CN110499092B - Rigid high-temperature-resistant polyurea anticorrosive paint and preparation method thereof - Google Patents

Rigid high-temperature-resistant polyurea anticorrosive paint and preparation method thereof Download PDF

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CN110499092B
CN110499092B CN201910739886.4A CN201910739886A CN110499092B CN 110499092 B CN110499092 B CN 110499092B CN 201910739886 A CN201910739886 A CN 201910739886A CN 110499092 B CN110499092 B CN 110499092B
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王道前
肖国亮
连联益
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

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Abstract

The invention discloses a rigid high-temperature-resistant polyurea anticorrosive coating which comprises a component A and a component B, wherein the component A comprises the following preparation raw materials in parts by mass: 80-90 parts of polyisocyanate and 10-20 parts of polyester polyol; the component B comprises the following preparation raw materials in parts by mass: 10-30 parts of amino-terminated polyether, 10-30 parts of amino chain extender and 40-70 parts of super-toughness polyether amine. The rigid high-temperature-resistant polyurea anticorrosive paint does not contain any catalyst, has low requirement on the humidity of a construction environment, has good toughness, and can be used for a long time at the temperature of 160 ℃.

Description

Rigid high-temperature-resistant polyurea anticorrosive paint and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurea coatings, and particularly relates to a rigid high-temperature-resistant polyurea anticorrosive coating and a preparation method thereof.
Background
The polyurea anticorrosive coating is a pure polyurea anticorrosive coating system, has excellent corrosion resistance and ageing resistance, particularly has excellent corrosion resistance in the aspects of atmospheric corrosion resistance, low-acid and alkali media and inorganic salt solution, is convenient to construct on site, has high adhesive force, is not easy to crack, has strong permeation resistance, is a novel material in the field of corrosion resistance at present, and has the characteristics of long acting and wide applicability.
Polyurea is generally formed by two-component reaction, but the polyurea is generally formed by special mechanical spraying because the reaction speed is very high, namely the polyurea is solidified within a few seconds, and manual operation cannot be realized at all. The spraying polyurea coating has the following main characteristics: (1) the curing speed after polyurea spraying is very fast, gel is not sticky within a few seconds generally, walking strength can be achieved after hours, and the construction site can enter the next procedure. The thickness of polyurea spraying molding can be set at will, and the polyurea spraying molding can be finished by one-time construction from less than 1mm to several millimeters. The spray construction on the vertical surface and even the top surface can also ensure the flatness and smoothness, and the phenomenon of flowing can not occur, which endows the spray polyurea process with great construction efficiency. (2) The polyurea can be constructed with moisture, and because the reaction speed of the polyurea at normal temperature is very high, water molecules in the polyurea can not react with isocyanate in time, therefore, moisture around the environment can not generate adverse effect on the quality and the surface of the coating, and the construction is greatly facilitated. (3) The spraying polyurea has high strength, the modulus of the spraying polyurea is similar to that of rubber, namely, the spraying polyurea has high elongation at break and can still maintain high strength, and the tensile strength of the spraying polyurea can be changed within 10-22MPa through formula adjustment, and the range basically covers the performances of plastics, rubber and glass fiber reinforced plastics, so that the spraying polyurea is very beneficial to being used as a waterproof material. (4) The aging resistance of the spray polyurea is excellent, the specific molecular structure of the polyurea and the formula do not contain a catalyst, the aging resistance of the spray polyurea is particularly excellent, although the aromatic system material can generate yellowing phenomenon shortly after use, the use performance can not be influenced, but the aging resistance of the aliphatic system polyurea coating is more excellent. (5) The spray polyurea coating has good salt corrosion resistance, can resist the corrosion of dilute acid and dilute alkali as an anticorrosive coating, has outstanding resistance to the corrosion of salt water or salt mist, and is particularly suitable for coastal areas.
The common polyurea anti-corrosive paint coating is required to be used at the temperature of 80 ℃ or below, and the mechanical property and the anti-corrosive property of the coating are rapidly reduced, and the coating is soft and foams and the like at an over high temperature. In order to expand the applicable temperature range of the polyurea anticorrosive paint, the invention provides a rigid high-temperature-resistant polyurea anticorrosive paint. The rigid high-temperature-resistant polyurea anticorrosive coating has the advantages of good mechanical property, corrosion resistance, bonding strength and impact resistance, has certain toughness and wear resistance, and has small influence on the environment.
