CN115044273A - High-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention - Google Patents
High-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention Download PDFInfo
- Publication number
- CN115044273A CN115044273A CN202210830695.0A CN202210830695A CN115044273A CN 115044273 A CN115044273 A CN 115044273A CN 202210830695 A CN202210830695 A CN 202210830695A CN 115044273 A CN115044273 A CN 115044273A
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy resin
- temperature
- wollastonite
- sericite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
-
- 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
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- 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
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
- C09D5/038—Anticorrosion agents
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
- F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
- F16L58/04—Coatings characterised by the materials used
- F16L58/10—Coatings characterised by the materials used by rubber or plastics
- F16L58/1009—Coatings characterised by the materials used by rubber or plastics the coating being placed inside the pipe
- F16L58/1045—Coatings characterised by the materials used by rubber or plastics the coating being placed inside the pipe the coating being an extruded or a fused layer
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention, which comprises the following components in parts by weight: 100-130 parts of composite epoxy resin; 60-70 parts of combined filler; 2-10 parts of adhesion promoter; 0.5-2 parts of degassing agent; 6-10 parts of a curing agent; 1-3 parts of a leveling agent; 2-10 parts of pigment and filler; wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the combined filler is the mixture of wollastonite and sericite. The high-temperature-resistant high-pressure-resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention provided by the invention has the advantages of high glass transition temperature, excellent toughness, strong adhesive force and excellent corrosion resistance, can meet the use requirements under a high-temperature and high-pressure environment, and can prolong the service life of the coating when used for pipeline protection.
Description
Technical Field
The invention relates to the field of coatings, in particular to a high-temperature and high-pressure resistant hot-melt epoxy powder coating for pipeline corrosion prevention.
Background
The inner layer of the oil and gas transmission pipeline is usually coated with hot-melt epoxy powder coating to enhance the corrosion resistance and high temperature resistance of the pipeline. However, with the continuous deepening of exploration and development of deep water oil and gas fields, the development of deep wells and ultra-deep wells leads to the increase of the internal environment temperature and pressure of deep wells, and the temperature of produced liquid is usually between 80 ℃ and 150 ℃; conventional FBE powders have failed to provide a safe and reliable corrosion resistant coating for pipes operating in such environments. In addition, the working environment in the petroleum drill pipe and the crude oil conveying pipe often contains corrosive medium H 2 S and the like can severely corrode the inner walls of drill rods and pipelines, and simultaneously, the anti-corrosion powder also needs to bear the action of tension, compression, bending, torsion, rotary centrifugation, additional dynamic load during drilling, and the like, so that the working conditions are quite severe, and the performance requirements under the severe conditions can not be met by common anti-corrosion powder. The glass transition temperature (Tg) of a coating film of the common epoxy powder is lower and is equal to or lower than the operating temperature, so that the coating is softened in use, the adhesion and the mechanical property are poor, the protective performance of the coating on a pipeline is influenced, and the service life of the pipeline is shortened.
Therefore, there is a need for improvements in the art to provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-temperature and high-pressure resistant hot-melt epoxy powder coating for pipeline corrosion prevention aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: the high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention is characterized by comprising the following components in parts by weight:
100-130 parts of composite epoxy resin;
60-70 parts of combined filler;
2-10 parts of adhesion promoter;
0.5-2 parts of degassing agent;
6-10 parts of a curing agent;
1-3 parts of a leveling agent;
2-10 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1-4: 1;
wherein the combined filler is a mixture of wollastonite and sericite, and the weight ratio of wollastonite: the mass ratio of the sericite is 1: 1-3: 1.
Preferably, the phenolic modified epoxy resin in the composite epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 2:1, wollastonite: the mass ratio of sericite is 1: 1.
Preferably, the curing agent is dicyandiamide or a dicyandiamide derivative.
Preferably, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, and the degassing agent is benzoin.
Preferably, the adhesion promoter is a silane coupling agent.
Preferably, the silane coupling agent is one or more of A151, A171, A172 and KH-602.
Preferably, the preparation method of the high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention comprises the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 40-60Hz, and the melting temperature of the extruder is controlled at 90-100 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding and sieving to obtain the epoxy powder coating.
Preferably, the combined filler is a mixture of wollastonite and sericite which are subjected to composite modification treatment, and is prepared by the following method:
1) dispersing wollastonite and sericite in water to prepare a combined filler dispersion liquid;
2) coating a nano silicon dioxide film;
3) and coating the composite modified membrane.
Preferably, the composite modified combined filler is prepared by the following method:
1) preparing a combined filler dispersion liquid:
respectively grinding wollastonite and sericite into powder, and then mixing the wollastonite: mixing sericite in a mass ratio of 1: 1-3: 1, adding the mixture into deionized water, stirring, adding a dispersing agent and a coupling agent, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 9-10;
2-2) heating the solution to 80-95 ℃, and then dropwise adding NaSiO into the solution under continuous stirring 3 After the solution is added dropwise, adjusting the pH value of the solution to 6-6.5 by using sulfuric acid or hydrochloric acid, and aging for 2-6 h;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano-silica coated composite filler obtained in the step 2) to 115-160 ℃, and keeping the temperature for 1-4 h;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, gadolinium acetate hydrate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 185-350 ℃ under continuous stirring, and reacting for 2-10 hours;
3-5) heating to 750-1100 ℃, calcining for 1-8 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
Preferably, the high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention comprises the following components in parts by weight:
120 parts of composite epoxy resin;
60 parts of combined filler;
2 parts of adhesion promoter;
0.8 part by weight of degassing agent;
6 parts of a curing agent;
1.6 parts of a leveling agent;
8 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1;
wherein the combined filler is a mixture of wollastonite and sericite, and the weight ratio of wollastonite: the mass ratio of sericite is 1: 1.
