CN114702882B - Petrochemical anticorrosive creep-resistant coating, and preparation method and application thereof - Google Patents
Petrochemical anticorrosive creep-resistant coating, and preparation method and application thereof Download PDFInfo
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- CN114702882B CN114702882B CN202210559729.7A CN202210559729A CN114702882B CN 114702882 B CN114702882 B CN 114702882B CN 202210559729 A CN202210559729 A CN 202210559729A CN 114702882 B CN114702882 B CN 114702882B
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- 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
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Abstract
The application discloses a petrochemical anticorrosive creep-resistant coating, and a preparation method and application thereof. The coating material comprises a first component and a second component; the first component comprises bisphenol A epoxy resin, F epoxy resin, pigment, filler, auxiliaries, solvent and the like, and the second component comprises modified resin, a curing agent, solvent and the like; the modified resin is mainly formed by the prepolymerization addition reaction of an amine-terminated butadiene-acrylonitrile copolymer and an F-type epoxy resin. The coating material is strong in binding force with the metal base material when being applied to the surface of the metal base material, has extremely high toughness and breaking strength, and can form strong constraint force for circumferential stress creep of the metal base material, so that the metal base material is guaranteed to be still capable of keeping small creep elongation under the action of long-time stress.
Description
Technical Field
The application relates to a coating material, in particular to a petrochemical anti-corrosion creep-resistant coating, a preparation method and application thereof, belonging to the technical field of material science.
Background
For metal containers such as large storage tanks and high-pressure pipelines, deformation in different degrees often occurs due to the continuous action of circumferential stress and the creep characteristic of metal under the long-term load state, so that the accident risk coefficient is greatly increased, and great safety risk is brought to operators and the surrounding environment. Although researchers propose various solutions such as changing the material of the metal container, changing the structural design of the metal container, etc., in order to solve such problems, the existing solutions are difficult to popularize and apply due to the technical difficulty or high cost.
Disclosure of Invention
The application mainly aims to provide a petrochemical anticorrosion creep-resistant coating, a preparation method and application thereof so as to overcome the defects in the prior art.
In order to achieve the above purpose, the present application adopts a technical solution comprising:
one aspect of the present application provides a petrochemical anticorrosive creep-resistant coating comprising a first component and a second component; the first component comprises bisphenol A epoxy resin, F epoxy resin, pigment, filler, auxiliary agent, solvent and the like; the second component comprises modified resin, amine epoxy resin curing agent, solvent and the like; the modified resin is mainly formed by carrying out prepolymerization addition reaction on an amine-terminated butadiene-acrylonitrile copolymer and F-type epoxy resin.
Another aspect of the present application provides a method for preparing the petrochemical anticorrosive creep-resistant coating, comprising:
uniformly mixing bisphenol A type epoxy resin, F type epoxy resin, pigment and filler, an auxiliary agent and a solvent to form a mixture, and adjusting the viscosity of the mixture to a proper range by using the solvent to obtain a first component;
uniformly mixing the amine-terminated butadiene-acrylonitrile copolymer with F-type epoxy resin, then fully reacting to prepare modified resin, and uniformly mixing the modified resin, an amine epoxy resin curing agent and a solvent to obtain a second component;
and uniformly mixing the first component and the second component to prepare the petrochemical anticorrosive creep-resistant coating.
Yet another aspect of the present application provides the use of the petrochemical, corrosion-resistant, creep-resistant coating in a method of controlling hoop stress creep of a metal substrate.
Compared with the prior art, the petrochemical anti-corrosion creep-resistant coating provided by the application has simple component design, and when the coating is coated on the surfaces of metal substrates such as metal containers, the formed coating has strong binding force with the metal substrates, has extremely high toughness and breaking strength, and can form strong constraint force on the circumferential stress creep of the metal substrates, so that the metal substrates can still keep very small creep elongation under the action of long-time stress.