In the 70 s, the technology of the rigid polyurea anticorrosive coating with 100 percent of solid is developed successfully in North America, is one of the most widely used anticorrosive coating technologies in North America at present, represents the development direction of the paint industry in the twenty-first century, has more than thirty years of successful application history in all over the world, has advanced spraying technology, stable quality, fast curing of the coating, convenient and fast construction and extremely high efficiency, and can be widely applied to corrosion prevention of various matrixes such as steel, cast iron, cement and the like.
At present, in China, a spray rigid polyurea anticorrosive coating consists of two components, one is isocyanate semi-prepolymer, and the other is polyether polyol, an alcohol chain extender, a water absorbent, a catalyst and the like. Because the activity of polyether is low, a catalyst needs to be added to accelerate the reaction, but the addition of the catalyst is very sensitive to moisture, and in the construction process, a system is easy to react with moisture and humidity in the surrounding environment to generate carbon dioxide to generate a foam elastomer, so that the mechanical property is reduced rapidly, and a coating is easy to foam and bulge, so that the requirements on the moisture and the humidity of the construction environment are high, and the development of the coating is limited.
For example, patent document CN201711129146.6 discloses a method for preparing a polyurea waterproof coating applied to a concrete surface, wherein an organotin catalyst, which is dibutyl tin dilaurate, is added when modified polyurethane is prepared by using materials such as TDI (toluene-2, 4-diisocyanate), polyether, and DMPA. The dibutyl tin dilaurate used as a catalyst is extremely sensitive to water in a construction environment, requires a dry environment for construction, is not suitable for the polyurea coating in southern areas with high humidity, and greatly reduces the application range of the polyurea coating.
For another example, patent document CN200810031397.5 discloses a high temperature resistant and acid resistant polyurea anticorrosive paint for a lining of a desulfurization flue, which is prepared by mixing a component a and a component B at a volume ratio of 1: 0.5-2.0. The component A is a mixture of a semi-prepolymer synthesized by 100 parts by weight of polyisocyanate with functionality of 2.0-2.9 and 35-50 parts by weight of polyester polyol and 2-10 parts by weight of reactive diluent; the component B is a product prepared by mixing and dehydrating 150-250 parts by weight of polyether polyamine, 1000-1200 parts by weight of polyester polyamine, 500-620 parts by weight of chain extender, 80-90 parts by weight of cross-linking agent, 130-160 parts by weight of diluent, 3-15 parts by weight of catalyst, 500-600 parts by weight of filler and 50-60 parts by weight of color paste. Similarly, the polyurea coating uses a tertiary amine compound or organic tin as a catalyst, and if the coating is constructed in an environment with high humidity, the coating is easy to foam, bulge, fall off and the like.
Patent document CN201811054697.5 discloses a polyurea elastic anticorrosive paint and a preparation method thereof, which comprises a component a and a component B in parts by weight, wherein the component a comprises: polyether polyol N220, polyether polyol N330 and isocyanate MDI-50; the component B comprises: amino-terminated polyether D-2000, amino-terminated polyether T-5000, amino chain extender E-100 and amino chain extender 6200. The raw materials for preparing the polyurea anticorrosive paint are conventional materials, and although various physical and mechanical property specifications of the paint coating are required, the application temperature is conventional, the high-temperature resistant effect is not achieved, and the polyurea anticorrosive paint is not suitable for a high-temperature environment above 100 ℃.
Disclosure of Invention
The invention provides a rigid high-temperature-resistant polyurea anticorrosive paint and a preparation method thereof, and also provides application of the rigid high-temperature-resistant polyurea anticorrosive paint.
In order to overcome the defects of the prior art, the invention provides the rigid high-temperature-resistant polyurea anticorrosive paint, which is insensitive to moisture and not high in humidity requirement of construction environment due to no addition of any catalyst in preparation during construction, keeps the characteristic of rigidity and flexibility, does not generate brittleness due to overhigh crosslinking density, can be used for a long time at the temperature of 160 ℃, and further increases the temperature use range of spray polyurea.