The invention has the beneficial effects that:
the high-temperature-resistant high-pressure-resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention provided by the invention has the advantages of high glass transition temperature, excellent toughness, strong adhesive force and excellent corrosion resistance, can meet the use requirements under a high-temperature and high-pressure environment, and can prolong the service life of the coating when used for pipeline protection.
In the invention, the combination of the phenolic aldehyde modified epoxy resin and the o-cresol formaldehyde epoxy resin is used as the composite epoxy resin, so that the requirements of high Tg and high flexibility of the coating can be met.
According to the invention, the mixture of wollastonite and sericite is used as a combined filler, so that the corrosion resistance and flexibility of the coating can be improved, and the needle-shaped or rod-shaped wollastonite is easy to form an intercrossed three-dimensional structure in the stacking process, and just corresponds to a three-dimensional network structure formed in the epoxy resin crosslinking and curing process, so that a more compact coating can be formed; and the sericite is in a scaly shape, and the sericite in a flaky structure is easy to be paved in the coating to form a scaly state due to liquid flow in the process of melting the epoxy resin into a liquid state, so that corrosive media are prevented or delayed from entering the coating, and the corrosion resistance and the boiling resistance of the coating can be improved.
According to the invention, the nanometer silicon dioxide film and the composite modified film are coated in a double-layer manner to modify the wollastonite powder and the sericite powder, so that on one hand, the dispersibility of the wollastonite powder and the sericite powder and the compatibility with a polymer material can be obviously improved, and the reinforcing effect of the nanometer silicon dioxide film and the composite modified film on the adhesion and mechanical properties of the coating can be fully exerted; on the other hand, the modified compound in the composite modified film can generate interaction with the phenolic aldehyde modified epoxy resin and the o-cresol formaldehyde epoxy resin in the coating system, and the temperature resistance and the flexibility of the composite epoxy resin base material can be improved at the same time.
The composite modified film is doped with rare earth elements Gd and Er, so that the modification of the combined filler can be obviously improved, the composite modified film can act on the whole coating system, and the comprehensive performance of the coating can be obviously improved: (1) ce and Er atoms have empty valence bond tracks, are active in chemical property, have large contact surface with other atoms, and can form a network structure taking Ce and Er as centers, so that the polymerization force of the composite modified film can be increased, the compactness and the strength of the composite modified film are improved, and the acid-base corrosion resistance of the coating can be improved; on the other hand, Er can effectively refine crystals and can form a plurality of compounds with Al and Fe, such as Al 3 Er can further improve the compactness of the composite modified film and improve the thermal stability of the coating; (2) 0 Gd is introduced into a coating system through a composite modified membrane 2 O 3 Gd has rich electronic energy level, large ionic radius, high charge and stronger complexing ability 2 O 3 The inorganic network and the composite epoxy resin matrix can generate the combination of chemical bonds to strengthen the bonding of interfaces, and Gd 2 O 3 The particles can bear certain load, so that the tensile strength of the coating is improved, and the toughness is enhanced; while Gd 2 O 3 The chain segment of the curable composite epoxy resin is difficult to move, so that the glass transition temperature Tg of the system is improved.
In the invention, rare earth elements Gd, Er and Fe 2 O 3 、Al 2 O 3 The introduction of the modified wollastonite powder can improve the dispersion performance of the wollastonite powder and the sericite powder, and the modified wollastonite powder and the sericite powder are loadedForm-introduced rare earth elements Gd and Er, and Fe 2 O 3 、Al 2 O 3 The components can be uniformly dispersed in a coating system, so that the effects of complementary and synergistic enhancement are achieved, and the enhancement effect of each component on the coating can be favorably exerted.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are all conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention, which comprises the following components in parts by weight:
100-130 parts of composite epoxy resin;
60-70 parts of combined filler;
2-10 parts of adhesion promoter;
0.5-2 parts of degassing agent;
6-10 parts of a curing agent;
1-3 parts of a leveling agent;
2-10 parts of pigment and filler;
in a preferred embodiment, the composite epoxy resin is a combination of a phenolic-modified epoxy resin and an o-cresol novolac epoxy resin, and the phenolic-modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1-4: 1; in a further preferred embodiment, the phenolic-modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 2: 1. As an anticorrosion pipe to be used in a high temperature and high pressure environment, the glass transition temperature Tg of the coating is at least 5 ℃ higher than the maximum design temperature of the pipe, and the coating needs to have sufficient flexibility to avoid cracking, peeling, and the like of the coating in the case of use such as bending of the pipe. However, the two features of high Tg and good flexibility are often contradictory in conventional epoxy coating systems, i.e., the higher the Tg, the less flexible the coating, the higher the Tg usually achieved by increasing the crosslink density of the polymer, which generally decreases the flexibility of the coating. Thus, it is a difficult but important application value to obtain coatings having both a high Tg and good flexibility. In the invention, the phenolic aldehyde modified epoxy resin and the o-cresol formaldehyde epoxy resin are used in combination, so that a good level can be obtained in the aspects of high Tg and good flexibility; in addition, the invention determines the optimized proportion of the phenolic aldehyde modified epoxy resin through a large amount of experiments and analyses: the mass ratio of the o-cresol formaldehyde epoxy resin is 2:1, and the requirements of high Tg and high flexibility of the coating can be met.
In a preferred embodiment, the combined filler is a mixture of wollastonite and sericite, and the weight ratio of wollastonite: the mass ratio of the sericite is 1: 1-3: 1. In a further preferred embodiment, wollastonite: the mass ratio of sericite is 1: 1. The acicular or rodlike wollastonite is selected and matched with the sericite to be used, so that the corrosion resistance and the flexibility of the coating can be improved, the acicular or rodlike wollastonite is easy to form an intercrossed three-dimensional structure in the stacking process, and the acicular or rodlike wollastonite is just corresponding to a three-dimensional mesh structure formed in the epoxy resin crosslinking and curing process, so that a more compact coating can be formed; and the sericite is in a scaly shape, and the sericite in a flaky structure is easy to be paved in the coating to form a scaly state due to liquid flow in the process of melting the epoxy resin into a liquid state, so that corrosive media are prevented or delayed from entering the coating, and the corrosion resistance and the boiling resistance of the coating can be improved.