Detailed Description
The present application will be more fully understood upon reading the following detailed description. However, it is to be understood that the following disclosed embodiments are merely exemplary of the application, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present application in virtually any appropriately detailed embodiment.
Some embodiments of the present application provide a petrochemical, corrosion-resistant, creep-resistant coating comprising a first component and a second component;
wherein the first component comprises the following components in parts by weight:
the second component comprises the following components in parts by weight:
74-79 parts of modified resin
16-18 parts of amine epoxy resin curing agent
5-10 parts of a solvent;
the modified resin is mainly formed by the prepolymerization addition reaction of amine-terminated butadiene-acrylonitrile copolymer and F-type epoxy resin with the reaction equivalent ratio of 8.8-11.5: 1. By adopting the reaction equivalent, a phenolic epoxy structure is introduced into ATBN partially in advance, so that the compatibility of the first component and the second component is improved on one hand, and the final reaction efficiency is improved on the other hand, thereby effectively improving the strength of the coating.
In one embodiment, the bisphenol A type epoxy resin has the epoxy equivalent weight of 450-520 and the weight-average molecular weight of 900-1100, has a relatively regular structure, and has good flexibility, so that the toughness of the coating can be compensated to a certain degree.
In one embodiment, the epoxy equivalent weight of the F-type epoxy resin is 170-200, and the epoxy functional groups are relatively dense, so that a relatively compact structure can be formed, and the tensile strength is enhanced.
In one embodiment, the amine-terminated butadiene-acrylonitrile copolymer has an amino content of 15 to 17%, an amine equivalent weight of 800 to 850, and a weight average molecular weight of 3000 to 3500.
In one embodiment, the first component comprises a bisphenol A type epoxy resin and a F type epoxy resin in a molar ratio of 0.77 to 0.85: 1. By adopting the proportion of the bisphenol A type epoxy resin to the F type epoxy resin, the elongation and the tensile strength of the coating can be obviously improved.
In one embodiment, the second component comprises the modified resin and the amine epoxy resin curing agent in a mass ratio of 4.4-4.7:1. Among them, m-xylylenediamine (MXDA), for example, industrial-grade xylylenediamine having a purity of not less than 99% is preferably used as the amine-based epoxy resin curing agent, but not limited thereto. Among them, MXDA has a relatively small weight average molecular weight, a relatively regular molecular structure, and a compact functional group, and at the above-mentioned amount ratio, compared with other amine-based curing agents, MXDA forms a structure having a higher density and a higher tensile strength after crosslinking with epoxy of F type, and if MXDA is used in an excessively small amount, it cannot exert a reinforcing effect on the coating layer, but if MXDA is used in an excessively large amount, the elongation of the coating layer is lost.
In one embodiment, the mass ratio of the first component to the second component is 5.5-6.0: 1.
In one embodiment, the pigment and filler includes any one or a combination of more of titanium dioxide, black iron oxide, red iron oxide, talc and silica powder, and is not limited thereto.
In one embodiment, the auxiliary agent includes any one or a combination of more of an antifoaming agent, a leveling agent, and a rheology auxiliary agent, and is not limited thereto.
In one embodiment, the solvent includes any one or a combination of more of xylene, PM, MIBK, acetone, and n-butanol, and is not limited thereto.
Some embodiments of the present application provide a method of preparing the petrochemical anticorrosive creep-resistant coating comprising:
uniformly mixing bisphenol A type epoxy resin, F type epoxy resin, pigment and filler, an auxiliary agent and a solvent to form a mixture, and adjusting the viscosity of the mixture to 110-120KU by using the solvent to obtain a first component;
uniformly mixing the amine-terminated butadiene-acrylonitrile copolymer with F-type epoxy resin, fully reacting at 55-65 ℃ to prepare modified resin, and uniformly mixing the modified resin with an amine epoxy resin curing agent and a solvent to obtain a second component;
and uniformly mixing the first component and the second component to prepare the petrochemical anticorrosive creep-resistant coating.
