metered polyether into a dehydration kettle, starting stirring and heating, keeping the rotating speed at 200rpm, opening a vacuum valve and maintaining the vacuum degree at 0.07MPa, keeping the temperature at 115 +/-5 ℃ for 2-3 h, stopping heating after dehydration, closing the vacuum valve, introducing nitrogen into the dehydration kettle, cooling until the material temperature is lower than 50 ℃, and adding the dehydrated raw material into a planetary stirring reaction kettle;
adding the dehydrated raw materials into a planetary stirring reaction kettle, starting a planetary stirring motor and a high-speed stirring motor, regulating the speed to 30-40 rpm and 1000-1200 rpm respectively, then continuing to add hydrogenated MDI into the planetary stirring reaction kettle, filling nitrogen into the planetary stirring reaction kettle after adding the hydrogenated MDI, reacting for 30min, then starting heating and raising the temperature to 70 ℃, controlling the temperature to be 70 +/-5 ℃, continuing to react for 2-3 h, stopping heating, and cooling to below 50 ℃;
after the material temperature in the planetary stirring reaction kettle is lower than 50 ℃, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 30-40 rpm and 1000-1200 rpm, adding the measured N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyl trimethoxysilane into the planetary stirring reaction kettle, introducing nitrogen after the addition is finished, heating to 80 ℃, keeping the temperature at 80 +/-5 ℃, stopping heating after reacting for 3-4h, and respectively regulating the speed of the planetary stirring motor and the high-speed stirring motor to 10-20 rpm and 500-800 rpm;
opening a vacuum valve, defoaming for 15-20 min under the vacuum degree of 0.07MPa, closing the vacuum valve, cooling to below 50 ℃, stopping stirring and discharging to obtain the polyurea modified silyl polyether resin;
mixing the silane modified polyether resin and the polyurea modified silane-based polyether resin according to the mass ratio of 1:1, and uniformly mixing to obtain the matrix polymer.
The invention has the following beneficial effects:
the embodiment of the invention provides an elastic anticorrosive adhesive and a preparation method thereof, wherein amino polyether is adopted in the formula of the component A, self-synthesized polyurea modified silyl polyether resin is adopted in the component B, and the polyurea modified silyl polyether resin contains trace residual isocyanate group for reaction, so that the stock of free amino polyether in the elastic anticorrosive adhesive is greatly reduced; meanwhile, the amino polyether reacts with the epoxy resin in the component B and part of epoxy groups in the gamma-glycidyl ether oxypropyltrimethoxysilane, so that the mechanical property of the elastic anticorrosive adhesive is improved, and the introduction of the epoxy groups is favorable for improving the chemical resistance of the elastic anticorrosive adhesive and can adapt to the erosion of acid rain and the like in industrial atmospheric environment; most of free-state amine-terminated polyether is reacted through reaction, migration and precipitation caused by excessive free-state amine-terminated polyether are avoided, the typical corrosion problems of pitting corrosion, crevice corrosion, galvanic corrosion, microbial corrosion and the like of the color steel plate part of a boiler unit can be effectively solved, the water-proof sealing performance is good, the water-proof sealing performance is not deteriorated after long-term use, the rust-proof sealing performance is strong, meanwhile, microorganisms such as iron bacteria, thiobacillus, sulfate reducing bacteria and the like can be effectively killed, microbial corrosion is prevented, the water-proof sealing agent can be widely applied to acidic or alkaline environments, and remarkable economic benefits are achieved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a scanning electron micrograph of intrinsic polyaniline and doped polyaniline in accordance with an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides an elastic anticorrosive adhesive and a preparation method thereof, which are suitable for anticorrosive protection of a contact part between a color steel plate of a ceiling and a steel purline, solve the defects of short protection life, poor antirust rust conversion effect, poor microbial corrosion protection effect and the like of an acrylic polyurethane anticorrosive paint, can effectively solve the typical corrosion problems of pitting corrosion, crevice corrosion, galvanic corrosion, microbial corrosion and the like of the color steel plate part of a boiler unit, have better waterproof sealing property, do not deteriorate after long-term use, have stronger antirust rust conversion function, can effectively kill microorganisms such as iron bacteria, thiobacillus, sulfate reducing bacteria and the like so as to prevent microbial corrosion, can be widely applied to various acidic and alkaline corrosion environments, and have remarkable economic benefits.
Example one
The elastic anticorrosive adhesive provided by the embodiment of the invention comprises a component A and a component B, wherein the component A and the component B are in a mass fraction ratio of 4:1, and the component A comprises the following raw materials in percentage by mass: 30-48% of amine-terminated polyether, 3-7% of fumed silica, 30-45% of pigment, 0.5-2.5% of catalyst, 0.5-4.5% of accelerator, 7-13% of metal corrosion inhibition additive and 1-8% of deionized water, wherein the component B comprises the following raw materials in percentage by mass: 45-60% of matrix polymer, 1-5% of liquid epoxy resin, 1.5-3.5% of stabilizer, 1-4% of adhesion promoter, 7.1-14% of fumed silica, 13.5-35% of nano reinforcing powder, 1.2-3.5% of antioxidant and 1.2-3.5% of ultraviolet absorbent.
The matrix polymer adopted in the component B in the embodiment of the invention comprises silane modified polyether resin and polyurea modified silyl polyether resin, wherein the silane modified polyether resin is at least one of methyl dimethoxy silane terminated polyether resin or trimethoxy silane terminated polyether resin. The polyurea modified silyl polyether resin contains urea bonds and ether bonds, wherein the urea bonds and the ether bonds are introduced into dehydrated hydrogenated MDI, and the terminal secondary amino polyether and the terminal primary amino polyether are reacted with N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyl trimethoxysilane. Specifically, the polyurea modified silane-based polyether resin comprises the following raw materials in percentage by mass: 17-23% of hydrogenated MDI, 36-67% of terminal secondary amino polyether, 2-39% of terminal primary amino polyether, 0.5-4.5% of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 3.5-8% of N-butylaminopropyltrimethoxysilane.