The purpose of the invention is realized by the following technical scheme:
the invention provides a rigid high-temperature-resistant polyurea anticorrosive coating which comprises a component A and a component B, wherein the component A comprises the following preparation raw materials in parts by mass: 80-90 parts of polyisocyanate and 10-20 parts of polyester polyol; the component B comprises the following preparation raw materials in parts by mass: 10-30 parts of amino-terminated polyether, 10-30 parts of amino chain extender and 40-70 parts of super-toughness polyether amine.
Wherein the polyisocyanate is selected from: one or more of polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate (MDI).
Preferably, the polyisocyanate is selected from: polymethylene polyphenyl polyisocyanates (PAPIs) comprising 60-70% MDI and other isomers and similar higher polyisocyanates.
Wherein, the molecular weight of the polyester polyol is 2000-3500, the hydroxyl value is 360-400mg KOH/g, the acid value is less than or equal to 2.0mg KOH/g, the water content is less than or equal to 0.1 percent, and the viscosity is less than or equal to 4000mPa & s.
Wherein, the amino-terminated polyether is polyether amine with molecular weight of 2000-5000, in the preferred embodiment of the invention, the amino-terminated polyether is Jaffamine D-2000 or Jaffamine T-5000.
Wherein the amino chain extender is one or the combination of more than two of diethyl toluene diamine (DETDA), Ethancure-100(E-100) and dimethyl sulfur toluene diamine (DMTDA). In a preferred embodiment of the present invention, the amino chain extender is DETDA.
Wherein the ultra-tough polyetheramine is selected from polyetheramines having 3 secondary amine end-caps.
In a preferred embodiment of the present invention, the structural formula of the ultra-tough polyetheramine is as follows:
Figure BDA0002163580960000041
wherein,
Figure BDA0002163580960000042
n is an integer of 6 to 12,
Figure BDA0002163580960000043
Figure BDA0002163580960000044
m is an integer between 9 and 18.
In the present invention, the preparation process of the super-tough polyetheramine of the general formula I is as follows:
Figure BDA0002163580960000045
wherein,
Figure BDA0002163580960000051
n is an integer of 6 to 12,
Figure BDA0002163580960000052
specifically, adding the compound 1 into a reactor, introducing nitrogen, slowly dropwise adding the compound 2 under stirring, adding a catalyst, and reacting for 12-24 hours under stirring to obtain the super-toughness polyetheramine with the general formula I.
Wherein the catalyst is selected from one or the combination of more than two of zinc chloride, sodium ethoxide, sodium hydride, sodium amide or organic alkali.
In the present invention, the preparation process of the ultra-tough polyetheramine of the general formula II is as follows:
Figure BDA0002163580960000053
wherein,
Figure BDA0002163580960000054
m is an integer between 9 and 18.
Specifically, 1-3 times of the molar weight of epoxy chloropropane is added into the compound 3, the reaction is carried out for 6-12 hours, alkaline solution is dripped, the reaction is carried out for 3-5 hours under the condition of heat preservation after the completion, reduced pressure distillation is carried out, 2-propylamine is added into the concentrated product, the temperature is 60-100 ℃, and the reaction is carried out for 5-10 hours, so as to obtain the super-toughness polyether amine with the general formula II.
In a preferred embodiment of the invention, the A component also comprises 3-7 parts of trimethylolpropane trimethacrylate (TMPTMA), and the TMPTMA is generally used for modifying epoxy acrylate, polyurethane and unsaturated polyester coatings, so as to shorten the curing time and improve the bonding strength. However, in the present invention, the inventors have found that the addition of TMPTMA to the a component increases the substrate adhesion and abrasion resistance of the polyurea anticorrosive coating, and increases the toughness of the coating.
Preferably, the component B also comprises one or a combination of more than two of 1-2 parts of a leveling agent, 0.1-1 part of an anti-ultraviolet agent, 0.01-1 part of an antioxidant and 0.1-2 parts of a pigment and filler.
Wherein, the flatting agent is selected from one or two of polyacrylate flatting agent and polyester modified polysiloxane flatting agent.
Wherein the anti-ultraviolet agent is selected from a triazine anti-ultraviolet agent, an oxybenzophenone anti-ultraviolet agent, a benzotriazole anti-ultraviolet agent, a salicylate anti-ultraviolet agent, a benzophenone anti-ultraviolet agent, a cyanoacrylate anti-ultraviolet agent or a nickel complex salt anti-ultraviolet agent.