In one embodiment, the preparation method of the petrochemical anticorrosive creep-resistant coating specifically comprises the following steps:
uniformly mixing bisphenol A type epoxy resin, F type epoxy resin, pigment and filler, an auxiliary agent and a solvent to form a mixture, dispersing at a high speed of 2000-3000r/min for 25-30min, and adjusting the viscosity of the mixture to 110-120KU by using the solvent to obtain a first component;
heating the amine-terminated butadiene-acrylonitrile copolymer to 55-65 ℃, then slowly adding F-type epoxy resin under the condition of continuous stirring, reacting for 2-4h at 55-65 ℃, then cooling to room temperature to obtain modified resin, then adding the modified resin into a solvent under the condition of continuous stirring, slowly adding an amine epoxy resin curing agent, and continuously stirring until the mixture is uniformly mixed to obtain a second component.
In a more specific embodiment, the preparation method of the petrochemical anti-corrosion creep-resistant coating specifically comprises the following steps:
s1, preparing a first component, which comprises the following steps: uniformly mixing bisphenol A epoxy resin with F epoxy resin, pigment and filler, an auxiliary agent and a solvent in sequence, dispersing at a high speed of 2000-3000r/min for 25-30min, and then adjusting the viscosity of the mixture to 110-120KU by using the solvent to obtain a first component;
s2, preparing a second component, which comprises the following steps:
adding a certain amount of amine-terminated butadiene-acrylonitrile copolymer (ATBN resin for short) into a container, starting a stirrer to stir at the rotating speed of 300-500r/min and heating to 55-65 ℃, then slowly adding the F type epoxy resin according to the equivalent ratio of ATBN to F type epoxy resin of 8.8-11.5:1 under the stirring condition, continuously stirring and controlling the temperature to react for 2-4h at 55-65 ℃, and cooling to room temperature to obtain modified resin;
adding the modified resin into the solvent under the low-speed stirring condition with the rotating speed of 300-500r/min, stirring for 5min, then slowly adding the amine epoxy resin curing agent according to the mass ratio of the modified resin to the amine epoxy resin curing agent of 4.4-4.7:1, and continuously stirring for 10-15min at the rotating speed of 300-500r/min until the mixture is uniformly mixed to obtain a second component;
s3, uniformly mixing the first component and the second component according to the mass ratio of 5.5-6.0:1 to obtain the petrochemical anticorrosive creep-resistant coating.
The steps S1 and S2 may be performed simultaneously, or the steps S2 and S1 may be performed first.
In the application, the F-type epoxy resin is adopted to modify the ATBN resin, because the F-type epoxy resin has high epoxy group density, most of epoxy groups are subjected to addition reaction with primary ammonia on terminal amino groups of the ATBN resin in the modification process, so that the ATBN is grafted in a structure, and simultaneously, a secondary amino group and the other terminal amino group of the ATBN are reserved due to the effect of steric hindrance, so that an amino prepolymer FEP-ATBN (namely the modified resin) with higher ATBN content is generated. In the FEP-ATBN, a plurality of ATBN takes F-shaped epoxy as a bridge graft together, and the epoxy group can be completely reacted due to excessive ATBN to become bonding anchor points of the plurality of ATBN, so that the weight average molecular weight is enlarged, and good elongation can be kept on the premise of ensuring dense crosslinking. After the prepolymer FEP-ATBN is cured and crosslinked with the epoxy resin in the first component, on one hand, the coating material is ensured to have higher crosslinking density, and on the other hand, the coating material has extremely high toughness and breaking strength by introducing a large amount of nitrile-butadiene rubber (NBR) structures. In particular, due to the modification of the F-type epoxy, compatibility between the ATBN and the epoxy is enhanced, and it is possible to prevent local phase separation from occurring after the first component and the second component are mixed. When the coating material is coated on the surface of a metal base material such as a metal container (such as a large-sized steel storage tank), the coating material can form a strong restraining force on the circumferential stress creep, so that the metal base material can still keep a small creep elongation rate under the action of long-time stress.
