CN114672242B - Super-hydrophobic super-oleophilic coating for inhibiting hydrate nucleation and adhesion as well as preparation method and application thereof - Google Patents
Super-hydrophobic super-oleophilic coating for inhibiting hydrate nucleation and adhesion as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion, and a preparation method and application thereof. The coating is prepared by adding a prepolymer of silicon hydroxyl-containing polyurethane into a prepolymer preheated to 58-62 ℃ and containing multiple inhibition functional groups under the protection of inert gas, stirring the mixture at 78-82 ℃ for reaction for 2-3 hours, dissolving the product in an ester solvent, mixing the product with a curing agent and hydrophobic nanoparticles, and performing ultrasonic treatment; the prepolymer is prepared by dissolving POSS containing hydroxyl into an ester solvent, heating to 58-62 ℃, adding a monomer containing isocyanate group dissolved in the ester solvent under a protective atmosphere, and stirring and reacting for 2-3 h at 58-62 ℃; the coating is coated on the pipe inner wall material of the pretreated oil and gas conveying pipeline, has the functions of inhibiting the nucleation of hydrate and preventing the adhesion of a complex, has the functions of scouring resistance, super hydrophobicity and super oleophylic property, and is particularly suitable for the application of the oil and gas conveying pipeline.
Description
Technical Field
The invention belongs to the technical field of petroleum and natural gas, and particularly relates to a super-hydrophobic-super-oleophylic coating for inhibiting hydrate nucleation and adhesion, and a preparation method and application thereof.
Background
Natural gas hydrate is the cleanest burning fossil fuel in natural gas resources and plays an important role in meeting global energy demand. However, during the exploitation and transportation of the natural gas hydrate, pipelines may be blocked, and huge economic losses and environmental problems are caused.
The primary method of preventing hydrate formation and plugging is by the addition of chemical inhibitors, i.e., hydrate inhibitor methods, including thermodynamic inhibitor methods, kinetic inhibitor methods, and anti-agglomerant methods. The defects of the thermodynamic inhibitor method are that the dosage of the thermodynamic inhibitor is large, the storage and injection equipment is huge, the recovery is difficult, the environmental pollution is caused, and the cost is high; the kinetic inhibitor method has less addition amount than a thermodynamic inhibitor, can reduce the requirements of storage and injection equipment, can also reduce the pollution of the inhibitor and reduce the cost, but has obvious defects of general inhibition effect, low applicability, low required supercooling degree, easy influence of external environment and the like; the anti-agglomerant in the anti-agglomerant method can play a role when the content of the anti-agglomerant in an oil-water system is 0.5 to 2 percent (w), and the anti-agglomerant is generally suitable for an oil-water mixed system, but the use of the anti-agglomerant is limited because the price is high.
Chinese patent application CN 105333265A discloses a method for preventing hydrate from blocking a pipeline in an oil and gas transmission pipeline. The preparation method comprises the steps of taking the inner wall surface of an oil and gas conveying pipeline as a substrate, manufacturing a minimally invasive structure by utilizing a surface micromachining technology, coating a hydrophobic compound coating on the surface, and drying to obtain a dry and clean hydrophobic compound surface. The structure can improve the contact characteristic of the inner wall surface of the oil and gas pipeline and hydrate particles, and reduce the adhesion force between the inner wall surface of the pipeline and the hydrate particles, thereby avoiding pipeline blockage caused by the accumulation of the hydrate on the wall surface. However, the coating only reduces the contact area of the hydrate particles with the wall surface, and cannot inhibit the formation of the hydrate, and the hydrate still forms far away from the wall surface to cause blockage.
Chinese patent application CN 109719013A discloses a waterproof composite coating and a preparation method thereof. Adding polytetrafluoroethylene, polyphenylene sulfide and hydrophobic fumed silica into a dispersing agent for ultrasonic dispersion, then stirring by using a magnetic stirrer, and simultaneously dropwise adding a leveling thickening agent to obtain a super-hydrophobic-super-oleophylic coating with the functions of inhibiting hydrate nucleation and preventing adhesion of a water compound, then immersing a pretreated substrate into the coating, taking out the substrate for drying, and sintering at a high temperature to obtain a water compound-preventing coating. The coating prevents aggregation and adhesion of hydrate particles in pipes and equipment by retarding hydrate nucleation and growth and reducing adhesion between the hydrate particles and the inner walls of the pipes and equipment. But the sintering of the coating needs high temperature of more than 360 ℃, the manufacturing cost is high, and the energy consumption is large; the coating only depends on the low surface energy of the polytetrafluoroethylene to delay the nucleation and growth of the hydrate, and the effect of inhibiting the hydrate is relatively common.