In the component B of the embodiment of the invention, the terminal secondary amino polyether and the terminal primary amino polyether are dehydrated and then reacted with hydrogenated MDI to obtain urea bonds and ether bonds, and the urea bonds and the ether bonds are introduced into the hydrogenated MDI to obtain the polyurea modified silyl polyether resin through the reaction with N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyl trimethoxysilane, and the polyurea modified silyl polyether resin is obtained because the component B adopts silane modified polyether resin (both the methyl dimethoxy silane terminated polyether resin and the trimethoxy silane terminated polyether resin are silane terminated polyether resin) and self-synthesized polyurea modified silyl polyether resin, and the urea bonds are introduced into the molecular structure of the polyurea modified silyl polyether resin through the reaction with isocyanate in the hydrogenated MDI and long-chain 2-functionality amino terminated polyether amino
Figure BDA0002520175800000081
And an ether linkage (-CH)2-O-CH2-) urea bond is introduced, which not only overcomes the general disadvantage of heat resistance of the adhesive using silane terminated polyether resin alone, but also improves the elastic mechanical property of the elastic anticorrosion adhesive; meanwhile, the introduction of urea bonds also improves the oil resistance of the elastic anticorrosive adhesive; the introduction of ether bond can ensure that the polyurea modified silyl polyether resin keeps certain elasticity, and the synergistic effect with the silane terminated polyether resin (namely, the methyl dimethoxysilane terminated polyether resin or the trimethoxy silane terminated polyether resin) ensures that the product has excellent fatigue resistance; hydrogenated MDI belongs to the aliphatic seriesThe hydrogenated MDI does not have unsaturated double bonds, so that the effect on light is very stable, the weather resistance is excellent, yellowing is not generated after long-time sunlight exposure, and further unsaturated double bonds do not exist with the hydrogenated MDI, so that the effect on light is very stable, the weather resistance is excellent, yellowing is not generated after long-time sunlight exposure, and further the urea bond-containing product formed by the urea bond-containing product and the elastic anticorrosion adhesive is greatly improved, so that the durability of the elastic anticorrosion adhesive can be improved, and yellowing and aging are not generated after long-time use.
According to the embodiment of the invention, amine-terminated polyether in the component A reacts with epoxy resin in the component B and epoxy groups in partial adhesion promoters (gamma-glycidyl ether oxypropyl trimethoxysilane and the like), and a chemical bond is introduced through the reaction of the amine groups and the epoxy groups, so that the crosslinking density of a final product is improved, and the mechanical property of the elastic anticorrosive adhesive is improved. In addition, after the component B reacts with itself, a small amount of unreacted isocyanate groups remain in the component B, and the remaining isocyanate groups can be completely consumed by the reaction with the amine-terminated polyether in the component A.
The polyurea modified silyl polyether resin adopted in the component B of the embodiment of the invention contains trace residual isocyanate groups, and can react with the free amino polyether in the component A, so that the storage amount of the free amino polyether in the elastic anti-corrosion adhesive is greatly reduced, and the phenomenon that the free amino-terminated polyether is excessive in the finished product of the elastic anti-corrosion adhesive and is migrated and separated out is effectively avoided; meanwhile, the amino polyether in the component A reacts with the epoxy resin in the component B and the epoxy group in part of gamma-glycidyl ether oxypropyltrimethoxysilane (adhesion promoter), so that the mechanical property of the elastic anticorrosive adhesive in the embodiment of the invention is further improved, and the introduction of the epoxy group is favorable for improving the chemical resistance of the elastic anticorrosive adhesive in the embodiment of the invention, so that the elastic anticorrosive adhesive can adapt to the erosion of acid rain and the like in industrial atmospheric environment; the chemical reaction of the amine-terminated polyether, the isocyanate group and the epoxy group and the main curing reaction (hydrolysis reaction of silane at the end) of the elastic anticorrosive adhesive disclosed by the embodiment of the invention are cooperatively generated, so that the elastic anticorrosive adhesive disclosed by the embodiment of the invention has the advantage of high surface drying rate, and the construction efficiency is greatly improved; the free amine-terminated polyether is consumed by a large part through the reaction, so that the phenomenon that the free amine-terminated polyether exists too much and is migrated and separated out in the elastic anticorrosive adhesive in the embodiment of the invention is avoided.
Specifically, in the component A of the elastic anticorrosive adhesive provided by the embodiment of the invention, the molecular weight of the amine-terminated polyether is 2000, and the fumed silica is hydrophobic-treated fumed silica with a specific surface area of 130-180; the pigment is a combination of rutile titanium dioxide and doped polyaniline, and illustratively, the mass ratio of rutile titanium dioxide to doped polyaniline in the pigment is 4: 1; the catalyst is one or more of bismuth neodecanoate, bismuth sulfonate, bismuth laurate, bismuth isooctanoate and bismuth naphthenate; the promoter is 2, 4, 6-tris (dimethylaminomethyl) phenol.
In the component B of the elastic anticorrosive adhesive, the liquid epoxy resin is bisphenol A resin with the epoxy equivalent of 170-200 g/eq; the stabilizer is vinyl trimethoxy silane; the adhesion promoter is gamma-glycidol ether oxygen propyl trimethoxy silane (promoting chain growth reaction and enhancing crosslinking density); the fumed silica has a specific surface area of 130-180, and belongs to a hydrophobic easily-dispersible type; the nano reinforcing powder is a mixture of nano calcium carbonate and carbon nano tubes, wherein the surface of the nano calcium carbonate is treated by organic acid, and the mass ratio of the nano calcium carbonate to the carbon nano tubes is 9: 1. Exemplary antioxidants are pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; the ultraviolet absorbent is 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole.