Wherein the antioxidant is selected from 2, 6-di-tert-butyl-p-cresol, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ].
Wherein, the pigment and filler is selected from one or a mixture of several of iron oxide red, titanium dioxide, barium sulfate, talcum powder and mica powder in any proportion.
On the other hand, the invention provides a preparation method of the rigid high-temperature-resistant polyurea anticorrosive paint, which comprises the following steps:
(1) dehydrating polyester polyol: dehydrating polyester polyol at the temperature of 110-120 ℃ and the vacuum degree of-0.08 to-0.1 Mpa for 2 to 3 hours, and cooling to room temperature for later use;
(2) preparation of component A: putting polymethylene polyphenyl polyisocyanate into a reaction kettle, heating to 45-50 ℃, slowly dripping the dehydrated polyester polyol prepared in the step (1), finishing dripping within 1-1.5 hours, heating to 80-90 ℃, preserving heat for 2-3 hours, sampling to measure the NCO content, cooling to room temperature when the NCO content is 23.0-24.5%, filtering, filling nitrogen, sealing and storing;
(3) preparation of the component B: adding the amino-terminated polyether into a stirring cylinder, adding the super-toughness polyether amine and the amino chain extender, stirring for 45-60 minutes at the speed of 400-500 r/min, filtering, and packaging for later use;
(4) and mixing the component A and the component B according to the ratio of 1:2-3 to obtain the rigid high-temperature-resistant polyurea anticorrosive coating.
Preferably, the step (2) further comprises adding trimethylolpropane trimethacrylate after the dropping of the dehydrated polyester polyol is finished, and uniformly stirring.
Preferably, the step (3) further comprises adding one or a combination of more than two of a leveling agent, an anti-ultraviolet agent, an antioxidant and a pigment and filler before filtering, and uniformly stirring.
Preferably, the rigid high-temperature-resistant polyurea anticorrosive paint is applied by spraying, the A component and the B component are combined and mixed under high pressure, and preferably, the A component and the B component are directly subjected to impact mixing in a high-pressure spraying device. Specifically, the A-component and the B-component are heated in two separate chambers, pressurized separately, and impacted or impinged upon each other at high velocity to achieve intimate mixing between the two components, and then applied to a substrate by a spray gun.
In the present invention, the rigid high temperature resistant polyurea anticorrosive paint coating can be used at a temperature of 160 ℃ or less.
The invention also provides application of the rigid high-temperature-resistant polyurea anticorrosive paint in surface corrosion prevention of metal or concrete with high temperature in the fields of electric power, petroleum, chemical industry, pharmacy, automobile manufacturing and railways, and preferably, the surface temperature of the metal or the concrete is less than or equal to 160 ℃.
The invention has the following beneficial effects: (1) the rigid polyurea anticorrosive paint is not sensitive to moisture because no catalyst is added, so that the requirement on the humidity of a construction environment is not high; (2) trimethylolpropane trimethacrylate and/or super-toughness polyether amine are added into the rigid polyurea anticorrosive paint, so that sufficient toughness and crosslinking density are provided for the paint, the coating has the characteristic of rigidity and flexibility, and brittleness caused by overhigh crosslinking density is avoided; (3) the polyurea anticorrosive paint prepared by the invention can be used for a long time at the temperature of 160 ℃, and has obvious improvement on the aspect of the use temperature of spraying polyurea compared with the prior art.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all 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.
Example 1
Preparation of ultra-tough polyetheramines of the general formula I
Adding 1.5mol of three-arm polyether amine raw material (the compound 1 in the invention, wherein the molecular weight is 1600-2100) into a four-neck flask with a stirrer and a thermometer, starting the stirrer, introducing nitrogen, slowly adding diethyl maleate with 3 times of the molar weight of polyether amine, adding catalysts of sodium hydride and zinc chloride (in equal molar proportion) to 0.05 wt%, and stirring for reacting overnight to obtain the super-toughness polyether amine.