Disclosure of Invention
The invention aims to provide a super-hydrophobic and super-oleophilic coating for inhibiting hydrate nucleation and adhesion and a preparation method thereof.
The invention also aims to provide the application of the super-hydrophobic and super-oleophilic coating for inhibiting hydrate nucleation and adhesion in preparing oil and gas conveying pipelines.
The purpose of the invention is realized by the following technical scheme:
the super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion is prepared by adding a silicon hydroxyl-containing polyurethane prepolymer into a prepolymer preheated to 58-62 ℃ and having multiple inhibiting functional groups at 78-82 ℃ under the protection of inert gas, stirring and reacting for 2-3 h to obtain a product, dissolving the product in an ester solvent, mixing the product with a curing agent and hydrophobic nano-particles, and performing ultrasonic treatment;
the prepolymer is prepared by dissolving hydroxyl-containing POSS in an ester solvent, heating to 58-62 ℃, adding an isocyanate-containing monomer dissolved in the ester solvent under a protective atmosphere, and stirring and reacting at 58-62 ℃ for 2-3 hours;
the multi-inhibition functional group prepolymer is obtained by dissolving an inhibition functional group-containing monomer in an ester solvent, adding the inhibition functional group-containing monomer into a mixture of a hydroxyl-terminated polymer, the ester solvent and an initiator, and stirring at 78-82 ℃ for reaction; the monomer containing inhibiting functional group is one or more of hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethyl 3-hydroxybutyrate, hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, vinyl caprolactam and vinyl pyrrolidine.
To further achieve the object of the present invention, preferably, the hydroxyl-terminated polymer is one or more of hydroxyl-terminated polyether, hydroxyl-terminated polyester, hydroxyl-terminated polyethylene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated polyacrylic acid.
Preferably, the hydroxyl-containing POSS is one or more of trisilanol isobutyl-cage polysilsesquioxane, trisilanol isooctyl-cage polysilsesquioxane, trisilanol phenyl-cage polysilsesquioxane; the monomer containing isocyanate group is one or more of toluene diisocyanate, lysine diisocyanate and hexamethylene diisocyanate.
Preferably, the hydrophobic nano-particles are one or more of hydrophobic nano-titanium dioxide, hydrophobic nano-silica and hydrophobic nano-calcium carbonate;
preferably, the inert gas is one or more of nitrogen, helium and argon; the initiator is one or more of azodiisobutyronitrile, cumene hydroperoxide and benzoyl peroxide; the curing agent is one or more of EDL-CR320, N95 and DEAPA.
Preferably, the raw materials are used in parts by weight: 1-10 parts of hydroxyl-terminated polymer, 0.01-0.1 part of initiator, 2-10 parts of monomer containing inhibiting functional group, 1-10 parts of POSS containing hydroxyl, 0.01-0.1 part of curing agent and 0.01-0.1 part of hydrophobic nano-particles.
Preferably, the ester solvents are one or more of methyl acetate, ethyl propionate, propyl acetate and ethyl acetate;
2-10 parts of ester solvent in the mixture; the monomer containing the inhibiting functional group is dissolved in 2 to 12 parts of ester solvent; the POSS containing the hydroxyl is dissolved in 2-12 parts of ester solvent; the monomer containing isocyanate group is dissolved in 2 to 12 parts of ester solvent; the product of stirring reaction at 78-82 ℃ for 2-3 h is dissolved in 2-12 parts of ester solvent.