The elastic anticorrosive adhesive disclosed by the embodiment of the invention has excellent adhesive force to most base materials (including surface porous base materials), the silane-terminated polyether resin and the polyurea modified silane-based polyether resin adopted in the formula have extremely low surface energy and good wettability and permeability to the base materials, and the adhesion promoter gamma-glycidyl ether oxypropyl trimethoxy silane can form a chemical bond with the surface of the base material, so that the bonding property of the anticorrosive adhesive is further enhanced.
The components of the elastic anticorrosive adhesive provided by the embodiment of the invention can be added with an anticorrosive composition, tannic acid, polyaspartic acid and the like contained in the anticorrosive composition can rapidly react with iron oxide on the surface of steel in the presence of a trace amount of water to form a firm iron rust chelate on the surface of the steel, so that the strong adhesion of resin and an adhesion promoter in the elastic anticorrosive adhesive to the surface of the steel can be realized, the part to be protected is sealed by the elastic anticorrosive adhesive layer after the elastic anticorrosive adhesive layer is completely cured, and the elastic anticorrosive adhesive can play a stable protection role for a long time due to the fatigue resistance of the elastic anticorrosive adhesive even under the condition of frequent micromotion.
Further, the metal corrosion inhibition additive adopted by the embodiment of the invention comprises a rust converting agent, polyaniline and a metal corrosion inhibitor in a mass ratio of 2:1:1, wherein the polyaniline is a mixture of intrinsic polyaniline and secondarily doped polyaniline. The rust converting agent is a polyphosphoric acid-tannic acid type rust converting agent, and the polyphosphoric acid-tannic acid type rust converting agent comprises the following raw materials in percentage by mass: 45% of polyphosphoric acid, 1% of tannic acid, 1% of urotropine and 10% of hydroxyl polyether.
Specifically, polyaniline in the metal corrosion inhibition additive provided by the embodiment of the invention is a mixture of doped polyaniline and intrinsic polyaniline, wherein the mass ratio of the doped polyaniline to the intrinsic polyaniline is 0.2: 1-5: 1. The main chain of polyaniline molecules of doped polyaniline captures protons to show positive electricity, and the molecular chain of polyaniline contains counter anions in a dopant; preferably, the doped polyaniline in the metal corrosion inhibition additive of the embodiment of the invention is a tannin system secondary doped polyaniline nanomaterial, and the molecular chain of the secondary doped polyaniline nanomaterial contains tannin pair anions introduced by secondary doping; the eigenstate polyaniline is the insulated eigenstate polyaniline which is changed from doped polyaniline by deprotonation and de-doping according to the unique doping-de-doping characteristics of polyaniline.
Referring to fig. 1, in fig. 1, a is a structural diagram of intrinsic polyaniline under a scanning electron microscope, and b is a structural diagram of doped polyaniline under a scanning electron microscope. Comparison of a scanning electron microscope shows that the eigenstate polyaniline has small molecular fragment structures such as nanoparticles and nano short rods, and an agglomeration phenomenon exists in the eigenstate polyaniline product; the secondary doping polyaniline product is subjected to de-doping and secondary doping treatment, the length of the fiber of the product is increased, the length-diameter ratio of the product is increased, the appearance of the fiber is more regular, the size of the product is more uniform, and the like, and the product is improved to different degrees, and a compact structure with a network structure and a parallel arrangement structure coexisting is formed. Besides, polyaniline is subjected to doping-de-doping-secondary doping treatment, when anions are introduced, originally curled molecular chains can be unfolded, and single polarons are converted from localized to delocalized, so that the arrangement and conformation of the polyaniline molecular chains are influenced, the regrowth of the polyaniline molecular chains is promoted, the appearance is obviously improved, the conformation of the polyaniline molecular chains is converted from winding to stretching, the interaction among the molecular chains is enhanced, and the polyaniline reactivity is further improved.
A large amount of data analysis shows that the eigenstate polyaniline can generate passivation reaction with metal materials, a strict passivation film is formed on the contact surface of metal and the eigenstate polyaniline, the corrosion of the metal is slowed down, but the eigenstate polyaniline has a single structure, and the corrosion prevention effect is mainly reflected on the passivation effect of the polyaniline. The difference is that the doped polyaniline has a corrosion inhibition effect on the metal surface under the action of tannic acid. The corrosion inhibition generally means that a monomolecular shielding layer is formed on the surface through the adsorption of metal on organic substances, so that the corrosion rate of an anode (cathode) is limited, and the anti-corrosion protection effect is achieved.
Specifically, the central nitrogen atom of the doped polyaniline compound has unshared electron pairs, and when the metal surface layer has an empty electron orbit, lone pair electrons of the central atom of the polar group can form a coordinate bond with the empty electron orbit, so that the adsorption effect of the metal surface layer on molecules is more obvious, and a hydrophobic adsorption layer is formed to achieve the effect of reducing the corrosion rate. The doped polyaniline has shielding effect and electric field effect on the metal surface to be protected under the action of tannic acid. The shielding action mechanism of the doped polyaniline on the metal surface to be protected is mainly to prevent a corrosive medium from contacting with a metal base material so as to protect the metal material.
The existence of doped polyaniline on the metal surface can effectively separate the metal material from the surrounding corrosive environment, the doped polyaniline can react with oxygen in the tannic acid environment to oxidize the polyaniline and reduce the oxygen, and O is2+2H2O+PAn0＝PAn++4OH-And the polyaniline coating acts with oxygen to block the penetration of oxygen and prevent the surface of the metal base material from oxygen absorption corrosion.
Due to the difference of reaction activity, the doped polyaniline and the eigen-state polyaniline in the coating formed by the elastic anticorrosive adhesive can generate a 'layering' phenomenon, namely the doped polyaniline is often gathered on the surface of the metal base material to be protected and reacts with the metal base material in a 'preferential' manner, and the eigen-state polyaniline is distributed on the 'outer layer'.
In addition, the elastic anti-corrosion adhesive disclosed by the embodiment of the invention contains the intrinsic polyaniline and the doped polyaniline, so that the elastic anti-corrosion adhesive can be widely applied to corrosion environments under different acid-base conditions, and can play a good anti-corrosion role in both acid environments and alkaline environments.