In a preferred embodiment, the curing agent is dicyandiamide or a dicyandiamide derivative, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, and the degassing agent is benzoin.
In a preferred embodiment, the adhesion promoter is a silane coupling agent; in a further preferred embodiment, the silane coupling agent is one or more of A151, A171, A172 and KH-602. The silane coupling agent is used as an adhesion promoter and is arranged between the inorganic filler and the organic resin interface, so that a bonding layer of an organic matrix, the silane coupling agent and the inorganic matrix can be formed, the inorganic filler is tightly bonded with an organic matter, and the adhesion of the coating is improved.
In a preferred embodiment, the pigment and filler is one or more of carbon black, titanium dioxide, iron oxide red, iron oxide yellow and phthalocyanine blue, and can be selected according to the use requirement.
In a preferred embodiment, the preparation method of the high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention comprises the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and fully mixing for 3-5 minutes at the speed of 1000-2000 r/m;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 40-60Hz, the melt temperature of the extruder is controlled at 90-100 ℃, and the temperature of a discharge port of the extruder is not higher than 110 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding and sieving to obtain the epoxy powder coating.
In a preferred embodiment, the combined filler is a mixture of wollastonite and sericite which are subjected to composite modification treatment, and is prepared by the following method:
1) wollastonite and sericite were dispersed in water to prepare a combined filler dispersion:
respectively grinding wollastonite and sericite into powder, and then mixing the wollastonite: mixing sericite in a mass ratio of 1: 1-3: 1, adding the mixture into deionized water, stirring, adding a dispersing agent and a coupling agent, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid; in a preferred embodiment, the dispersant is sodium hexametaphosphate and the aluminate coupling agent is distearoyl oxy isopropyl aluminate, DL-411 or DL-411D.
2) Coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 9-10;
2-2) heating the solution to 80-95 ℃, and then dropwise adding NaSiO into the solution under continuous stirring 3 After the solution is added dropwise, adjusting the pH value of the solution to 6-6.5 by using sulfuric acid or hydrochloric acid, and aging for 2-6 h;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano silicon dioxide coated combined filler obtained in the step 2) to 115-160 ℃, and keeping the temperature for 1-4 h;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, gadolinium acetate hydrate (C) 6 H 11 GdO 7 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Adding into a reaction vessel, mixing, stirring uniformly, and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 185-350 ℃ under continuous stirring, and reacting for 2-10 hours;
3-5) heating to 750-1100 ℃, calcining for 1-8 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
Wollastonite has the characteristics of chemical corrosion resistance, good thermal stability, excellent mechanical property and the like, and is widely applied as a reinforcing filler of polymer materials. Sericite is silicate with a layered structure, can be split into extremely thin sheets, has large diameter-thickness ratio, good wear resistance and wear resistance, heat resistance, insulation, stable chemical property and strong acid-base corrosion resistance; also sericite can be used as a reinforcing material of the coating. The matching use of the wollastonite and the sericite can achieve a synergistic enhancement effect in the aspect of improving the performance of the coating.
However, wollastonite and sericite have obvious defects: the defects of poor dispersibility, easy agglomeration and poor compatibility with polymer materials cause the practical application effect to be greatly reduced, the reinforcing effect is difficult to be fully exerted, and particularly, the defects of poor dispersibility and poor compatibility are more obvious when the two are matched for use. The invention can overcome the defects by modifying the wollastonite and the sericite together, so that the reinforcing performance of the wollastonite and the sericite can be fully exerted, and the effect of synergistically enhancing the comprehensive performance of the coating can be further realized by the action of the modified compound and the coating system.
According to the invention, the nanometer silicon dioxide film and the composite modified film are coated in a double-layer manner to modify the wollastonite powder and the sericite powder, so that on one hand, the dispersibility of the wollastonite powder and the sericite powder and the compatibility with a polymer material can be obviously improved, and the reinforcing effect of the nanometer silicon dioxide film and the composite modified film on the adhesion and mechanical properties of the coating can be fully exerted; on the other hand, the modified compound in the composite modified film can generate interaction with the phenolic aldehyde modified epoxy resin and the o-cresol formaldehyde epoxy resin in the coating system, and the temperature resistance and the flexibility of the composite epoxy resin base material can be improved at the same time.
The modification of the wollastonite powder in the invention comprises two steps:
1. nano SiO produced by reaction 2 Coating the surfaces of the wollastonite powder and the sericite powder; by depositing nano SiO on the surfaces of wollastonite powder and sericite powder 2 Particle formation of nano SiO 2 The layer can improve sharp edges and corners formed when the wollastonite powder and the sericite powder are crushed and flatten the cleavage surface of the wollastonite, thereby improving the strength of the wollastonite powder and the sericite powder to a certain extent, improving the bonding interface of the wollastonite powder and the sericite powder with the composite epoxy resin substrate and enhancing the compatibility of the wollastonite powder and the sericite powder with the substrate.
2. Single nano SiO 2 The film coating modification has limited improvement on the dispersibility and compatibility of wollastonite powder and sericite powder and the improvement on the mechanical strength and adhesive force of the coating, mainly because the nano SiO obtained by adopting an inorganic nano coating method 2 The thickness uniformity of the film is difficult to control, and the density of the film layer is not enough. In the present invention,through the second step, the nanometer SiO film is covered with the wollastonite powder and the sericite powder, and then the aluminum oxide-ferric oxide composite modified film doped with rare earth gadolinium and erbium is covered, so that the nanometer SiO film can be compensated 2 The film is insufficient.