Example 2
Preparation of ultra-tough polyetheramines of the general formula II
S1: adding epoxy chloropropane into 1.2mol of a three-arm polyether polyol raw material (a compound 3 in the invention, wherein the molecular weight is 1800-2400), wherein the molar weight of the epoxy chloropropane is 3 times of the molar number of hydroxyl groups in the polyether polyol, reacting for 10 hours, slowly adding a KOH alkali solution, wherein the amount of alkali is 1.3 times of the molar number of the epoxy chloropropane, finishing the addition after 2 hours, and keeping the temperature at 75 ℃ for reacting for 5 hours;
s2: washing the product obtained in the step S1 with water to remove salts and residual alkaline substances, and then carrying out reduced pressure distillation and dehydration to obtain a polyether polyol glycidyl ether intermediate;
s3: and (4) adding 2-propylamine with 3 times of molar weight into the polyether polyol glycidyl ether intermediate obtained in the step S2, and slowly stirring and reacting at 100 ℃ for 10 hours to obtain the super-toughness polyether amine with the general formula II.
Example 3
Preparation of rigid high-temperature-resistant polyurea anticorrosive paint
S1: dehydrating polyester polyol: dehydrating 12 parts of polyester polyol at 120 ℃ and under the vacuum degree of-0.08 Mpa for 2 hours, and cooling to room temperature for later use;
s2: preparation of component A: putting 88 parts of polymethylene polyphenyl polyisocyanate into a reaction kettle, heating to 45 ℃, slowly dripping the dehydrated polyester polyol prepared in the step (1), after finishing dripping for 1 hour, heating to 80 ℃, preserving heat for 2 hours, sampling to measure the NCO content, cooling to room temperature when the NCO content is 23.0%, filtering, filling nitrogen, and sealing for storage;
s3: preparation of the component B: adding Jaffamine T-500015 parts of amino-terminated polyether into a stirring cylinder, adding 60 parts of super-toughness polyetheramine I and 25 parts of amino chain extender diethyl toluenediamine, stirring for 45 minutes at 500 revolutions per minute, filtering, and packaging for later use;
s4: and mixing the component A and the component B according to the weight ratio of 1:2.5 to obtain the rigid high-temperature-resistant polyurea anticorrosive coating.
Example 4
Preparation of rigid high-temperature-resistant polyurea anticorrosive paint
S1: the procedure is as in example 3;
s2: the procedure is as in example 3;
s3: preparation of the component B: adding Jaffamine T-500015 parts of amino-terminated polyether into a stirring cylinder, adding 60 parts of super-toughness polyetheramine II and 25 parts of amino chain extender diethyl toluenediamine, stirring for 45 minutes at 500 revolutions per minute, filtering, and packaging for later use;
s4: the same as in example 3.
Example 5
Preparation of rigid high-temperature-resistant polyurea anticorrosive paint
S1: the same as in example 3;
s2: the same as in example 3;
s3: preparation of the component B: adding Jaffamine T-500015 parts of amino-terminated polyether into a stirring cylinder, adding 30 parts of super-toughness polyetheramine I, 30 parts of super-toughness polyetheramine II and 25 parts of amino chain extender diethyl toluenediamine, stirring for 45 minutes at 500 revolutions per minute, filtering, and packaging for later use;
s4: the same as in example 3.
Example 6
Preparation of rigid high-temperature-resistant polyurea anticorrosive paint
S1: the same as example 5;
s2: preparation of component A: putting 88 parts of polymethylene polyphenyl polyisocyanate into a reaction kettle, heating to 45 ℃, slowly dripping the dehydrated polyester polyol prepared in the step (1), after dripping for 1 hour, adding 5 parts of trimethylolpropane trimethacrylate, heating to 80 ℃, keeping the temperature for 2 hours, sampling to measure the NCO content, cooling to room temperature when the NCO content is 23.0%, filtering, filling nitrogen, and sealing for storage;
s3: the same as example 5;
s4: the same as in example 5.
Example 7
Preparation of rigid high-temperature-resistant polyurea anticorrosive paint
S1: the same as in example 6;
s2: the same as in example 6;
s3: preparation of the component B: adding Jaffamine T-500015 parts of amino-terminated polyether into a stirring cylinder, adding 30 parts of super-toughness polyetheramine I, 30 parts of super-toughness polyetheramine II and 25 parts of amino chain extender diethyl toluenediamine, stirring for 45 minutes at 500 revolutions per minute, adding 1 part of polyester modified polysiloxane flatting agent, 0.4 part of triazine uvioresistant agent, 0.1 part of antioxidant 2, 6-di-tert-butyl-p-cresol and 1 part of talcum powder, stirring uniformly, filtering and packaging for later use;
s4: the same as in example 6.
Comparative example 1
Preparation of polyurea anticorrosive paint without containing super-toughness polyether amine
S1: the same as in example 3;
s2: the same as in example 3;
s3: preparation of the component B: adding Jaffamine T-500015 parts of amino-terminated polyether into a stirring cylinder, stirring 25 parts of amino chain extender diethyl toluene diamine for 45 minutes at 500 r/min, adding 1 part of polyester modified polysiloxane flatting agent, 0.4 part of triazine uvioresistant agent, 0.1 part of antioxidant 2, 6-di-tert-butyl-p-cresol and 1 part of talcum powder, stirring uniformly, filtering and packaging for later use;
s4: and mixing the component A and the component B according to the ratio of 1:2.5 to obtain the rigid high-temperature-resistant polyurea anticorrosive coating.
Effect example 1
The conventional performances of the rigid high-temperature-resistant polyurea anticorrosive paint are compared
The rigid high-temperature-resistant polyurea anticorrosive paint prepared in example 3 is used as a test group, and a common solvent-containing epoxy anticorrosive paint and a common solvent-free epoxy anticorrosive paint in the market are used as a control group to carry out coating performance test. Under the conditions that the temperature is 25 ℃ and the relative air humidity is 55%, 3 pieces of 120X 50X 0.28mm horse-mouth iron plates are taken as base materials, the component A and the component B are mixed according to the ratio of 1:2.5 in a test group, the spraying is carried out by adopting a Guruike polyurea spraying device HPX-3 according to the dosage of 0.25 kg/square meter, the spraying is carried out on a control group according to the instruction, the performance is tested after the curing is carried out for 7 days, and the detection results are shown in the following table.
TABLE 1 comparison of the performances of rigid high-temperature-resistant polyurea anticorrosive coatings with ordinary epoxy anticorrosive coatings
Figure BDA0002163580960000101
Figure BDA0002163580960000111
According to the comparison results in the table, it can be found that the rigid high temperature resistant polyurea anticorrosive coating prepared in example 3 of the present invention has stronger adhesion to the base material, better wear resistance and cathodic disbonding resistance, stronger impact strength and bending property, and no significant difference among salt spray resistance, chemical corrosion resistance and aging resistance compared with the common epoxy anticorrosive coating. The coating of the 3 kinds of anticorrosive coatings is placed at 160 ℃ for 7 days, the coating of the polyurea anticorrosive coating prepared by the invention has no phenomena of brittleness, cracking, bulging and falling, and the coating of the epoxy anticorrosive coating of the control group has the phenomena of cracking, bulging and falling. The polyurea anti-corrosive paint coating prepared by the invention has stronger high temperature resistance.
Effect example 2
Effect of ultra-tough polyetheramines on polyurea anticorrosive coating Properties
In the invention, the super-toughness polyether amine is added into the component B to provide sufficient crosslinking density and toughness for the polyurea anticorrosive coating, so that the anticorrosive coating has good impact strength, wear resistance and toughness. In the test, the polyurea anticorrosive coatings prepared in example 3 (only containing super-toughness polyetheramine I), example 4 (only containing super-toughness polyetheramine II) and example 5 (simultaneously containing super-toughness polyetheramine I and super-toughness polyetheramine II) are used as test groups, and the polyurea anticorrosive coating without super-toughness polyetheramine is used as a control group, so that the influence of the super-toughness polyetheramine on the properties of the polyurea anticorrosive coating is detected. Under the conditions that the temperature is 25 ℃ and the relative air humidity is 55%, 10 pieces of 120X 50X 0.28mm galvanized iron plates in each group are taken as base materials, the component A and the component B are mixed according to the ratio of 1:2.5, the spraying is carried out by adopting a Guruyi polyurea spraying device HPX-3 according to the dosage of 0.25 kg/square meter, the performance is tested after 7 days of curing, the yield is obtained in the bending performance test, the other performance indexes are the best values, and the detection results are shown in the following table.