When the material is in a corrosive environment with the pH value less than or equal to 7, the eigenstate polyaniline distributed on the outer layer can capture H in the environment and an anticorrosive system+So that protons enter the main chain of polyaniline and are electropositive, and to maintain electroneutrality, the counter anions in the doped acid system also enter the main chain of the polymer, and simultaneously, H in the environment and the system+And also provides acidity required for synthesizing polyaniline. When the polyaniline is in a corrosion environment with the pH value larger than 7, the doped polyaniline is subjected to de-doping in an alkaline environment, tannin is released to anions, and eigenstate polyaniline is obtained, the eigenstate polyaniline can generate a passivation reaction with a metal material, a strict passivation film is formed at the contact position of metal and polyaniline, and the corrosion of the metal is slowed down.
Specifically, when the polyaniline is in a slightly acidic corrosive environment with the pH value less than or equal to 7, the eigenstate polyaniline distributed on the outer layer can capture H in the environment and the system+Ions, such thatThe proton enters the main chain of the intrinsic polyaniline, which is electropositive, and is doped with anions in an acid system and Cl in the environment to maintain an electrically neutral environment-(main component causing pitting corrosion) also enters the main chain of the polyaniline polymer. Through the process, when the doped polyaniline is in contact with metal, an electric field can be generated on the surface layer of the metal, the direction of the electric field is opposite to the moving direction of electrons, so that the electron transmission process is hindered, electrons can be effectively shielded from being transferred from the metal material to an oxide material, namely, the doped polyaniline has the effect of the electric field on the surface of the metal material, and the oxidation corrosion of the surface of the metal material can be hindered. In addition, tannic acid has a strong anti-corrosion function to anions (functional groups), is also diffused into polyaniline molecular chains for balancing electric neutrality, can form a synergistic effect in the reaction of metal and polyaniline, and enhances the protection effect on metal materials. At the same time, H in the environment and in the system+And also provides acidity required for synthesizing polyaniline.
When the polyaniline is in an alkaline corrosion environment with the pH value more than 7, the doped polyaniline is subjected to de-doping in the alkaline environment, tannin is released to anions, and eigenstate polyaniline is obtained, the eigenstate polyaniline can generate a passivation reaction with a metal material, a strict passivation film is formed at the contact position of metal and polyaniline, and the corrosion of the metal is slowed down.
The tannic acid functional group in the secondary doped polyaniline of tannic acid system contains special ortho-phenolic hydroxyl group, and the structure can be matched with Fe3+Reaction, in which corrosion reaction takes place to produce Fe3+Then, the tannin functional group can be separated from the polyaniline molecular chain, and Fe3+The reaction generates black compact ferric tannate chelate with better stability, the ferric tannate chelate can firmly cover the surface of the metal material once being generated, the development of corrosion is greatly limited, and the further inward development of the corrosion reaction can be effectively prevented by matching with a passivating oxide film generated by the reaction of eigenstate polyaniline and the metal surface.
In summary, when the corrosive environment of the metal to be treated is changed from pH less than or equal to 7 to pH greater than 7, doping is carried outPerforming de-doping process on polyaniline in state, and allowing tannic acid in main chain to react with anions (functional groups) and Cl-The polyaniline is released and converted into the polyaniline in an eigen state, on one hand, the polyaniline in the eigen state can generate passivation reaction with metal materials, a tight passivation film is formed at the contact position, and the corrosion of the metal is slowed down; meanwhile, the released tannic acid functional group can react with a metal substrate to generate a black compact ferric tannate chelate with better stability, so that the development of rust is hindered. The presence of a passivating oxide film and an iron tannate chelate can effectively shield Cl-The corrosion effect of the catalyst ensures that the system can be stably transited from the corrosion environment pH of less than or equal to 7 to the pH of more than 7.
When the corrosion environment of the metal to be treated is changed from pH being more than 7 to pH being less than or equal to 7, the intrinsic polyaniline in the system is influenced by the acid environment, the insulated intrinsic polyaniline is changed into conductive doped polyaniline, and the intrinsic polyaniline captures H in the environment+The proton entering the main chain is electropositive, and in order to maintain electroneutrality, it is also possible to react with anions and Cl in the environment-And correspondingly enters the main chain to be converted into doped polyaniline. The doped polyaniline inhibits metal corrosion through the action of an electric field. In addition, the tannic acid has strong anti-corrosion function to anions (functional groups) and strengthens the protection effect to metal materials.
The metal corrosion inhibitor provided by the embodiment of the invention is a compound metal corrosion inhibitor, and the compound metal corrosion inhibitor comprises sodium tungstate, zinc sulfate, thiourea, calcium gluconate, sodium polyphosphate, polyaspartic acid and sodium silicate in a mass fraction ratio of 1:3:4:3:2.5: 2.
Wherein sodium tungstate is colorless crystal or white crystalline powder, and belongs to anode type corrosion inhibitor, and tungstate radical WO in sodium tungstate4 2-Can replace Cl adsorbed on metal surface-With SO4 2-Combined with metals to form FeWO4And Fe2(WO4)3And the insoluble matters are dissolved, so that a passivation film is formed on the surface of the metal, the effect of filling gaps and defects is achieved, and reaction activation points can be reduced. The zinc sulfate is colorless or white crystal, granule or powder. In the process of compounding the zinc sulfate with the metal corrosion inhibitor,Zn2+ions are adsorbed on the metal surface and depolarized with the dissolved oxygen in the cathode to generate OH-Reaction to form Zn (OH)2And precipitating to deposit on the metal cathode, and isolating the metal cathode from contact with dissolved oxygen to inhibit the cathode corrosion reaction. However, stress damage caused by uneven film thickness is more likely to accelerate corrosion, so that the corrosion inhibitor is often compounded with other corrosion inhibitors, and the pores of the corrosion inhibitor are filled with the other corrosion inhibitors to achieve a good corrosion inhibition effect.