The forming and coating principle of the composite modified film is as follows:
1、AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 decomposition of O to AlCl under heating 3 、FeCl 3 And steam, further heating to remove AlCl 3 、FeCl 3 Sublimed into gas (AlCl) 3 Subliming at about 183 deg.C to obtain FeCl 3 Sublimable at about 300 deg.C), AlCl 3 Combined with steam to form Al (OH) 3 FeCl adsorbed on the surface of wollastonite powder or sericite powder 3 Combined with steam to produce Fe (OH) 2 、Fe(OH) 3 Also adsorbed on the surfaces of wollastonite powder and sericite powder; gadolinium (C) acetate hydrate 6 H 11 GdO 7 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Decomposition to gadolinium oxide (Gd) under heating 2 O 3 ) Erbium oxide (Er) 2 O 3 ）、CO 2 And steam, etc., acting on these streams and Al (OH) 3 、Fe(OH) 2 、Fe(OH) 3 Under the entrainment effect of the particles, gadolinium oxide and erbium oxide are also adsorbed on the surface of the wollastonite powder; so that Al (OH) is contained in the wollastonite powder and the sericite powder 3 、Fe(OH) 2 、Fe(OH) 3 、Gd 2 O 3 、Er 2 O 3 A composite modified film of a plurality of compounds;
2. further heated, Al (OH) 3 Conversion to Al 2 O 3 ，Fe(OH) 2 、Fe(OH) 3 Then dehydrated and oxidized to form Fe 2 O 3 Finally, the surface of the wollastonite powder is coated to form dense doped Gd 2 O 3 And Er 2 O 3 Al of (2) 2 O 3 -Fe 2 O 3 A composite modified film, the dispersibility and the fluidity of the composite modified film to the wollastonite powder and the sericite powder, the compatibility of the composite modified film to the composite epoxy resin base material, the flexibility and the vitrification of a coatingThe transformation temperature and the adhesion promotion have obvious enhancement effect.
3. Due to the formation of AlCl in the gas phase by sublimation 3 、FeCl 3 Combined with steam to form Al (OH) 3 、Fe(OH) 2 、Fe(OH) 3 The aluminum and iron compounds can be more uniformly and fully coated on the surface of the wollastonite powder in the form of nanoparticles, and compared with single Al 2 O 3 Film, Fe 2 O 3 The compounding of the composite material can improve the viscosity of the film layer so that the film layer can be firmly coated on the surfaces of the wollastonite powder and the sericite powder, and meanwhile, the toughness of the film layer is also improved; and the nano fine particles obtained by high-temperature calcination dehydration can form a sufficiently dense composite modified film. Fe 2 O 3 The bonding strength between the coating and the metal substrate can be improved, and the adhesive force is improved.
The composite modified film is doped with rare earth elements Gd and Er, so that the composite modified film can play at least the following roles:
A. ce and Er atoms have a vacant bond track, have active chemical properties, have large contact surface with other atoms and can form a network structure taking Ce and Er as centers, so that the polymerization force of the composite modified film can be increased, the compactness and the strength of the composite modified film are improved, and the acid and alkali corrosion resistance of a coating can be improved; on the other hand, Er can effectively refine crystals and can form a plurality of compounds with Al and Fe, such as Al 3 Er can further improve the compactness of the composite modified film and improve the thermal stability of the coating.
B. Gd is introduced into a coating system through a composite modified film 2 O 3 Gd has rich electronic energy level, large ionic radius, high charge and stronger complexing ability 2 O 3 The inorganic network and the composite epoxy resin matrix can generate the combination of chemical bonds to enhance the bonding of the interface, and Gd 2 O 3 The particles can bear certain load, so that the tensile strength of the coating is improved, and the toughness is enhanced; while Gd 2 O 3 The chain segment of the curable composite epoxy resin is difficult to move, so that the glass transition temperature Tg of the system is improved.
According to the invention, the nano silicon dioxide film and the composite modified film are subjected to double-layer coating modification, so that the comprehensive performances such as dispersibility and strength of wollastonite powder and sericite powder are remarkably improved, the improvement of the performances of the wollastonite powder and the sericite powder can be acted on the finally formed coating, the adhesion performance, mechanical strength and the like of the coating are improved, and meanwhile, various doped compounds introduced by the composite modified film can also be acted on the coating, so that the toughness, acid-base corrosion resistance, high temperature and high pressure resistance and the like of the coating are further improved.
After the modified wollastonite powder and the sericite powder which are coated by the nano silicon dioxide film and the composite modified film are blended into the epoxy powder coating to finally form the coating, the compactness of the coating and the binding force between the coating and a substrate can be improved by virtue of the characteristics that the rare earth element Er has high reaction activity and can react with epoxy resin to obtain a compound with extremely strong bond energy, the oxidation rate of the coating is reduced, the anti-stripping performance of the coating is improved, the drying of the coating can be promoted, and the adhesion performance of the coating is improved.
In the invention, rare earth elements Gd, Er and Fe 2 O 3 、Al 2 O 3 The introduction of the rare earth element can improve the dispersion performance of the wollastonite powder and the sericite powder, and rare earth elements Gd, Er and Fe are introduced in a form of modifying the wollastonite powder and the sericite powder to load 2 O 3 、Al 2 O 3 The components can be uniformly dispersed in a coating system, so that the effects of complementary and synergistic enhancement are achieved, and the enhancement effect of each component on the coating can be favorably exerted.
The present invention is further illustrated by the following examples and comparative examples, which are given above as a general idea of the present invention.
Example 1
A high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention comprises the following components in parts by weight:
120 parts of composite epoxy resin;
60 parts of combined filler;
2 parts of adhesion promoter;
0.8 part by weight of degassing agent;
6 parts of a curing agent;
1.6 parts of a leveling agent;
8 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1;
wherein the curing agent is dicyandiamide, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, the degassing agent is benzoin, and the adhesion promoter is a silane coupling agent A17. The pigment and filler is titanium dioxide.