The preparation method of the super-hydrophobic and super-oleophilic coating for inhibiting hydrate nucleation and adhesion comprises the following steps:
1) Heating a hydroxyl-terminated polymer, an ester solvent and an initiator in an oil bath to 78-82 ℃, purging with inert gas and evacuating for 2-3 times, adding a monomer containing an inhibiting functional group dissolved in the ester solvent, and stirring the reaction mixture at 78-82 ℃ for 2-3 hours to obtain a multi-inhibiting functional group prepolymer;
2) Dissolving POSS containing hydroxyl in an ester solvent, heating the mixture to 58-62 ℃ in an oil bath, purging the mixture with inert gas and evacuating the mixture for 2-3 times, dripping a monomer containing isocyanate group dissolved in the ester solvent, and stirring the reaction mixture for 2-3 hours at 58-62 ℃ to obtain a prepolymer containing the silicon hydroxyl polyurethane;
3) Heating the product obtained in the step 1) to 58-62 ℃ in an oil bath, purging with inert gas and evacuating for 2-3 times, adding the product obtained in the step 2), and stirring the reaction mixture at 78-82 ℃ for 2-3 h;
4) Dissolving the product obtained in the step 3) in an ester solvent, adding a curing agent and hydrophobic nano-particles, and carrying out ultrasonic treatment for 0.5-1 h to obtain the super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion.
The application of the super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion in preparing oil and gas conveying pipelines comprises the following steps: coating the super-hydrophobic super-oleophylic coating for inhibiting the nucleation and adhesion of the hydrate on the pipe inner wall material of the pretreated oil and gas transmission pipeline, wherein the pipe inner wall material is one or more of foamed nickel, foamed iron and permeable steel.
Preferably, the pretreatment is to wash the tube wall material in acetone, ethanol hydrochloride solution and deionized water subjected to ultrasonic treatment for 10 to 20 minutes respectively to remove surface pollutants and oxides; the concentration of hydrochloric acid in the hydrochloric acid ethanol solution is 0.1-0.2M; the coating mode is spray coating, spin coating or dip coating.
Compared with the prior art, the invention has the advantages that:
1. according to the coating, the hydrophobic nano-particles and the POSS containing hydroxyl are introduced, so that the surface roughness of the coating is increased, the hydrophobicity and lipophilicity are further enhanced, the oil phase is promoted to form a barrier film on the surface of the coating, the hydrate particles are isolated from the surface of the coating, and the adhesion between the coating and the hydrate is greatly reduced;
2. the coating of the invention maintains the super-hydrophobic performance, and simultaneously, the surface contains a large number of inhibiting functional groups, thus enhancing the disturbance effect of the coating on water molecules, forming a large number of hydrogen bonds with the water molecules, destroying the ordered arrangement of the water molecules and having good inhibiting effect on the nucleation and growth of hydrates;
3. the coating of the invention uses a three-dimensional porous material as a substrate, the high specific surface area of the coating can obviously improve the concentration of the inhibiting functional groups in the coating, and the porous framework can form a vortex to reduce the flow rate of the fluid and show excellent scouring resistance.
4. The coating synthesized by applying the super-hydrophobic super-oleophilic coating has super-hydrophobic and super-oleophilic properties, reduces the contact area between water drops and the surface of the coating, prolongs the nucleation induction time of hydrates, effectively reduces the adhesion between the coating and the hydrates, has excellent scouring resistance, and can be used as an inner pipe wall material for inhibiting the nucleation of the hydrates and preventing the adhesion and aggregation of hydrate particles to block a pipeline.
Drawings
FIG. 1 is a graph of the measurement of the contact angle of the coating layer with water in example 1.
FIG. 2 is a graph of the measurement of the wetting behavior of the oil droplets on the surface of the coating in example 1.
FIG. 3 is a graph of the erosion time of the coating as a function of the change in contact angle in example 1.
FIG. 4 is a graph of the wetting behavior of water droplets on the surface of the coating and stainless steel as a function of the scouring time in example 1.
Detailed Description
For better understanding of the present invention, the present invention will be further described with reference to the following drawings and examples, but the present invention is not limited thereto.