The thiourea is white and glossy crystal, the surface of sulfur atom in thiourea has lone pair electrons, iron belongs to transition element, and the outermost layer of atomic structure is 3d64s2The iron atom loses electrons and becomes ions, the surface of the iron atom has an empty electron orbit so as to be more easily accepted by electrons, and lone pair electrons of the sulfur atom are combined with the iron atom and the iron ions to form a coordination bond so as to prevent the dissolution of iron and inhibit the corrosion of carbon steel on the surface of metal. The calcium gluconate is white crystalline or granular powder, contains hydroxy acid radical and hydroxyl group, belongs to the hard alkali, and is Fe3+Belongs to stearic acid, so that hydroxy acid radicals and hydroxyl groups in calcium gluconate are easy to react with Fe3+The composite material is adsorbed on a cathode passivation film, the formed film is compact, the pores on the passivation film and a precipitation film can be filled, the protective film is perfected, and the carbon steel corrosion is slowed down.
The sodium polyphosphate is white granule or powder, belongs to cathode corrosion inhibitor, and is mixed with some metal ions (such as Ca)2+、Zn2+) When coexisting, the metal ions in the water can form metal salt precipitates which are deposited on the metal surface to form a precipitation film, thus inhibiting the metal corrosion. Wherein the polyaspartic acid is amber transparent liquid, belongs to an anode type corrosion inhibitor, and polar groups (-COOH, -NH) of a film of the polyaspartic acid2) The metal surface is adsorbed to form an adsorption film, and the nonpolar group (composed of C, H atoms) forms a hydrophobic film due to the hydrophobicity, so that the metal is isolated from contacting with a corrosive medium, and the corrosion inhibitor has an excellent corrosion inhibition effect. The sodium silicate is colorless orthogonal bipyramid crystals or white to offwhite blocks or powder, belongs to a mixed corrosion inhibitor capable of inhibiting both an anode and a cathode, and has a large inhibiting effect on the cathode. Reaction of silicates with oxides on the iron surfaceFormation of Fe2O3、Fe2SiO4And Fe7SiO10And a precipitation film is formed on the surface of the metal, and the newly formed precipitation film has stronger corrosion resistance.
According to the embodiment of the invention, sodium tungstate is adopted as a passive film type corrosion inhibitor, zinc sulfate forms a precipitation film at a metal cathode, calcium gluconate and polyaspartic acid are both adsorption film type corrosion inhibitors, and further, the corrosion inhibitors are compounded and cooperated to form a complete protective film on the metal surface to inhibit further corrosion of steel. In the compounding process, Zn in zinc sulfate2+Ion and tungstate radical WO in sodium tungstate4 2-There is competitive adsorption of Zn2+Preferentially adsorb on the metal surface, and react with OH on the metal cathode-And sodium tungstate forms a passivation film on the anode to inhibit metal corrosion. The calcium gluconate contains hydroxyl acid radical and hydroxyl group, belongs to the hard alkali, and is Fe3+Belongs to stearic acid, so that hydroxy acid radicals and hydroxyl groups in calcium gluconate are easy to react with Fe3+The combination is adsorbed on the cathode passivation film, and the formed film is compact. Sodium tungstate and polyaspartic acid form a passivation film and an adsorption film on the surface of the metal respectively. Tungstate ions in sodium tungstate can be mixed with Fe in solution3+、Fe2+The complex is formed to cover the metal surface to form a passivation film, which not only can reduce the activation points of corrosion, but also can fill the gaps of the metal oxide film to inhibit the metal corrosion.
The compound metal corrosion inhibitor provided by the embodiment of the invention can play a good role in metal corrosion inhibition in both acidic corrosion environment and alkaline corrosion environment.
Wherein, sodium polyphosphate and polyaspartic acid play a main role in the acidic corrosive environment, and other corrosion inhibitors play a synergistic role. The polyphosphate forms metal salt precipitates with metal ions in water, the metal salt precipitates are deposited on the metal surface to form a precipitation film, and the precipitation film is a macromolecular metal salt, is thick, has few pores, stably exists on the metal surface, and forms an environment for isolating metal from corrosion. However, researches show that polyphosphate is easy to hydrolyze, so that a small amount of zinc salt is frequently added to be compounded with the polyphosphate to prevent hydrolysis when the polyphosphate is used as a corrosion inhibitor, and the formation of a film can be accelerated. The polyaspartic acid contains a large amount of hydroxyl and carboxyl, and is extremely easy to adsorb on the metal surface, so that the macromolecular adsorption film is more compact and stable, the polyaspartic acid is alkaline, acid radical ions around the metal can be neutralized, thiourea can inhibit the dissolution of iron in an acid environment, the adsorption effect of the polyaspartic acid is more benefited, the adsorption film formed by the polyaspartic acid is firmer, the pores of a passivation film and a precipitation film are filled, and the protective film is more compact.
Sodium tungstate and calcium gluconate play a main role in a neutral corrosive environment, and other corrosion inhibitors play a synergistic role. The complex compound is formed by tungstate radical ions and metal ions in the sodium tungstate, and an insoluble passivation film is formed on the surface of metal, and when the sodium tungstate is used alone, the dosage is high, the corrosion inhibition effect is limited, and the good corrosion inhibition effect is achieved by compounding with other corrosion inhibitors. In the compounding process of the calcium gluconate, gluconate radicals and Cl in the calcium gluconate-Competitive adsorption is carried out on the surface of carbon steel, cathode polarization is increased, an adsorption film formed by the adsorption film is compact, a passivation film and a precipitation film on the surface of metal can be further perfected, an excellent synergistic effect is formed by the adsorption film and sodium tungstate, and metal corrosion is relieved. The metal surface may be covered with H in a neutral environment3O+、FeCl+、Fe2+Positive ions are generated and carry positive charges, the surface potential is relatively positive, and PASP is difficult to further adsorb on the surface of Fe, so that the synergistic effect is achieved, and the protective film is jointly enhanced by other corrosion inhibitors.