In this embodiment, the preparation method of the high-temperature and high-pressure resistant hot-melt epoxy powder coating for pipeline corrosion prevention includes the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and fully mixing for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 95 ℃, and the temperature of a discharge port of the extruder is not higher than 110 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) grinder, removing superfine particles by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
In this embodiment, the combined filler is a mixture of wollastonite and sericite after composite modification, and the wollastonite: the mass ratio of the sericite is 1:1, and the combined filler is prepared by the following method:
1) wollastonite and sericite were dispersed in water to prepare a combined filler dispersion:
respectively grinding rod-shaped wollastonite and sericite into powder, and then mixing the rod-shaped wollastonite and the sericite into powder according to the weight ratio of wollastonite: mixing sericite in a mass ratio of 1:1, adding the mixture into deionized water, stirring, adding sodium hexametaphosphate and distearoyl isopropyl aluminate, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 10;
2-2) heating the solution to 90 ℃, and then dropwise adding NaSiO to the solution under continuous stirring 3 After the solution is dropwise added, adjusting the pH value of the solution to 6.5 by using sulfuric acid or hydrochloric acid, and aging for 5 hours;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano-silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano silicon dioxide coated combined filler obtained in the step 2) to 130 ℃, and keeping the temperature for 2 hours;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, gadolinium acetate hydrate (C) 6 H 11 GdO 7 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Adding into a reaction vessel, mixing, stirring uniformly, and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 320 ℃ under continuous stirring, and reacting for 7 hours;
3-5) heating to 1050 ℃, and calcining for 5 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
Example 2
A high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention comprises the following components in parts by weight:
130 parts of composite epoxy resin;
65 parts of combined filler;
6 parts of adhesion promoter;
1 part by weight of degassing agent;
7 parts of a curing agent;
2 parts of a leveling agent;
9 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1;
wherein the curing agent is dicyandiamide, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, the degassing agent is benzoin, and the adhesion promoter is a silane coupling agent A17. The pigment and filler is titanium dioxide.
In this embodiment, the preparation method of the high-temperature and high-pressure resistant hot-melt epoxy powder coating for pipeline corrosion prevention includes the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and fully mixing for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 95 ℃, and the temperature of a discharge port of the extruder is not higher than 110 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) grinder, removing superfine particles by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
In this embodiment, the combined filler is a mixture of wollastonite and sericite after composite modification, and the wollastonite: the mass ratio of the sericite is 1:1, and the combined filler is prepared by the following method:
1) rod-like wollastonite and sericite were dispersed in water to prepare a combined filler dispersion:
respectively grinding wollastonite and sericite into powder, and then mixing the wollastonite: mixing sericite in a mass ratio of 1:1, adding the mixture into deionized water, stirring, adding sodium hexametaphosphate and distearoyl isopropyl aluminate, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 10;
2-2) heating the solutionTo 90 ℃, then NaSiO is added into the solution dropwise under continuous stirring 3 After the solution is dropwise added, adjusting the pH value of the solution to 6.5 by using sulfuric acid or hydrochloric acid, and aging for 5 hours;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano silicon dioxide coated combined filler obtained in the step 2) to 130 ℃, and keeping the temperature for 2 hours;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, gadolinium acetate hydrate (C) 6 H 11 GdO 7 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Adding into a reaction vessel, mixing, stirring uniformly, and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 320 ℃ under continuous stirring, and reacting for 7 hours;
3-5) heating to 1050 ℃, and calcining for 5 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
Example 3
A high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention comprises the following components in parts by weight:
120 parts of composite epoxy resin;
65 parts of combined filler;
2 parts of adhesion promoter;
0.8 part by weight of degassing agent;
6 parts of a curing agent;
1.6 parts of a leveling agent;
8 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1;
wherein the curing agent is dicyandiamide, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, the degassing agent is benzoin, and the adhesion promoter is a silane coupling agent A17. The pigment and filler is titanium dioxide.
In this embodiment, the preparation method of the high-temperature and high-pressure resistant hot-melt epoxy powder coating for pipeline corrosion prevention includes the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and fully mixing for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 95 ℃, and the temperature of a discharge port of the extruder is not higher than 110 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) grinder, removing superfine particles by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
In this embodiment, the combined filler is a mixture of wollastonite and sericite after composite modification, and the wollastonite: the mass ratio of the sericite is 1:1, and the combined filler is prepared by the following method:
1) wollastonite and sericite were dispersed in water to prepare a combined filler dispersion:
respectively grinding rod-shaped wollastonite and sericite into powder, and then mixing the rod-shaped wollastonite and the sericite into powder according to the weight ratio of wollastonite: mixing sericite in a mass ratio of 1:1, adding the mixture into deionized water, stirring, adding sodium hexametaphosphate and distearoyl isopropyl aluminate, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 10;
2-2) heating the solution to 90 ℃, and then dropwise adding NaSiO to the solution under continuous stirring 3 After the solution is dropwise added, adjusting the pH value of the solution to 6.5 by using sulfuric acid or hydrochloric acid, and aging for 5 hours;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano-silica coated combined filler obtained in the step 2) to 130 ℃, and keeping the temperature for 2 hours;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, gadolinium acetate hydrate (C) 6 H 11 GdO 7 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Adding into a reaction vessel, mixing, stirring uniformly, and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 320 ℃ under continuous stirring, and reacting for 7 hours;
3-5) heating to 1050 ℃, and calcining for 5 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
Example 4
A high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention comprises the following components in parts by weight:
120 parts of composite epoxy resin;
70 parts of combined filler;
2 parts of adhesion promoter;
0.8 part by weight of degassing agent;
6 parts of a curing agent;
1.6 parts of a leveling agent;
8 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1;
wherein the curing agent is dicyandiamide, the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, the degassing agent is benzoin, and the adhesion promoter is a silane coupling agent A17. The pigment and filler is titanium dioxide.