The bending performance test adopts ASTM D522 as a detection standard, and the qualification index is as follows: the diameter of the bent cylinder is 13mm, and the coating of the test piece is free from peeling or cracking by visual inspection.
TABLE 2 results of the Effect of ultra-tough polyetheramines on polyurea anti-corrosive coating Properties
Figure BDA0002163580960000112
Figure BDA0002163580960000121
As can be seen from the data in Table 2, the adhesion, wear resistance, cathodic disbonding resistance and impact strength of the polyurea anticorrosive paint containing both the super-toughness polyetheramine I and the super-toughness polyetheramine II are superior to those of the polyurea anticorrosive paint containing only the super-toughness polyetheramine I or II and are superior to those of the polyurea anticorrosive paint containing no super-toughness polyetheramine. Meanwhile, the polyurea anticorrosive paint containing the super-toughness polyetheramine I and the super-toughness polyetheramine II has the best bending performance, the detection qualified rate is 100%, and the qualified rate of the polyurea anticorrosive paint containing no super-toughness polyetheramine is only 50%. The addition of the super-toughness polyether amine can also increase the high-temperature resistance of the coating, so that the coating is not easy to bulge and fall off at the high temperature of 160 ℃. Therefore, the addition of the super-toughness polyetheramine can increase the crosslinking density of the anticorrosive coating, improve the rigidity of the coating, improve the toughness, achieve the characteristic of 'hardness and softness in the middle', and the simultaneous matching and addition effects of the super-toughness polyetheramine I and the super-toughness polyetheramine II are better.
Effect example 3
Effect of trimethylolpropane trimethacrylate on polyurea anticorrosive coating Properties
In the test, the polyurea anticorrosive coatings prepared in examples 5 and 6 (in which trimethylolpropane trimethacrylate is added on the basis of example 5) are used as test groups, and the influence of the trimethylolpropane trimethacrylate on the properties of the polyurea anticorrosive coatings is detected. Under the conditions that the temperature is 25 ℃ and the relative air humidity is 55%, 10 pieces of 120X 50X 0.28mm galvanized iron plates in each group are taken as base materials, the component A and the component B are mixed according to the ratio of 1:2.5, the spraying is carried out by adopting a Guruyi polyurea spraying device HPX-3 according to the dosage of 0.25 kg/square meter, the performance is tested after 7 days of curing, the yield is obtained in the bending performance test, the other performance indexes are the best values, and the detection results are shown in the following table.
TABLE 3 influence of trimethylolpropane trimethacrylate on polyurea anticorrosive coating Properties results
Figure BDA0002163580960000122
Figure BDA0002163580960000131
According to the comparison results in the table 3, on the basis of the example 5, after trimethylolpropane trimethacrylate is added in the preparation process of the component A, the polyurea anticorrosive paint has stronger adhesive force and better wear resistance, the yield of the bending property test is kept at 100%, and the impact strength is basically unchanged. The trimethylolpropane trimethacrylate is added as a micromolecular hydroxyl compound, so that the toughness and elasticity of the A-component prepolymer are improved, the brittleness caused by overhigh crosslinking density is reduced, the toughness of the polyurea anticorrosive coating is finally enhanced, the adhesive force of the coating to a base material is increased, and the wear resistance is better.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. The rigid high-temperature-resistant polyurea anticorrosive paint is characterized by comprising a component A and a component B, wherein the component A comprises the following preparation raw materials in parts by mass: 80-90 parts of polyisocyanate and 10-20 parts of polyester polyol; the component B comprises the following preparation raw materials in parts by mass: 10-30 parts of amino-terminated polyether, 10-30 parts of amino chain extender and 40-70 parts of super-toughness polyether amine;
the polyisocyanate is selected from: one or more of polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate;
the molecular weight of the polyester polyol is 2000-3500, the hydroxyl value is 360-400mg KOH/g, the acid value is less than or equal to 2.0mg KOH/g, the water content is less than or equal to 0.1 percent, and the viscosity is less than or equal to 4000mPa & s;
the amino-terminated polyether is polyether amine with the molecular weight of 2000-5000-;
the amino chain extender is selected from one or the combination of more than two of diethyl toluene diamine, etharcure-100 and dimethyl sulfur toluene diamine;
the structure of the super-toughness polyether amine is as follows:
Figure 288586DEST_PATH_IMAGE002
and
Figure 205726DEST_PATH_IMAGE004
wherein,
Figure 985463DEST_PATH_IMAGE006
n is an integer of 6 to 12,
Figure 442990DEST_PATH_IMAGE008
，
Figure 257362DEST_PATH_IMAGE010
and m is an integer of 9 to 18.
2. The rigid high-temperature-resistant polyurea anticorrosive coating according to claim 1, wherein the preparation process of the super-tough polyether amine of the general formula I is as follows:
Figure 892874DEST_PATH_IMAGE012
wherein,
Figure 159907DEST_PATH_IMAGE014
n is an integer of 6 to 12,
Figure 358807DEST_PATH_IMAGE016
；
specifically, adding the compound 1 into a reactor, introducing nitrogen, slowly dropwise adding the compound 2 under stirring, adding a catalyst, and reacting for 12-24 hours under stirring to obtain the super-toughness polyetheramine with the general formula I; the catalyst is selected from one or the combination of more than two of zinc chloride, sodium ethoxide, sodium hydride, sodium amide and organic alkali;
the preparation process of the super-toughness polyetheramine with the general formula II is as follows:
Figure 90003DEST_PATH_IMAGE018
wherein,
Figure 83367DEST_PATH_IMAGE020
m is an integer between 9 and 18;
specifically, 1-3 times of the molar weight of epoxy chloropropane is added into the compound 3, the reaction is carried out for 6-12 hours, alkaline solution is dripped, the reaction is carried out for 3-5 hours under the condition of heat preservation after the completion, reduced pressure distillation is carried out, 2-propylamine is added into the concentrated product, the temperature is 60-100 ℃, and the reaction is carried out for 5-10 hours, so as to obtain the super-toughness polyether amine with the general formula II.
3. The rigid high-temperature-resistant polyurea anticorrosive coating according to any one of claims 1 to 2, wherein the component A further comprises 3 to 7 parts of trimethylolpropane trimethacrylate.
4. The rigid high-temperature-resistant polyurea anticorrosive paint according to any one of claims 1 to 2, wherein the component B further comprises one or a combination of more than two of 1 to 2 parts of leveling agent, 0.1 to 1 part of anti-ultraviolet agent, 0.01 to 1 part of antioxidant and 0.1 to 2 parts of pigment and filler.
5. A method for preparing the rigid high-temperature-resistant polyurea anticorrosive paint according to claim 1, which comprises the following steps:
(1) dehydrating polyester polyol: dehydrating polyester polyol at the temperature of 110-120 ℃ and the vacuum degree of-0.08 to-0.1 Mpa for 2 to 3 hours, and cooling to room temperature for later use;
(2) preparation of component A: putting polymethylene polyphenyl polyisocyanate into a reaction kettle, heating to 45-50 ℃, slowly adding the dehydrated polyester polyol prepared in the step (1), after dropwise adding for 1-1.5 hours, heating to 80-90 ℃, preserving heat for 2-3 hours, sampling to measure the NCO content, cooling to room temperature when the NCO content is 23.0-24.5%, filtering, filling nitrogen, and sealing for storage;
(3) preparation of the component B: adding the amino-terminated polyether into a stirring cylinder, adding the super-toughness polyether amine and the amino chain extender, stirring for 45-60 minutes at the speed of 400-500 r/min, filtering, and packaging for later use;
(4) and mixing the component A and the component B according to the weight ratio of 1:2-3 to obtain the rigid high-temperature-resistant polyurea anticorrosive coating.
6. The method according to claim 5, wherein the step (2) further comprises adding trimethylolpropane trimethacrylate after the addition of the dehydrated polyester polyol is completed, and stirring the mixture uniformly.
7. The preparation method according to claim 5, wherein the step (3) further comprises adding one or a combination of more than two of a leveling agent, an anti-ultraviolet agent, an antioxidant and a pigment and filler before filtering, and uniformly stirring.
8. Use of the rigid high temperature resistant polyurea anticorrosive coating of claim 1 to produce high temperature corrosion protection of metal or concrete surfaces.
9. Use according to claim 8, wherein the metal or concrete surface temperature is 160 ℃ or less.
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