Calcium gluconate and sodium silicate play a major role in alkaline corrosive environments, and other corrosion inhibitors play an assisting role. The calcium gluconate contains hydroxyl acid radical and hydroxyl group, belongs to the hard alkali, and is Fe3+Belongs to stearic acid, so that hydroxy acid radicals and hydroxyl groups in calcium gluconate are easy to react with Fe3+The combination is adsorbed on the cathode passivation film, and the formed film is compact. In alkaline environment, a thin oxide film is easily formed on the surface of the metal, and the addition of sodium silicate can generate more (OH)-Contributes to the formation of oxide film, and sodium silicate reacts with oxides on the iron surface to generate Fe2O3、Fe2SiO4And Fe7SiO10Forming a precipitate film on the surface of the metal, these newly formed substancesHas stronger corrosion resistance, but the precipitation film has porosity and is often compounded with polyphosphate, organic phosphonic acid, zinc salt and the like for use.
The common characteristics of the pitting corrosion, the gap corrosion and the stress corrosion cracking are that the convection and the diffusion of the bottom or the top of the hole and the external banyan liquid are blocked, and a 'blocking corrosion battery' is formed. The hole bottom and the slit tip are the key parts for the hole erosion and the stress corrosion cracking expansion. In the corrosive environment, Cl-Are among the characteristic ions that cause them to corrode. The composition and pH of the solution in the occlusion area are essentially different from those of the main solution, mainly represented by oxygen deficiency, low pH value and high Cl-And metal ion concentration. The blocking battery generated by crevice corrosion has the characteristics of autocatalysis accelerated corrosion: (1) the convection and diffusion of the solution inside and outside the holes (slits) are blocked, resulting in oxygen depletion in the occlusion area; (2) the oxygen reduction reaction is carried out on the outer surface, and the metal in the pores (slits) is continuously dissolved. The blocking region generates excessive positive charges and external anions (Cl) under the action of an electric field-) Moving inwards; (3) hydrolyzing the high-concentration metal ions in the blocking area, and reducing the pH value of the solution in the blocking area; (4) h+And Cl-Promoting the dissolution of metals in the occlusion area and causing Cl-The migration is increased, the pH value is further reduced, and an autocatalysis effect is generated; (5) as erosion of the dead zone increases, the rate of oxidation reactions on the outer surface also increases, leaving the outer surface cathodically protected.
Because the metal corrosion inhibition additive of the embodiment of the invention contains the intrinsic polyaniline, the doped polyaniline and the compound metal corrosion inhibitor, the mutual cooperation of the intrinsic polyaniline, the doped polyaniline and the compound metal corrosion inhibitor can effectively control the corrosion of the blocked battery, and the metal corrosion inhibition additive is embodied in the following 4 aspects: (1) the relationship between the corrosion potential and the critical potential of the system is changed, or the critical potential is increased, or the corrosion potential is decreased. When the corrosion potential is equal to or lower than the critical level, the corrosion hole or crack is not initiated. (2) The relation between the outer surface potential and the blocking area potential is changed, the corrosion inhibitor migrates into the blocking area to ensure that the blocking area potential is positive to the outer surface potential, and the macroscopic corrosion battery can not be formed. (3) Inhibition of acidification and Cl of occlusion solutions-To retard or prevent the passive/active transition of the occlusion region. (4) Influencing anodic or cathodic processes in the dead zone to increase the rate of erosion in the dead zoneThe degree or the hydrogen release rate is slowed down and the propagation of cracks or corroded holes is inhibited.
Example two
Based on the same inventive concept, the second embodiment of the present invention provides a method for preparing the above elastic anti-corrosive adhesive, including:
(1) adding amine-terminated polyether into a planetary stirring kettle, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 10-20 rpm and 500-800 rpm, sequentially adding fumed silica, pigment, a catalyst, an accelerant and a metal corrosion inhibition additive, respectively regulating the speed of the planetary stirring motor and the high-speed stirring motor to 30-40 rpm and 1000-1200 rpm after the addition is finished, starting a heating device, heating to 60 ℃, and stirring for 1-1.5 hours at the temperature of 60 +/-5 ℃;
(2) stopping heating, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 10-20 rpm and 500-800 rpm, adding deionized water, continuously stirring for 1-1.5 h, then opening a vacuum valve, defoaming for 10-15 min under the vacuum degree of 0.07MPa, then closing the vacuum valve, and closing the planetary stirring kettle to discharge after the temperature is lower than 50 ℃ to prepare a component A of the elastic anticorrosive adhesive;
(3) metering a matrix polymer, nano reinforcing powder, fumed silica and liquid epoxy resin, adding the metered matrix polymer, nano reinforcing powder, fumed silica and liquid epoxy resin into an empty planetary stirring kettle, starting a planetary stirring motor and a high-speed stirring motor, respectively regulating the speeds to 10-20 rpm and 500-800 rpm, and continuously stirring until the powder material is completely wetted;
(4) regulating the speed of a planetary stirring motor and a high-speed stirring motor to 30-40 rpm and 1000-1200 rpm respectively, stirring at a high speed for 1-1.5 h, starting a heating device, starting a vacuum valve after the temperature is raised to 110 ℃, and dehydrating for 20-30 min under the negative pressure of 0.07 MPa;
(5) stopping heating after dehydration is finished, adding a stabilizer, an adhesion promoter, an antioxidant and an ultraviolet absorbent, continuously stirring for 1-1.5 h, then opening a vacuum valve, keeping the negative pressure at 0.07MPa, continuously degassing for 20-30 min, and then discharging to obtain a component B of the elastic anticorrosive adhesive;
(6) before use, the component A and the component B are mixed with each other according to the volume ratio of 4:1 to obtain the elastic anti-corrosion adhesive.