Example 1
4g of hydroxyl-terminated polybutadiene, 6g of propyl acetate and 0.03g of the initiator cumene hydroperoxide are charged to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 80 ℃, the flask was purged with nitrogen and evacuated 3 times. Then 4g of hydroxyethyl methacrylate dissolved in 6g of ethyl acetate were added dropwise using a 100ml constant pressure separatory funnel and the reaction mixture was stirred at 80 ℃ for 3 hours to obtain a multi-inhibiting functional group prepolymer;
4g of trisilanolphenyl-cage polysilsesquioxane was dissolved in 6g of ethyl acetate and charged to a 250ml three necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 60 ℃, the flask was purged with nitrogen and evacuated 3 times. Then 6g of isophorone diisocyanate dissolved in 6g of ethyl acetate solvent was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 60 ℃ for 3 hours to obtain a prepolymer of silicone hydroxyl-containing polyurethane;
the multi-inhibiting functional prepolymer was added to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 60 ℃, the flask was purged with nitrogen and evacuated 3 times. Dropwise adding the silicon-hydroxyl-containing polyurethane prepolymer into a 100ml constant-pressure separating funnel, and stirring the reaction mixture at 80 ℃ for 3 hours to obtain a silicon-hydroxyl-containing multi-inhibition functional polyurethane prepolymer;
dissolving the obtained prepolymer containing the hydroxyl-containing poly-inhibition functional polyurethane into 6g of ethyl acetate, adding 0.05g of curing agent (N95) and 0.05g of hydrophobic silicon dioxide, and carrying out ultrasonic treatment for 1 hour to obtain the super-hydrophobic-super-oleophylic coating with the effects of inhibiting hydrate nucleation and preventing adhesion of a hydrate;
foamed nickel of size 1cm x 2cm x 0.3cm was washed in acetone, 0.1M ethanol hydrochloride and sonicated deionized water for 10 minutes to remove surface contaminants and oxides, and the cleaned foamed nickel was dip-coated in a covered 4ml plastic centrifuge tube containing the above coating, and the substrate was placed in an oven and dried at 100 ℃ for 12 hours to obtain a wash-resistant superhydrophobic-superoleophilic coating with inhibited hydrate nucleation and anti-binder adhesion.
The wetting properties of the coating were tested using a contact angle analyzer (shanghai zhongchen Powereach JP (HHIP) 000D 1A) with a water or oil drop volume of 5 mul, and 10 seconds after deposition of the drop, the contact angle of the 5 mul drop was measured, with the water contact angle of each sample being the average of five different positions at 152 °, as shown in fig. 1; oil droplets (5 μ L of dichloroethane) quickly wetted the surface of the coating within 0.05s, as shown in figure 2.
The nucleation induction times of aqueous THF solutions in the presence of coatings and stainless steel sheets were compared with reference to the hydrate nucleation test method and apparatus in the Investigation of the nucleation time for THF hydrate formation in porous media (Weiguo Liu et al, journal of Natural Gas Science and Engineering, 24-357-364). The result shows that the nucleation induction time of the THF aqueous solution put into the coating is 128min, and the nucleation induction time of the stainless steel sheet put into the coating is 63min, which indicates that the coating has the performance of delaying the nucleation of the hydrate.
The Adhesion between cyclopentane hydrate particles and the coating and stainless steel sheet was measured with reference to the Adhesion test method and apparatus of Reduction Clathrate Hydrates Growth Rates and Adhesion force formulations on Surfaces of Inorganic or Polymer Coatings (Shuanshi Fan et al, energy Fuels 2020,34, 13566-13579), and it was found that under the experimental conditions the Adhesion between cyclopentane hydrate and coating was 0.001mN/m and the Adhesion between stainless steel sheet and hydrate was 0.450mN/m, indicating that the coating can significantly reduce the Adhesion between the hydrate particles and the substrate.
The coating is put into a stirring system with the rotating speed of 1500r/min, 1L of water and 100g of fine sand are added, the pipeline transmission process is simulated, the sand washes the surface of the coating at a high speed, and the change of the wettability of the coating surface along with the washing time is shown in attached figures 3 and 4. Wherein, FIG. 3 is a relation graph of the change of the contact angle of the coating surface and water along with the change of the scouring time, the coating still has super-hydrophobicity after being scoured for 4h, and the contact angle is 151 degrees; FIG. 4 is a graph showing that the water drops roll on the surface of the coating and the stainless steel sheet at the same inclination angle and change along with the washing time, the water drops can quickly roll off from the surface of the coating within 4h of the washing time, and the water drops on the surface of the stainless steel cannot roll off after 0.5h of washing, which shows that the coating has good impact resistance and washing resistance.