Specifically, when the petrochemical anticorrosive creep-resistant coating of the embodiment of the application is coated on the surface of a steel substrate for a large storage tank, the creep elongation of the coating is between 0.013 and 0.016 percent under the action of a continuous stress of 100 Nx 720h, which is far lower than that of a similar steel substrate coated with a common epoxy-based storage tank protective coating and uncoated with the coating. And the petrochemical anti-corrosion creep-resistant coating has excellent physical properties, the bonding strength of the coating and a steel substrate is 18.5-20.6MPa, and the tensile strength reaches 25.3-28.2MPa.
Some embodiments of the present application provide a method of circumferential stress creep control of a metal substrate comprising: and continuously coating the petrochemical anticorrosive creep-resistant coating on the surface of the metal base material along the circumferential direction to form a protective coating for resisting circumferential stress creep.
Some embodiments of the present application provide a metal substrate's circumferential stress resistance protective structure includes by the petrochemical industry anticorrosion creep resistant coating forms the coating, the coating covers metal substrate surface along the circumference in succession.
In the present application, the metal substrate includes various metal containers, such as large steel storage tanks, metal furnace tubes, metal pressure tubes (e.g., crude oil pipelines, natural gas pipelines, various heat-resistant and pressure-resistant pipelines used in chemical industry, etc.).
The thickness of the coating can be determined according to the actual working condition of the metal base material.
Some embodiments of the present application provide a method of manufacturing a metal container, including:
manufacturing a metal container body by adopting a metal processing method; and
and continuously coating the petrochemical anticorrosion creep-resistant coating on the outer wall of the metal container body along the circumferential direction to form a protective coating resisting circumferential stress creep.
Wherein the metal container body may be a can, a tube, etc., and may be manufactured using various metal processing methods known in the art. For example, the storage tank or the like can be manufactured by processes such as blanking and forming, beveling, tank wall plate assembling, welding, drilling, and coating. Therefore, it will not be described in detail herein.
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The reagents and starting materials used in the following examples are commercially available, and the test methods in which specific conditions are not specified are generally carried out under conventional conditions or conditions recommended by the respective manufacturers. For example, the bisphenol A type epoxy resin used in the following examples has an epoxy equivalent of 450 to 520 (south Asia NPES-901), the F type epoxy resin has an epoxy equivalent of 170 to 200 (south Asia NPPN-638S), the ATBN resin has an amino group content of 15 to 17%, and an amine equivalent of 800 to 850 (Hycar-ATBN). The defoamer employed in the examples below may be Pick BYK-066N and the dispersant may be Pasteur
Ultra PX 4575 and the rheological additive may be Pico BYK-410. In the following examples, the low-speed stirring means a rotation speed of 500r/min or less, the high-speed stirring or dispersion means a rotation speed of 2000r/min or more, and the medium-speed stirring is 1500 to 2000 r/min.
Example 1 a method for preparing a petrochemical anticorrosive creep-resistant coating includes the steps of:
(1) Adding 105g of dimethylbenzene and 45g of n-butyl alcohol into a stirring kettle, adding 350g of bisphenol A epoxy resin under the condition of low-speed stirring, starting high-speed dispersion for 20min until the resin is completely dissolved in a solvent, then reducing the stirring speed to 500r/min, adding 100g of F-type epoxy resin, 11g of rheological additive, 5g of dispersing agent, 2g of defoaming agent, 10g of PM and 15g of dimethylbenzene, stirring at medium speed for 5-10min, then sequentially adding 120g of titanium dioxide, 50g of talcum powder and 170g of silicon powder, dispersing at high speed for 25-30min, and finally adjusting the viscosity to 110-120KU by using 17g of dimethylbenzene to obtain a first component.
(2) 670g of ATBN resin is added into a container, a stirrer is started to stir at the rotating speed of 300r/min and heat to 65 ℃, then 76g of F-type epoxy resin is slowly added under the stirring condition, the stirring is continued, the temperature is controlled at 65 ℃, the reaction is carried out for 2h, and the modified resin (FEP-ATBN) is prepared after the cooling to the room temperature.