Wherein, the matrix polymer is prepared by the following method:
the first step is as follows: metering secondary amine-terminated polyether and primary amine-terminated polyether, adding the metered polyether into a dehydration kettle, starting stirring and heating, keeping the rotating speed at 200rpm, opening a vacuum valve and maintaining the vacuum degree at 0.07MPa, keeping the temperature at 115 +/-5 ℃ for 2-3 h, stopping heating after dehydration, closing the vacuum valve, introducing nitrogen into the dehydration kettle, cooling until the material temperature is lower than 50 ℃, and adding the dehydrated raw material into a planetary stirring reaction kettle;
the second step is that: adding the dehydrated raw materials into a planetary stirring reaction kettle, starting a planetary stirring motor and a high-speed stirring motor, regulating the speed to 30-40 rpm and 1000-1200 rpm respectively, then continuing to add hydrogenated MDI into the planetary stirring reaction kettle, filling nitrogen into the planetary stirring reaction kettle after adding the hydrogenated MDI, reacting for 30min, then starting heating and raising the temperature to 70 ℃, controlling the temperature to be 70 +/-5 ℃, continuing to react for 2-3 h, stopping heating, and cooling to below 50 ℃;
the third step: after the material temperature in the planetary stirring reaction kettle is lower than 50 ℃, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 30-40 rpm and 1000-1200 rpm, adding the measured N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyl trimethoxysilane into the planetary stirring reaction kettle, introducing nitrogen after the addition is finished, heating to 80 ℃, keeping the temperature at 80 +/-5 ℃, stopping heating after reacting for 3-4h, and respectively regulating the speed of the planetary stirring motor and the high-speed stirring motor to 10-20 rpm and 500-800 rpm;
the fourth step: opening a vacuum valve, defoaming for 15-20 min under the vacuum degree of 0.07MPa, closing the vacuum valve, cooling to below 50 ℃, stopping stirring and discharging to obtain the polyurea modified silyl polyether resin;
the fifth step: mixing the silane modified polyether resin and the polyurea modified silane-based polyether resin according to the mass ratio of 1:1, and uniformly mixing to obtain the matrix polymer.
The embodiment of the invention provides an elastic anticorrosive adhesive and a preparation method thereof, wherein amino polyether is adopted in the formula of the component A, self-synthesized polyurea modified silyl polyether resin is adopted in the component B, and the polyurea modified silyl polyether resin contains trace residual isocyanate group for reaction, so that the stock of free amino polyether in the elastic anticorrosive adhesive is greatly reduced; meanwhile, the amino polyether reacts with the epoxy resin in the component B and part of epoxy groups in the gamma-glycidyl ether oxypropyltrimethoxysilane, so that the mechanical property of the elastic anticorrosive adhesive is improved, and the introduction of the epoxy groups is favorable for improving the chemical resistance of the elastic anticorrosive adhesive and can adapt to the erosion of acid rain and the like in industrial atmospheric environment; most of free-state amine-terminated polyether is reacted through reaction, migration and precipitation caused by excessive free-state amine-terminated polyether are avoided, the typical corrosion problems of pitting corrosion, crevice corrosion, galvanic corrosion, microbial corrosion and the like of the color steel plate part of a boiler unit can be effectively solved, the water-proof sealing performance is good, the water-proof sealing performance is not deteriorated after long-term use, the rust-proof sealing performance is strong, meanwhile, microorganisms such as iron bacteria, thiobacillus, sulfate reducing bacteria and the like can be effectively killed, microbial corrosion is prevented, the water-proof sealing agent can be widely applied to acidic or alkaline environments, and remarkable economic benefits are achieved.
The elastic anticorrosive adhesive provided by the embodiment of the invention does not contain limited heavy metals such as tin, lead, mercury, cadmium, chromium and the like, formaldehyde and VOC components, and the cured elastic anticorrosive adhesive does not contain isocyanate monomers, thereby belonging to an environment-friendly material. The elastic anti-corrosion adhesive provided by the embodiment of the invention has paintability, contains more long-chain ether bonds, has moderate proportion of low-surface-energy-group siloxane, moderate surface tension and can be used for coating other coatings on the surface, and the service life of the elastic anti-corrosion adhesive layer provided by the embodiment of the invention can be further prolonged through the protection of the surface coating.
It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments of the present invention without departing from the spirit or scope of the embodiments of the invention. Thus, if such modifications and variations of the embodiments of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to encompass such modifications and variations.

Claims (9)

1. The elastic anti-corrosion adhesive comprises a component A and a component B, wherein the component A and the component B are in a mass ratio of 4:1, and the component A is characterized by comprising the following raw materials in percentage by mass: 30-48% of amine-terminated polyether, 3-7% of fumed silica, 30-45% of pigment, 0.5-2.5% of catalyst, 0.5-4.5% of accelerator, 7-13% of metal corrosion inhibition additive and 1-8% of deionized water, wherein the component B comprises the following raw materials in percentage by mass: 45-60% of matrix polymer, 1-5% of liquid epoxy resin, 1.5-3.5% of stabilizer, 1-4% of adhesion promoter, 7.1-14% of fumed silica, 13.5-35% of nano reinforcing powder, 1.2-3.5% of antioxidant and 1.2-3.5% of ultraviolet absorbent.
2. The elastic anti-corrosion adhesive according to claim 1, wherein the metal corrosion inhibition additive comprises a rust converting agent, polyaniline and a metal corrosion inhibitor in a mass ratio of 2:1:1, wherein the polyaniline is a mixture of intrinsic polyaniline and secondarily doped polyaniline.
3. The elastic anticorrosive adhesive according to claim 2, wherein the rust converting agent is a polyphosphoric acid-tannic acid type rust converting agent, and the polyphosphoric acid-tannic acid type rust converting agent comprises the following raw materials by mass percent: 45% of polyphosphoric acid, 1% of tannic acid, 1% of urotropine and 10% of hydroxyl polyether.
4. The elastic anti-corrosion adhesive according to claim 2, wherein the metal corrosion inhibitor is a complex metal corrosion inhibitor, and the complex metal corrosion inhibitor comprises sodium tungstate, zinc sulfate, thiourea, calcium gluconate, sodium polyphosphate, polyaspartic acid and sodium silicate in a mass ratio of 1:3:4:3:2.5: 2.
5. The elastic anti-corrosive binder according to claim 4, wherein the matrix polymer comprises silane modified polyether resin and polyurea modified silyl polyether resin, wherein the silane modified polyether resin is at least one of methyldimethoxysilane terminated polyether resin or trimethoxysilane terminated polyether resin.
6. The elastic anticorrosion adhesive as claimed in claim 5, wherein the polyurea modified silyl polyether resin contains urea bonds and ether bonds, wherein the introduction of the urea bonds and ether bonds is the reaction of dehydrated and hydrogenated MDI, and then the reaction of the terminal secondary amino polyether and the terminal primary amino polyether with N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyltrimethoxysilane is carried out.
7. The elastic anticorrosion adhesive as claimed in claim 6, wherein the polyurea modified silane based polyether resin comprises the following raw materials by mass percent: 17-23% of hydrogenated MDI, 36-67% of terminal secondary amino polyether, 2-39% of terminal primary amino polyether, 0.5-4.5% of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 3.5-8% of N-butylaminopropyltrimethoxysilane.
8. A method of preparing the elastic anti-corrosive binder of any one of claims 1 to 7, comprising:
(1) adding amine-terminated polyether into a planetary stirring kettle, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 10-20 rpm and 500-800 rpm, sequentially adding fumed silica, pigment, a catalyst, an accelerant and a metal corrosion inhibition additive, respectively regulating the speed of the planetary stirring motor and the high-speed stirring motor to 30-40 rpm and 1000-1200 rpm after the addition is finished, starting a heating device, heating to 60 ℃, and stirring for 1-1.5 hours at the temperature of 60 +/-5 ℃;
(2) stopping heating, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 10-20 rpm and 500-800 rpm, adding deionized water, continuously stirring for 1-1.5 h, then opening a vacuum valve, defoaming for 10-15 min under the vacuum degree of 0.07MPa, then closing the vacuum valve, and closing the planetary stirring kettle to discharge after the temperature is lower than 50 ℃ to prepare a component A of the elastic anticorrosive adhesive;
(3) metering a matrix polymer, nano reinforcing powder, fumed silica and liquid epoxy resin, adding the metered matrix polymer, nano reinforcing powder, fumed silica and liquid epoxy resin into an empty planetary stirring kettle, starting a planetary stirring motor and a high-speed stirring motor, respectively regulating the speeds to 10-20 rpm and 500-800 rpm, and continuously stirring until the powder material is completely wetted;
(4) regulating the speed of a planetary stirring motor and a high-speed stirring motor to 30-40 rpm and 1000-1200 rpm respectively, stirring at a high speed for 1-1.5 h, starting a heating device, starting a vacuum valve after the temperature is raised to 110 ℃, and dehydrating for 20-30 min under the negative pressure of 0.07 MPa;
(5) stopping heating after dehydration is finished, adding a stabilizer, an adhesion promoter, an antioxidant and an ultraviolet absorbent, continuously stirring for 1-1.5 h, then opening a vacuum valve, keeping the negative pressure at 0.07MPa, continuously degassing for 20-30 min, and then discharging to obtain a component B of the elastic anticorrosive adhesive;
(6) before use, the component A and the component B are mixed with each other according to the volume ratio of 4:1 to obtain the elastic anti-corrosion adhesive.
9. The method of claim 8, wherein the matrix polymer is prepared by:
metering secondary amine-terminated polyether and primary amine-terminated polyether, adding the metered polyether into a dehydration kettle, starting stirring and heating, keeping the rotating speed at 200rpm, opening a vacuum valve and maintaining the vacuum degree at 0.07MPa, keeping the temperature at 115 +/-5 ℃ for 2-3 h, stopping heating after dehydration, closing the vacuum valve, introducing nitrogen into the dehydration kettle, cooling until the material temperature is lower than 50 ℃, and adding the dehydrated raw material into a planetary stirring reaction kettle;
adding the dehydrated raw materials into a planetary stirring reaction kettle, starting a planetary stirring motor and a high-speed stirring motor, regulating the speed to 30-40 rpm and 1000-1200 rpm respectively, then continuing to add hydrogenated MDI into the planetary stirring reaction kettle, filling nitrogen into the planetary stirring reaction kettle after adding the hydrogenated MDI, reacting for 30min, then starting heating and raising the temperature to 70 ℃, controlling the temperature to be 70 +/-5 ℃, continuing to react for 2-3 h, stopping heating, and cooling to below 50 ℃;
after the material temperature in the planetary stirring reaction kettle is lower than 50 ℃, respectively regulating the speed of a planetary stirring motor and a high-speed stirring motor to 30-40 rpm and 1000-1200 rpm, adding the measured N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N-butylaminopropyl trimethoxysilane into the planetary stirring reaction kettle, introducing nitrogen after the addition is finished, heating to 80 ℃, keeping the temperature at 80 +/-5 ℃, stopping heating after reacting for 3-4h, and respectively regulating the speed of the planetary stirring motor and the high-speed stirring motor to 10-20 rpm and 500-800 rpm;
opening a vacuum valve, defoaming for 15-20 min under the vacuum degree of 0.07MPa, closing the vacuum valve, cooling to below 50 ℃, stopping stirring and discharging to obtain the polyurea modified silyl polyether resin;
mixing the silane modified polyether resin and the polyurea modified silane-based polyether resin according to the mass ratio of 1:1, and uniformly mixing to obtain the matrix polymer.
CN202010488935.4A 2020-06-02 2020-06-02 Elastic anti-corrosion adhesive and preparation method thereof Pending CN111574949A (en)

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