Example 2
6g of hydroxy-terminated polyether, 10g of ethyl propionate and 0.05g of the initiator 2,2' -Azobisisobutyronitrile (AIBN) were charged to a 250ml three-necked round-bottomed flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 81 ℃, the flask was purged with nitrogen and evacuated 2 times. Then 5g of vinylpyrrolidine dissolved in 8g of ethyl acetate was added dropwise using a 100ml constant pressure separatory funnel and the reaction mixture was stirred at 81 ℃ for 3h to give a multi-inhibiting functional group prepolymer;
6g of trisilanolisobutyl-cage polysilsesquioxane was dissolved in 8g of ethyl acetate and charged to a 250ml three necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 62 ℃, the flask was purged with nitrogen and evacuated 2 times. Then 8g of isophorone diisocyanate dissolved in 8g of ethyl acetate solvent was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 62 ℃ for 2 hours to obtain a prepolymer of silicone hydroxyl group-containing polyurethane;
the multi-inhibiting functional prepolymer was added to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 62 ℃, the flask was purged with nitrogen and evacuated 2 times. Dropwise adding the silicon-hydroxyl-containing polyurethane prepolymer into a 100ml constant-pressure separating funnel, and stirring the reaction mixture at 82 ℃ for 2 hours to obtain a silicon-hydroxyl-containing multi-inhibition functional polyurethane prepolymer;
dissolving the obtained silicon hydroxyl group-containing poly-inhibition functional polyurethane prepolymer in 8g of ethyl propionate, adding 0.06g of curing agent DEAPA and 0.06g of hydrophobic calcium carbonate, and carrying out ultrasonic treatment for 0.5h to obtain the super-hydrophobic-super-oleophylic coating with the effects of inhibiting hydrate nucleation and preventing adhesion of a hydrate;
foam iron of size 1cm x 2cm x 0.3cm was washed in acetone, 0.2M ethanol hcl and sonicated deionized water for 15 minutes to remove surface contaminants and oxides, then clean foam nickel was dip coated in a covered 4ml plastic centrifuge tube containing the above described coating, then the substrate was placed in an oven and dried at 120 ℃ for 10 hours to obtain a scour resistant superhydrophobic-superoleophilic coating with inhibited hydrate nucleation and inhibited adhesion of water.
Example 3
A250 ml three neck round bottom flask equipped with a magnetic stirrer, temperature and condenser was charged with 8g of hydroxyl terminated fluoropolyester polysiloxane, 11g of methyl acetate and 0.08g of initiator cumene hydroperoxide. The flask was placed in a silicon oil bath and after the oil bath temperature reached 78 ℃, the flask was purged with nitrogen and evacuated 3 times. Then, 6g of 2-hydroxyethyl acrylate dissolved in 8g of ethyl acetate was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 78 ℃ for 3 hours to obtain a multi-inhibiting functional group prepolymer;
8g of trisilol isooctyl-cage polysilsesquioxane was dissolved in 8g of ethyl acetate and charged to a 250ml three neck round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 58 ℃, the flask was purged with nitrogen and evacuated 2 times. Then 6g of isophorone diisocyanate dissolved in 6g of ethyl acetate solvent was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 58 ℃ for 3 hours to obtain a silicone-hydroxyl-containing polyurethane prepolymer;
the multi-inhibiting functional prepolymer was added to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 58 ℃, the flask was purged with nitrogen and evacuated 3 times. Dropwise adding the silicon-hydroxyl-containing polyurethane prepolymer into a 100ml constant-pressure separating funnel, and stirring the reaction mixture at 78 ℃ for 3 hours to obtain a silicon-hydroxyl-containing multi-inhibition functional polyurethane prepolymer;
dissolving the obtained prepolymer containing the hydroxyl-containing poly-inhibition functional polyurethane in 5g of ethyl acetate, adding 0.04g of curing agent EDL-CR320 and 0.08g of hydrophobic silicon dioxide, and carrying out ultrasonic treatment for 1 hour to obtain the super-hydrophobic-super-oleophilic coating with the effects of inhibiting hydrate nucleation and preventing adhesion of hydrates;
air-permeable steel with the size of 1cm x 2cm x 0.3cm is washed in acetone, 0.1M ethanol hydrochloride and deionized water treated by ultrasound for 20 minutes respectively to remove surface pollutants and oxides, clean foamed nickel is put into a 4ml plastic centrifuge tube with a cover and filled with the coating for dip coating, and then the substrate is put into an oven and dried for 15 hours at 110 ℃ to obtain the scour-resistant super-hydrophobic-super-oleophilic coating with the functions of inhibiting hydrate nucleation and preventing adhesion of the hydrates.