(3) Under the low-speed stirring condition of the rotating speed of 300-500r/min, 746g of modified resin is added into 84g of dimethylbenzene to be stirred for 5min, then 170g of m-xylylenediamine is slowly added, and the stirring is continued for 10min at the rotating speed of 300r/min until the mixture is uniformly mixed, so that the second component is obtained.
(4) And uniformly mixing the first component and the second component according to the mass ratio of 5.5: 1 to obtain the petrochemical anticorrosive creep-resistant coating.
In the embodiment, macromolecular bisphenol A epoxy resin with a relatively regular structure is selected, and the characteristic of good flexibility of the epoxy resin is utilized, so that the toughness of the coating can be compensated to a certain degree. And by selecting the F-type epoxy resin, on one hand, a branched structure can be provided to connect the ATBN together, and on the other hand, the F-type epoxy resin can form a relatively dense crosslinking density to enhance the tensile strength of the whole structure. Furthermore, the modified FEP-ATBN and m-xylylenediamine can be mixed and crosslinked with each other to form a coating film having good tensile strength and elongation and good adhesion.
Embodiment 2 a method for preparing a petrochemical anticorrosive creep-resistant coating comprises the following steps:
(1) Adding 105g of dimethylbenzene and 45g of n-butyl alcohol into a stirring kettle, adding 350g of bisphenol A epoxy resin under the condition of low-speed stirring, starting high-speed dispersion for 15min until the resin is completely dissolved in a solvent, then reducing the stirring speed to 500r/min, adding 90g of F-type epoxy resin, 11g of rheological additive, 5g of dispersing agent, 2g of defoaming agent, 10g of PM and 25g of dimethylbenzene, stirring at medium speed for 5-10min, then sequentially adding 120g of titanium dioxide, 50g of talcum powder and 170g of silicon powder, dispersing at high speed for 25min, and finally adjusting the viscosity to 110-120KU by using 17g of dimethylbenzene to obtain the first component.
(2) Adding 720g of ATBN resin into a container, starting a stirrer to stir at the rotating speed of 500r/min and heat to 55 ℃, then slowly adding 63g of F-type epoxy resin under the stirring condition, continuously stirring and controlling the temperature to react for 3h at 55 ℃, and cooling to room temperature to obtain the modified resin.
(3) Under the low-speed stirring condition with the rotating speed of 300-500r/min, 783g of modified resin is added into 50g of dimethylbenzene and stirred for 5min, then 167g of m-xylylenediamine is slowly added, and the stirring is continued for 10min at the rotating speed of 500r/min until the mixture is uniformly mixed, so that the second component is obtained.
(4) And uniformly mixing the first component and the second component according to the mass ratio of 6: 1 to obtain the petrochemical anticorrosive creep-resistant coating.
Example 3 a petrochemical anticorrosive creep-resistant coating was prepared substantially the same as in example 1, except that:
the reaction equivalent ratio of the ATBN resin to the F-type epoxy resin in the step (2) is 10.0: 1.
The mass ratio of the modified resin to the m-xylylenediamine in the step (3) is 4.5: 1.
The mass ratio of the first component to the second component in the step (4) is 5.8: 1.
Comparative example 1 this comparative example provides a method of preparing a coating material for a storage tank in which the epoxy resin of type F in example 1 is replaced with a bisphenol a type epoxy resin and the other components are kept in accordance with example 1. The preparation method comprises the following steps:
(1) Adding 105g of dimethylbenzene and 45g of n-butyl alcohol into a stirring kettle, starting low-speed stirring, adding 450g of bisphenol A epoxy resin under the stirring condition, starting high-speed dispersion for 15-20min until the resin is completely dissolved in a solvent, then reducing the stirring speed to 500r/min, adding 11g of rheological additive, 5g of dispersing agent, 2g of defoaming agent, 10g of PM and 15g of dimethylbenzene, stirring at medium speed for 5-10min, then sequentially adding 120g of titanium dioxide, 50g of talcum powder and 170g of silicon micropowder, dispersing at high speed for 25-30min, and finally adjusting the viscosity to 110-120KU by using 17g of dimethylbenzene to obtain the first component.