In this embodiment, the preparation method of the high-temperature and high-pressure resistant hot-melt epoxy powder coating for pipeline corrosion prevention includes the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and fully mixing for 5 minutes at the speed of 1500 rpm;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 50Hz, the melt temperature of the extruder is controlled at 95 ℃, and the temperature of a discharge port of the extruder is not higher than 110 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding by an ACM (Acrylonitrile-butadiene-styrene) grinder, removing superfine particles by using a cyclone separator, sieving by a 160-mesh sieve to obtain the epoxy powder coating, and packaging.
In this embodiment, the combined filler is a mixture of wollastonite and sericite after composite modification, and the wollastonite: the mass ratio of the sericite is 1:1, and the combined filler is prepared by the following method:
1) wollastonite and sericite were dispersed in water to prepare a combined filler dispersion:
respectively grinding rod-shaped wollastonite and sericite into powder, and then mixing the rod-shaped wollastonite and the sericite into powder according to the weight ratio of wollastonite: mixing sericite in a mass ratio of 1:1, adding the mixture into deionized water, stirring, adding sodium hexametaphosphate and distearoyl isopropyl aluminate, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 10;
2-2) heating the solution to 90 ℃, and then dropwise adding NaSiO to the solution under continuous stirring 3 After the solution is dropwise added, adjusting the pH value of the solution to 6.5 by using sulfuric acid or hydrochloric acid, and aging for 5 hours;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano-silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano silicon dioxide coated combined filler obtained in the step 2) to 130 ℃, and keeping the temperature for 2 hours;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, gadolinium acetate hydrate (C) 6 H 11 GdO 7 ) And erbium acetate tetrahydrate (C) 6 H 17 ErO 10 ) Adding into a reaction vessel, mixing, stirring uniformly, and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 320 ℃ under continuous stirring, and reacting for 7 hours;
3-5) heating to 1050 ℃, and calcining for 5 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
Comparative example 1
This example is substantially the same as example 1, except that: the composite epoxy resin in this example is replaced by o-cresol formaldehyde epoxy resin.
Comparative example 2
This example is substantially the same as example 1, except that: in this example, no adhesion promoter was added: silane coupling agent a 17.
Comparative example 3
This example is substantially the same as example 1, except that: in this example no combined filler was added.
Comparative example 4
This example is substantially the same as example 1, except that: the combined filler in this example was replaced with rod-shaped wollastonite.
Comparative example 5
This example is substantially the same as example 1, except that: the composite filler in this example was replaced with sericite.
Comparative example 6
This example is substantially the same as example 1, except that: the combined filler in this example was a mixture of wollastonite and sericite, and the weight ratio of wollastonite: the mass ratio of sericite was 1:1, but no composite modification treatment was performed.
Comparative example 7
This example is substantially the same as example 1, except that:
the combined filler in the embodiment is a mixture of modified wollastonite powder and sericite powder coated by a nano silica film, and is prepared by the following method:
1) dispersing wollastonite and sericite in water to prepare a combined filler dispersion:
respectively grinding rod-shaped wollastonite and sericite into powder, and then mixing the rod-shaped wollastonite and the sericite into powder according to the weight ratio of wollastonite: mixing sericite in a mass ratio of 1:1, adding the mixture into deionized water, stirring, adding sodium hexametaphosphate and distearoyl isopropyl aluminate, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 10;
2-2) heating the solution to 90 ℃, and then dropwise adding NaSiO to the solution under continuous stirring 3 After the solution is dropwise added, adjusting the pH value of the solution to 6.5 by using sulfuric acid or hydrochloric acid, and aging for 5 hours;
2-3) filtering, washing and drying the solid product, and grinding to obtain the nano silicon dioxide coated combined filler.
Comparative example 8
This example is substantially the same as example 1, except that:
the combined filler in the embodiment is a mixture of modified wollastonite powder and sericite powder which are compositely coated by a nano silicon dioxide film and an aluminum dioxide film, and is prepared by the following method:
1) dispersing wollastonite and sericite in water to prepare a combined filler dispersion:
respectively grinding rod-shaped wollastonite and sericite into powder, and then mixing the rod-shaped wollastonite and the sericite into powder according to the weight ratio of wollastonite: mixing sericite in a mass ratio of 1:1, adding the mixture into deionized water, stirring, adding sodium hexametaphosphate and distearoyl isopropyl aluminate, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 10;
2-2) heating the solution to 90 ℃, and then dropwise adding NaSiO to the solution under continuous stirring 3 After the solution is dropwise added, adjusting the pH value of the solution to 6.5 by using sulfuric acid or hydrochloric acid, and aging for 5 hours;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano silicon dioxide coated combined filler obtained in the step 2) to 130 ℃, and keeping the temperature for 2 hours;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O, adding the mixture into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 320 ℃ under continuous stirring, and reacting for 7 hours;
3-5) heating to 1050 ℃, and calcining for 5 hours;
3-6) cooling to room temperature, and grinding to obtain the nano silicon dioxide film-aluminum dioxide film composite coated combined filler.
The epoxy powder coatings prepared in examples 1 to 4 and comparative examples 1 to 8 were prepared as coating samples and tested for properties. Coating the epoxy powder coating on the surface of a metal substrate by adopting electrostatic spraying, wherein the voltage is as follows: 60-80KV and 2-3KG/CM 2 And obtaining a coating sample for testing.
The detection items comprise:
1. DSC testing glass transition temperature Tg of coating, and inspection standard and method
《ISO11357-5-1999》；
2. Boiling adhesion force (2 h), and testing standard and method GB/T9286-2014;
3. cathodic disbondment resistance (1.5V, 20 ℃, 28 d), test standard and method SY/T0315-1997.
The results of the measurements are shown in Table 1 below.
TABLE 1
The adhesive force is classified into grades, the grade 0 is best, the grade 1 is the highest, and the larger the number is, the worse the adhesive force is; the larger the above peeling radius, the worse the corrosion resistance of the coating.