Example 4
5g of hydroxyl-terminated polybutadiene, 7g of ethyl propionate and 0.08g of the initiator benzoyl peroxide were charged to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 80 ℃, the flask was purged with nitrogen and evacuated 3 times. Then 4g of ethyl 3-hydroxybutyrate dissolved in 4g of ethyl propionate was added dropwise using a 100ml constant pressure separatory funnel and the reaction mixture was stirred at 80 ℃ for 3h to give a multi-inhibiting functional group prepolymer;
7g of trisilanol isooctyl-cage polysilsesquioxane was dissolved in 5g of ethyl acetate and charged to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 60 ℃, the flask was purged with nitrogen and evacuated 3 times. Then, 7g of isophorone diisocyanate dissolved in 5g of ethyl acetate solvent was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 60 ℃ for 3 hours to obtain a prepolymer of silicone hydroxyl group-containing polyurethane;
the multi-inhibiting functional prepolymer was added to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 60 ℃, the flask was purged with nitrogen and evacuated 3 times. Dropwise adding the silicon-hydroxyl-containing polyurethane prepolymer into a 100ml constant-pressure separating funnel, and stirring the reaction mixture at 80 ℃ for 3 hours to obtain a silicon-hydroxyl-containing multi-inhibition functional polyurethane prepolymer;
dissolving the obtained hydroxyl-containing poly-inhibition-functional polyurethane prepolymer in 8g of ethyl acetate, adding 0.04g of curing agent (N95) and 0.04g of hydrophobic silica, and carrying out ultrasonic treatment for 1.5 hours to obtain the super-hydrophobic-super-oleophylic coating with the effects of inhibiting hydrate nucleation and preventing adhesion of water complexes;
foamed nickel of size 1cm x 2cm x 0.3cm was washed in acetone, 0.1M ethanol hcl and sonicated deionized water for 10 minutes to remove surface contaminants and oxides, then the cleaned foamed nickel was dip coated in a covered 4ml plastic centrifuge tube containing the above described coating, then the substrate was placed in an oven and dried at 90 ℃ for 10 hours to obtain a scour resistant superhydrophobic-superoleophilic coating with inhibited hydrate nucleation and inhibited adhesion of water.
Example 5
5g of hydroxyl-terminated polyacrylic acid, 8g of ethyl propionate and 0.05g of the initiator 2,2' -Azobisisobutyronitrile (AIBN) were charged into a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 81 ℃, the flask was purged with argon and evacuated 2 times. Then 5g of vinylcaprolactam dissolved in 8g of ethyl acetate were added dropwise using a 100ml constant pressure separatory funnel and the reaction mixture was stirred at 81 ℃ for 3 hours to give a multi-inhibiting functional group prepolymer;
5g of trisilanolphenyl-cage polysilsesquioxane was dissolved in 8g of ethyl acetate and charged to a 250ml three necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 60 ℃, the flask was purged with nitrogen and evacuated 2 times. Then 8g of isophorone diisocyanate dissolved in 8g of ethyl acetate solvent was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 60 ℃ for 2 hours to obtain a prepolymer of silicon hydroxyl polyurethane;
the multi-inhibiting functional prepolymer was added to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 60 ℃, the flask was purged with nitrogen and evacuated 2 times. Dropwise adding the silicon-hydroxyl-containing polyurethane prepolymer into a 100ml constant-pressure separating funnel, and stirring the reaction mixture at 82 ℃ for 2 hours to obtain a silicon-hydroxyl-containing multi-inhibition functional polyurethane prepolymer;
dissolving the obtained prepolymer containing the hydroxyl-containing poly-inhibition functional polyurethane into 8g of ethyl acetate, adding 0.06g of curing agent EDL-CR320 and 0.06g of hydrophobic titanium dioxide, and carrying out ultrasonic treatment for 1 hour to obtain the super-hydrophobic-super-oleophilic coating with the effects of inhibiting hydrate nucleation and preventing adhesion of a hydrate;
foamed nickel of size 1cm x 2cm x 0.3cm was washed in acetone, 0.2M ethanol hydrochloride and sonicated deionized water for 20 minutes to remove surface contaminants and oxides, and the cleaned foamed nickel was dip-coated in a covered 4ml plastic centrifuge tube containing the above coating, and the substrate was placed in an oven and dried at 100 ℃ for 15 hours to obtain a wash-resistant superhydrophobic-superoleophilic coating with inhibited hydrate nucleation and resistance to adhesion of the hydrates.