(2) 670g of ATBN resin is added into a container, a stirrer is started to stir at the rotating speed of 300-500r/min and is heated to 55-65 ℃, then 76g of bisphenol A epoxy resin is slowly added under the stirring condition, the stirring is continuously carried out, the temperature is controlled to be 55-65 ℃, the reaction is carried out for 4 hours, and the modified ATBN resin is prepared after the cooling to the room temperature.
(3) Under the low-speed stirring condition of the rotating speed of 300-500r/min, 746g of modified ATBN resin is added into 84g of dimethylbenzene to be stirred for 5min, then 170g of m-xylylenediamine is slowly added, and the stirring is continued for 10min at the rotating speed of 300-500r/min until the mixture is uniformly mixed, so as to obtain a second component.
(4) And uniformly mixing the first component and the second component according to the mass ratio of 5.5: 1 to obtain the coating material of the storage tank.
Comparative example 2 this comparative example provides a method of preparing a coating material for storage tanks wherein the FEP-ATBN of example 1 is replaced with ATBN and the other components are in accordance with example 1. The preparation method comprises the following steps:
(1) Adding 105g of dimethylbenzene and 45g of n-butyl alcohol into a stirring kettle, starting low-speed stirring, adding 350g of bisphenol A epoxy resin under the stirring condition, starting high-speed dispersion for 15-20min until the resin is completely dissolved in a solvent, then reducing the stirring speed to 500r/min, adding 100g of F-type epoxy resin, 11g of rheological additive, 5g of dispersing agent, 2g of defoaming agent, 10g of PM and 15g of dimethylbenzene, stirring at medium speed for 5-10min, then sequentially adding 120g of titanium dioxide, 50g of talcum powder and 170g of silicon micropowder, dispersing at high speed for 25-30min, and finally adjusting the viscosity to 110-120KU by using 17g of dimethylbenzene to obtain the first component.
(2) 746g ATBN resin and 84g dimethylbenzene are added into a container and stirred for 5min, then 170g m-xylylenediamine is slowly added, and the stirring is continuously carried out for 10min at the rotating speed of 300-500r/min until the mixture is uniformly mixed, thus obtaining a second component.
(3) And uniformly mixing the first component and the second component according to the mass ratio of 5.5: 1 to obtain the coating material of the storage tank.
Comparative example 3 this comparative example provides a coating material for storage tanks prepared in substantially the same manner as in example 1, except that: the epoxy equivalent of the commercially available bisphenol A type epoxy resin used therein was about 380.
Comparative example 4 this comparative example provides a coating material for storage tanks prepared in substantially the same manner as in example 1, except that: the epoxy equivalent of the commercially available type F epoxy resin used therein was about 220.
Comparative example 5 this comparative example provides a coating material for storage tanks prepared in substantially the same manner as in example 1, except that:
the commercially available ATBN resin used therein had an amino group content of 14% and an amine equivalent of about 900.
Comparative example 6 this comparative example provides a coating material for storage tanks prepared in substantially the same manner as in example 1, except that: in the step (2), the reaction equivalent ratio of the ATBN resin to the F-type epoxy resin is 8.5: 1.
Comparative example 7 this comparative example provides a coating material for storage tanks prepared in substantially the same manner as in example 1, except that: the reaction equivalent ratio of the ATBN resin to the F-type epoxy resin in the step (2) is 12.2: 1.
Comparative example 8 this comparative example provides a coating material for storage tanks prepared in substantially the same manner as in example 1, except that: in the step (3), isophoronediamine (IPDA) with the same dosage is used for replacing m-xylylenediamine.