From the above detection results, it can be seen that the epoxy powder coatings provided in embodiments 1 to 4 of the present invention have relatively high glass transition temperature, and are excellent in boiling resistance and corrosion resistance. The use requirement under high temperature and high pressure can be met, and the use requirement of a high-temperature environment within 150 ℃ can be met according to the design that the Tg operation temperature is higher than 5 ℃.
The comparison between the comparative example 3 and the example 1 can show the comprehensive performance strengthening effect of the combined filler on the coating system.
From comparison of the results of comparative examples 4 to 8 with those of example 1, it can be seen that the combination of the filler of example 1 is replaced by wollastonite powder or sericite powder alone or a mixture of wollastonite powder and sericite powder without modification, or a nano silica film alone or a nano silica film-alumina film alone without doping with rare earth elements, and the combination of the filler of example 1 has a lower overall performance than that of example 1.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. The high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention is characterized by comprising the following components in parts by weight:
100-130 parts of composite epoxy resin;
60-70 parts of combined filler;
2-10 parts of adhesion promoter;
0.5-2 parts of degassing agent;
6-10 parts of a curing agent;
1-3 parts of a leveling agent;
2-10 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1-4: 1;
wherein the combined filler is a mixture of wollastonite and sericite, and the weight ratio of wollastonite: the mass ratio of the sericite is 1: 1-3: 1.
2. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention according to claim 1, wherein the phenolic modified epoxy resin in the composite epoxy resin: the mass ratio of the o-cresol formaldehyde epoxy resin is 2:1, wollastonite: the mass ratio of sericite is 1: 1.
3. The high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for preventing corrosion of pipelines according to claim 1, wherein the curing agent is dicyandiamide or a dicyandiamide derivative.
4. The high-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for preventing corrosion of pipelines as claimed in claim 1, wherein the leveling agent is an acrylate leveling agent adsorbed by silicon dioxide, and the degassing agent is benzoin.
5. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for pipeline corrosion prevention according to claim 1, wherein the adhesion promoter is a silane coupling agent.
6. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for preventing corrosion of pipelines according to claim 5, wherein the silane coupling agent is one or more of A151, A171, A172 and KH-602.
7. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for preventing corrosion of pipelines according to claim 1, wherein the preparation method comprises the following steps:
s1, weighing the raw materials according to the weight part ratio, pouring the raw materials into a premixing container, and uniformly mixing;
s2, adding the uniformly mixed raw materials into a double-screw extruder for melt extrusion, wherein the rotating speed frequency of an extrusion screw of the extruder is 40-60Hz, and the melting temperature of the extruder is controlled at 90-100 ℃;
and S3, pressing the extruded material into a roller for cooling, tabletting, grinding and sieving to obtain the epoxy powder coating.
8. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for preventing corrosion of pipelines as claimed in claim 1, wherein the combined filler is a mixture of wollastonite and sericite which are subjected to composite modification treatment, and is prepared by the following method:
1) dispersing wollastonite and sericite in water to prepare a combined filler dispersion liquid;
2) coating a nano silicon dioxide film;
3) and coating the composite modified membrane.
9. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for preventing corrosion of pipelines according to claim 8, wherein the combined filler is prepared by the following method:
1) preparing a combined filler dispersion liquid:
respectively grinding wollastonite and sericite into powder, and then mixing the wollastonite: mixing sericite in a mass ratio of 1: 1-3: 1, adding the mixture into deionized water, stirring, adding a dispersing agent and a coupling agent, and performing ultrasonic dispersion to obtain a combined filler dispersion liquid;
2) coating a nano silicon dioxide film:
2-1) adding NaOH into the combined filler dispersion liquid, and adjusting the pH value of the solution to 9-10;
2-2) heating the solution to 80-95 ℃, and then dropwise adding NaSiO into the solution under continuous stirring 3 After the solution is added dropwise, adjusting the pH value of the solution to 6-6.5 by using sulfuric acid or hydrochloric acid, and aging for 2-6 h;
2-3) filtering, washing and drying the solid product, and grinding the solid product into powder to obtain the nano silicon dioxide coated combined filler;
3) coating a composite modified film:
3-1) preheating the nano silicon dioxide coated combined filler obtained in the step 2) to 115-160 ℃, and keeping the temperature for 1-4 h;
3-2) reacting AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 Adding O, gadolinium acetate hydrate and erbium acetate tetrahydrate into a reaction container, mixing, uniformly stirring and grinding;
3-3) adding the combined filler coated by the nano silicon dioxide treated in the step 3-1) into a reaction vessel, mixing with the product obtained in the step 3-2), and stirring uniformly;
3-4) heating to 185-350 ℃ under continuous stirring, and reacting for 2-10 hours;
3-5) heating to 750-1100 ℃, calcining for 1-8 hours;
3-6) cooling to room temperature, and grinding to obtain the composite modified filler.