Example 6
3g of hydroxy-terminated polydimethylsiloxane, 5g of ethyl propionate and 0.04g of the initiator cumene hydroperoxide are charged to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 78 ℃, the flask was purged with argon and evacuated 3 times. Then, 4g of 2-hydroxyethyl acrylate dissolved in 5g of ethyl acetate was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 78 ℃ for 3 hours to obtain a multi-inhibitory functional group prepolymer;
3g of trisilanolisobutyl-cage polysilsesquioxane was dissolved in 5g of ethyl propionate and charged to a 250ml three necked round bottom flask equipped with magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 58 ℃, the flask was purged with helium and evacuated 3 times. Then 5g of hexamethylene diisocyanate dissolved in 5g of ethyl propionate solvent was added dropwise using a 100ml constant pressure separatory funnel, and the reaction mixture was stirred at 58 ℃ for 3 hours to obtain a silicone hydroxyl group-containing polyurethane prepolymer;
the multi-inhibiting functional prepolymer was added to a 250ml three-necked round bottom flask equipped with a magnetic stirrer, temperature and condenser. The flask was placed in a silicon oil bath and after the oil bath temperature reached 58 ℃, the flask was purged with nitrogen and evacuated 3 times. Dropwise adding the silicon hydroxyl-containing polyurethane prepolymer into a 100ml constant-pressure separating funnel, and stirring the reaction mixture at 78 ℃ for 3 hours to obtain a silicon hydroxyl-containing multi-inhibition functional polyurethane prepolymer;
dissolving the obtained prepolymer containing the hydroxyl-containing poly-inhibition functional polyurethane into 5g of ethyl acetate, adding 0.04g of curing agent (N95) and 0.04g of hydrophobic silicon dioxide, and carrying out ultrasonic treatment for 1 hour to obtain the super-hydrophobic-super-oleophylic coating with the effects of inhibiting hydrate nucleation and preventing adhesion of a hydrate;
air-permeable steel with the size of 1cm x 2cm x 0.3cm is washed in acetone, 0.1M ethanol hydrochloride and deionized water treated by ultrasound for 10 minutes respectively to remove surface pollutants and oxides, clean foamed nickel is put into a 4ml plastic centrifuge tube with a cover and filled with the coating for dip coating, and then the substrate is put into an oven and dried for 15 hours at 110 ℃ to obtain the scour-resistant super-hydrophobic-super-oleophilic coating with the functions of inhibiting hydrate nucleation and preventing adhesion of the hydrates.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion is characterized in that a product which is obtained by adding a silicon hydroxyl-containing polyurethane prepolymer into a prepolymer preheated to 58-62 ℃ and having multiple inhibiting functional groups and reacting for 2-3 hours at 78-82 ℃ under the protection of inert gas, stirring and dissolving the product in an ester solvent, mixing the ester solvent with a curing agent and hydrophobic nano-particles, and performing ultrasonic treatment to obtain the super-hydrophobic super-oleophylic coating;
the prepolymer is prepared by dissolving hydroxyl-containing POSS in an ester solvent, heating to 58-62 ℃, adding an isocyanate-containing monomer dissolved in the ester solvent under a protective atmosphere, and stirring and reacting at 58-62 ℃ for 2-3 hours;
the multi-inhibition functional group prepolymer is prepared by adding an inhibition functional group-containing monomer in a dissolved ester solvent into a mixture of a hydroxyl-terminated polymer, an ester solvent and an initiator, and stirring at 78-82 ℃ for reaction; the monomer containing inhibiting functional group is one or more of hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethyl 3-hydroxybutyrate, hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, vinyl caprolactam and vinyl pyrrolidine.
2. The superhydrophobic, superoleophilic coating for inhibiting hydrate nucleation and adhesion as claimed in claim 1, wherein the hydroxyl terminated polymer is one or more of hydroxyl terminated polyether, hydroxyl terminated polyester, hydroxyl terminated polyethylene, hydroxyl terminated polybutadiene, hydroxyl terminated polydimethylsiloxane, and hydroxyl terminated polyacrylic acid.
3. The superhydrophobic, superoleophilic coating that inhibits hydrate nucleation and adhesion as recited in claim 1, wherein the hydroxyl-containing POSS is one or more of trisilanol isobutyl-cage polysilsesquioxane, trisilanol isooctyl-cage polysilsesquioxane, trisilanol phenyl-cage polysilsesquioxane; the monomer containing isocyanate group is one or more of toluene diisocyanate, lysine diisocyanate and hexamethylene diisocyanate.
4. The superhydrophobic and superoleophilic coating for inhibiting hydrate nucleation and adhesion according to claim 1, wherein the hydrophobic nano-particles are one or more of hydrophobic nano-titanium dioxide, hydrophobic nano-silica, and hydrophobic nano-calcium carbonate.
5. The super hydrophobic super oleophilic coating to inhibit hydrate nucleation and adhesion as claimed in claim 1 wherein the inert gas is one or more of nitrogen, helium and argon; the initiator is one or more of azodiisobutyronitrile, cumene hydroperoxide and benzoyl peroxide; the curing agent is one or more of EDL-CR320, N95 and DEAPA.
6. The super-hydrophobic and super-oleophilic coating for inhibiting hydrate nucleation and adhesion as claimed in claim 1, wherein the raw materials comprise, in parts by mass: 1-10 parts of hydroxyl-terminated polymer, 0.01-0.1 part of initiator, 2-10 parts of monomer containing inhibiting functional group, 1-10 parts of POSS containing hydroxyl, 0.01-0.1 part of curing agent and 0.01-0.1 part of hydrophobic nano-particles.
7. The super-hydrophobic super-oleophilic coating for inhibiting hydrate nucleation and adhesion as claimed in claim 1, wherein the ester solvents are all one or more of methyl acetate, ethyl propionate, propyl acetate, ethyl acetate;
2-10 parts of ester solvent in the mixture; the monomer containing the inhibiting functional group is dissolved in 2 to 12 parts of ester solvent; the POSS containing the hydroxyl is dissolved in 2 to 12 parts of ester solvent; the monomer containing isocyanate group is dissolved in 2 to 12 parts of ester solvent; the product of stirring reaction at 78-82 ℃ for 2-3 h is dissolved in 2-12 parts of ester solvent.
8. A method of preparing a superhydrophobic, superoleophilic coating that inhibits hydrate nucleation and adhesion as claimed in any one of claims 1-7, comprising the steps of:
1) Heating a hydroxyl-terminated polymer, an ester solvent and an initiator in an oil bath to 78-82 ℃, purging with inert gas, evacuating for 2-3 times, adding a monomer containing an inhibiting functional group dissolved in the ester solvent, and stirring the reaction mixture at 78-82 ℃ for 2-3 hours to obtain a multi-inhibiting functional group prepolymer;
2) Dissolving POSS containing hydroxyl in an ester solvent, heating the mixture to 58-62 ℃ in an oil bath, purging the mixture with inert gas and evacuating the mixture for 2-3 times, dripping a monomer containing isocyanate group dissolved in the ester solvent, and stirring the reaction mixture for 2-3 hours at 58-62 ℃ to obtain a prepolymer containing the silicon hydroxyl polyurethane;
3) Heating the product obtained in the step 1) to 58-62 ℃ in an oil bath, purging with inert gas and evacuating for 2-3 times, adding the product obtained in the step 2), and stirring the reaction mixture for 2-3 h at 78-82 ℃;
4) Dissolving the product obtained in the step 3) in an ester solvent, adding a curing agent and hydrophobic nano-particles, and carrying out ultrasonic treatment for 0.5-1 h to obtain the super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion.
9. Use of the superhydrophobic, superoleophilic coating inhibiting hydrate nucleation and adhesion as claimed in any one of claims 1-7 in the preparation of an oil and gas transport pipe: the method is characterized in that a super-hydrophobic super-oleophylic coating for inhibiting hydrate nucleation and adhesion is coated on a pipe inner wall material of a pretreated oil and gas transmission pipeline, wherein the pipe inner wall material is one or more of foamed nickel, foamed iron and permeable steel.
10. Use of the superhydrophobic, superoleophilic coating that inhibits hydrate nucleation and adhesion according to claim 9 in the preparation of an oil and gas transport conduit: the method is characterized in that the pretreatment is to wash the wall material in the tube in acetone, ethanol solution of hydrochloric acid and deionized water subjected to ultrasonic treatment for 10 to 20 minutes respectively to remove surface pollutants and oxides; the concentration of hydrochloric acid in the hydrochloric acid ethanol solution is 0.1-0.2M; the coating mode is spray coating, spin coating or dip coating.
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