The performance of the petrochemical corrosion resistant and creep resistant coating of examples 1-2 and the storage tank coating material of comparative examples 1-2 were further tested according to the method specified in GB/T2039-2012 (metal material uniaxial tensile creep test method) and compared to the creep secondary growth rate of steel substrates not coated with the coating material. The corresponding test results are shown in table 1. The test results in table 1 are the average of the test results of multiple batches of products.
TABLE 1 data of the performance tests on the products obtained in examples 1-3 and comparative examples 1-8
| Numbering | Adhesive strength/MPa | Tensile Strength/MPa | Creep secondary growth rate (100N × 720 h)/% |
| Example 1 | 20.6 | 28.2 | 0.016 |
| Example 2 | 18.5 | 25.3 | 0.013 |
| Example 3 | 19.2 | 26.4 | 0.014 |
| Comparative example 1 | 12.4 | 7.3 | 0.237 |
| Comparative example 2 | 9.5 | 3.6 | 0.522 |
| Comparative example 3 | 9.2 | 22.3 | 0.143 |
| Comparative example 4 | 18.6 | 10.6 | 0.388 |
| Comparative example 5 | 20.5 | 12.4 | 0.167 |
| Comparative example 6 | 10.6 | 22.6 | 0.464 |
| Comparative example 7 | 15.5 | 8.6 | 0.296 |
| Comparative example 8 | 19.6 | 11.9 | 0.267 |
| Uncoated coated steel substrate | / | / | 0.601 |
The storage tank petrochemical anti-corrosion creep-resistant coating prepared in the above examples 1-3 has a creep elongation of 0.013-0.016 under the action of a continuous circumferential stress of 100 Nx 720 h. The creep resistance performance of the product on steel substrates is far better than that of the common epoxy storage tank protective coating material.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. The petrochemical anticorrosive creep-resistant coating is characterized by comprising a first component and a second component in a mass ratio of 5.5-6.0;
wherein the first component comprises the following components in parts by weight:
35-40 parts of bisphenol A epoxy resin
9-12 parts of F-type epoxy resin
30-35 parts of pigment and filler
1.5-3 parts of assistant
15-25 parts of a solvent;
the second component comprises the following components in parts by weight:
74-79 parts of modified resin
16-18 parts of amine epoxy resin curing agent
5-10 parts of a solvent;
wherein the epoxy equivalent of the bisphenol A type epoxy resin is 450-520, the weight-average molecular weight is 900-1100, the epoxy equivalent of the F type epoxy resin is 170-200, and the amine type epoxy resin curing agent is m-xylylenediamine;
the modified resin is mainly formed by carrying out prepolymerization addition reaction on an amine-terminated butadiene-acrylonitrile copolymer with a reaction equivalent ratio of 8.8-11.5 and an F-type epoxy resin, wherein the amine-terminated butadiene-acrylonitrile copolymer has the amino content of 15-17%, the amine equivalent of 800-850 and the weight-average molecular weight of 3000-3500;
and the molar ratio of the bisphenol A type epoxy resin to the F type epoxy resin in the first component is 0.77-0.85, and the mass ratio of the modified resin to the amine type epoxy resin curing agent in the second component is 4.4-4.7.
2. The petrochemical anticorrosive creep-resistant coating according to claim 1, characterized in that: the pigment and filler comprises any one or combination of more of titanium dioxide, black iron oxide, red iron oxide, talcum powder and silica powder.
3. The petrochemical corrosion-resistant creep-resistant coating according to claim 1, characterized in that: the auxiliary agent comprises any one or combination of more of a defoaming agent, a leveling agent and a rheological auxiliary agent.
4. The petrochemical corrosion-resistant creep-resistant coating according to claim 1, characterized in that: the solvent comprises any one or combination of xylene, PM, MIBK, acetone and n-butanol.
5. The method for preparing a petrochemical anti-corrosion creep-resistant coating according to any one of claims 1 to 4, comprising:
uniformly mixing bisphenol A type epoxy resin, F type epoxy resin, pigment and filler, an auxiliary agent and a solvent to form a mixture, and adjusting the viscosity of the mixture to 110-120KU by using the solvent to obtain a first component;
uniformly mixing the amine-terminated butadiene-acrylonitrile copolymer with F-type epoxy resin, fully reacting at 55-65 ℃ to prepare modified resin, and uniformly mixing the modified resin with an amine epoxy resin curing agent and a solvent to obtain a second component;
and uniformly mixing the first component and the second component to prepare the petrochemical anticorrosive creep-resistant coating.
6. The method for preparing the petrochemical corrosion-resistant and creep-resistant coating according to claim 5, which comprises the following steps:
uniformly mixing bisphenol A type epoxy resin, F type epoxy resin, pigment and filler, an auxiliary agent and a solvent to form a mixture, dispersing at a high speed of 2000-3000r/min for 25-30min, and adjusting the viscosity of the mixture to 110-120KU by using the solvent to obtain a first component;
heating the amine-terminated butadiene-acrylonitrile copolymer to 55-65 ℃, then slowly adding the F-type epoxy resin under the condition of continuous stirring, reacting for 2-4h at 55-65 ℃, then cooling to room temperature to prepare modified resin, then adding the modified resin into a solvent under the condition of continuous stirring, then slowly adding the amine-type epoxy resin curing agent, and continuously stirring until the mixture is uniformly mixed to obtain a second component.
7. A method for controlling circumferential stress creep of a metal substrate, comprising: the petrochemical corrosion-resistant creep-resistant coating according to any one of claims 1 to 4 is continuously coated on the surface of a metal substrate along the circumferential direction to form a protective coating resisting circumferential stress creep.
8. A circumferential stress resistant protective structure for a metal substrate, comprising a coating layer formed of the petrochemical corrosion-resistant and creep-resistant coating material according to any one of claims 1 to 4, wherein the coating layer continuously covers the surface of the metal substrate in a circumferential direction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265469B1 (en) * | 1999-09-02 | 2001-07-24 | Du Pont Wirex Ltd | Epoxy resin adhesive for flexible printed circuits |
| WO2014073789A1 (en) * | 2012-11-09 | 2014-05-15 | 주식회사 두산 | Resin composition, and laminate for printed circuit board comprising same |
| CN104004483A (en) * | 2014-06-09 | 2014-08-27 | 北京天山新材料技术股份有限公司 | Impact-resistant, high-flexibility and high-temperature-resistant epoxy adhesive and preparation process thereof |
| CN113337234A (en) * | 2021-05-14 | 2021-09-03 | 武汉理工大学 | Epoxy resin-based vitrimer adhesive cured at normal temperature and preparation method thereof |
| EP3931238A1 (en) * | 2019-02-25 | 2022-01-05 | SHPP Global Technologies B.V. | Cross-linkable network from functionalized polyetherimide and thermoset polymer resulting therefrom |
-
2022
- 2022-05-20 CN CN202210559729.7A patent/CN114702882B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265469B1 (en) * | 1999-09-02 | 2001-07-24 | Du Pont Wirex Ltd | Epoxy resin adhesive for flexible printed circuits |
| WO2014073789A1 (en) * | 2012-11-09 | 2014-05-15 | 주식회사 두산 | Resin composition, and laminate for printed circuit board comprising same |
| CN104004483A (en) * | 2014-06-09 | 2014-08-27 | 北京天山新材料技术股份有限公司 | Impact-resistant, high-flexibility and high-temperature-resistant epoxy adhesive and preparation process thereof |
| EP3931238A1 (en) * | 2019-02-25 | 2022-01-05 | SHPP Global Technologies B.V. | Cross-linkable network from functionalized polyetherimide and thermoset polymer resulting therefrom |
| CN113337234A (en) * | 2021-05-14 | 2021-09-03 | 武汉理工大学 | Epoxy resin-based vitrimer adhesive cured at normal temperature and preparation method thereof |
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| CN114702882A (en) | 2022-07-05 |
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