10. The high-temperature and high-pressure resistant hot-melt bonding epoxy powder coating for corrosion prevention of pipelines according to any one of claims 1 to 9, characterized by comprising the following components in parts by weight:
120 parts of composite epoxy resin;
60 parts of combined filler;
2 parts of adhesion promoter;
0.8 part by weight of degassing agent;
6 parts of a curing agent;
1.6 parts of a leveling agent;
8 parts of pigment and filler;
wherein the composite epoxy resin is the combination of phenolic aldehyde modified epoxy resin and o-cresol formaldehyde epoxy resin, and the phenolic aldehyde modified epoxy resin comprises the following components in percentage by weight: the mass ratio of the o-cresol formaldehyde epoxy resin is 1: 1;
wherein the combined filler is a mixture of wollastonite and sericite, and the weight ratio of wollastonite: the mass ratio of sericite is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210830695.0A CN115044273B (en) | 2022-07-15 | 2022-07-15 | High-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210830695.0A CN115044273B (en) | 2022-07-15 | 2022-07-15 | High-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115044273A true CN115044273A (en) | 2022-09-13 |
| CN115044273B CN115044273B (en) | 2023-04-07 |
Family
ID=83164820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210830695.0A Active CN115044273B (en) | 2022-07-15 | 2022-07-15 | High-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115044273B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746664A (en) * | 2022-11-23 | 2023-03-07 | 新乡学院 | Preparation method of silane modified nanoparticle epoxy resin coating on aluminum alloy surface |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08112879A (en) * | 1994-10-14 | 1996-05-07 | Tonen Corp | Sio2-covered plastic film and manufacture thereof |
| WO2008006308A1 (en) * | 2006-07-03 | 2008-01-17 | Yigang Zhang | Powder coated by aluminium phosphate and its making method |
| CN103525239A (en) * | 2013-09-25 | 2014-01-22 | 中国石油天然气股份有限公司 | Special wear-resistant powder coating for corrosion prevention of down-hole oil tubes and sucker rods |
| CN110951279A (en) * | 2019-12-05 | 2020-04-03 | 江西广源化工有限责任公司 | Preparation method of superfine acicular wollastonite modified spherical silicon dioxide composite powder |
| CN114539871A (en) * | 2022-01-27 | 2022-05-27 | 福建万安实业集团有限公司 | Anticorrosive powder coating for deep well pipeline and preparation method and application thereof |
| CN115058174A (en) * | 2022-07-11 | 2022-09-16 | 南通美怡彩新材料科技有限公司 | Epoxy powder coating with high adhesive force to metal substrate |
-
2022
- 2022-07-15 CN CN202210830695.0A patent/CN115044273B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08112879A (en) * | 1994-10-14 | 1996-05-07 | Tonen Corp | Sio2-covered plastic film and manufacture thereof |
| WO2008006308A1 (en) * | 2006-07-03 | 2008-01-17 | Yigang Zhang | Powder coated by aluminium phosphate and its making method |
| CN103525239A (en) * | 2013-09-25 | 2014-01-22 | 中国石油天然气股份有限公司 | Special wear-resistant powder coating for corrosion prevention of down-hole oil tubes and sucker rods |
| CN110951279A (en) * | 2019-12-05 | 2020-04-03 | 江西广源化工有限责任公司 | Preparation method of superfine acicular wollastonite modified spherical silicon dioxide composite powder |
| CN114539871A (en) * | 2022-01-27 | 2022-05-27 | 福建万安实业集团有限公司 | Anticorrosive powder coating for deep well pipeline and preparation method and application thereof |
| CN115058174A (en) * | 2022-07-11 | 2022-09-16 | 南通美怡彩新材料科技有限公司 | Epoxy powder coating with high adhesive force to metal substrate |
Non-Patent Citations (3)
| Title |
|---|
| 史建公;苏海霞;张新军;任靖;尹国海;: "稀土元素对氧化铝性能影响的研究进展" * |
| 陈国斌: "硅灰石粉的包膜改性研究" * |
| 黄佳木,吴美升,盖国胜: "纳米SiO_2包覆硅灰石粉填充改性聚丙烯的研究" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746664A (en) * | 2022-11-23 | 2023-03-07 | 新乡学院 | Preparation method of silane modified nanoparticle epoxy resin coating on aluminum alloy surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115044273B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101481575B (en) | Epoxy phenolic-titanium-structure amine nano composite heatproof heavy-duty anti-corrosive paint and preparation | |
| CN115044273B (en) | High-temperature-resistant high-pressure-resistant hot-melt epoxy powder coating for pipeline corrosion prevention | |
| CN112063200B (en) | MXene-based solvent-free nano fluid and preparation method thereof | |
| CN102329553B (en) | Eccentric wear resisting powder paint of oil well pipe | |
| EP0959102A3 (en) | Silica particles surface-treated with silane, process for producing the same and uses thereof | |
| CN103214914B (en) | A kind of nanometer heavy-duty coating | |
| CN108753107B (en) | Strong acid and alkali resistant composite ceramic anticorrosive paint and preparation method thereof | |
| CN111892857A (en) | Industrial pipeline anticorrosion powder coating and preparation method thereof | |
| CN110183934A (en) | A kind of wear-resisting type bi-component graphene anticorrosive paint | |
| CN113388311A (en) | Preparation method of nano titanium dioxide modified hexagonal boron nitride modified coating | |
| CN115028894B (en) | Preparation method of composite slurry for preparing two-dimensional mica composite film, two-dimensional mica composite film and preparation method thereof | |
| CN114574072A (en) | Nano powder coating and preparation method and application thereof | |
| CN114085596B (en) | Fusion bonding epoxy powder coating and application thereof in low-surface treatment of rusty steel pipe | |
| CN115058174B (en) | Epoxy powder coating with high adhesive force to metal substrate | |
| CN101323715B (en) | Method for composite modification of microcrystalline antonite powder using epoxy silane and aluminate | |
| CN113930133A (en) | Heavy-duty anticorrosion fusion-bonding epoxy powder coating special for roll coating of large-diameter steel pipe and preparation method thereof | |
| CN111944390B (en) | Modified phenolic epoxy coating and preparation method and application thereof | |
| CN115895394B (en) | Interface passivation type heavy-duty anticorrosive powder coating and preparation method and application thereof | |
| CN116948616A (en) | Pressure-bearing epoxy resin plugging material for oil-based drilling fluid | |
| WO2021077502A1 (en) | Nano silicon-carbon modified graphene special anti-corrosion coating and preparation method therefor | |
| CN114591671B (en) | Preparation method and application of polypyrrole@ZIF-8 modified epoxy resin anticorrosive paint | |
| KR101848241B1 (en) | Method for manufacturing epoxy composites comprising boron nitride | |
| CN115232492A (en) | Water-based phosphate ceramic coating and preparation method thereof | |
| Liu et al. | SCF-NiFe 2 O 4/epoxy composites with high thermal conductivity and electromagnetic interference resistance | |
| CN111334044A (en) | Organic silicone gel for precise electronic component encapsulation and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |