Anti-adhesion light-weight underwater oil bag material and preparation method thereof

Abstract

The application provides a kind of anti-adhesion light underwater oil bag material and preparation method thereof, belong to underwater oil and gas storage technical field, the anti-adhesion light underwater oil bag material provided by the application is sequentially from outside to inside anti-adhesion layer, ultra-light support layer and oil-resistant layer;Wherein, anti-adhesion layer and ultra-light support layer are laminated into composite;Oil-resistant layer is combined with ultra-light support layer in the form of spraying.At the same time, the application also provides the preparation method of anti-adhesion layer, ultra-light support layer and oil-resistant layer, the application is mainly prepared by fluorine-containing polyurethane PFU-X.The -CF3 in it can be assembled at interface, reduce surface energy, prevent the adhesion of material surface biology, and have better repellency to biological liquid.Other structures strengthen other properties of composite material.The material provided by the application is excellent in comprehensive performance.

Description

Technical Field

[0001] This invention belongs to the field of underwater oil and gas storage technology, and particularly relates to an anti-adhesion lightweight underwater oil bladder and its preparation method. Background Technology

[0002] Subsea oil bladders are lightweight, portable, and easily movable flexible storage devices for storing hydraulic oil. Compared to surface oil storage, subsea oil bladders have a smaller internal and external pressure difference, eliminating the need to consider overall pressure resistance; they are less affected by external wind, waves, currents, and ice; they do not increase the environmental load on the oil production platform and do not require expensive transfer mooring systems. These advantages significantly reduce the technical costs of platform construction and oil storage devices. The development and improvement of subsea oil bladder systems will contribute to the high-level development of my country's future seabed mineral resource development technology, enabling efficient, stable, and safe mining of seabed ores, which is of great significance to my country's deep-sea mineral resource development.

[0003] However, existing underwater facilities are not as sophisticated as surface facilities, and marine biofouling is a significant factor affecting the safety and lifespan of these facilities. Marine biofouling primarily consists of microscopic marine organisms such as bacteria and diatoms, as well as protein biomolecules. Underwater oil bladders are susceptible to the attachment and growth of marine biofouling organisms. This attachment increases the weight of the oil bladder, increasing its drag and hindering its maneuverability. Furthermore, the cumulative buildup of marine biofouling organisms increases the surface roughness of the oil bladder material, significantly increasing the cost of cleaning the bladder surface.

[0004] Traditional marine biofouling antifouling coatings are based on biocidal technology, but their use can lead to the widespread release of toxic compounds into the marine environment and ultimately into the food chain, posing a threat to the marine ecosystem. Underwater oil bladder materials containing the antifouling agent oxyketone also face the risk of being banned. Therefore, developing a non-release antifouling oil bladder material that is lightweight, high-strength, chemically resistant, seawater resistant, superhydrophobic, and self-cleaning is of great significance. Summary of the Invention

[0005] The technical problem to be solved by this invention is to provide a method for preparing a high-performance lightweight oil bladder material for underwater biofouling prevention. This lightweight underwater oil bladder material is lightweight, high-strength, seawater resistant, anti-fouling, and self-cleaning. It also possesses excellent puncture resistance, weldability, and ease of processing. The structure of the lightweight underwater oil bladder material, from the outside in, consists of an anti-fouling layer, an ultra-lightweight support layer, and an oil-resistant layer. The anti-fouling layer and the ultra-lightweight support layer are laminated together. The oil-resistant layer is coated onto the ultra-lightweight support layer. The anti-fouling layer is a fluorinated polyurethane functional film, prepared by combining fluorinated polyurethane PFU-X and polypyrrole-coated halloysite nanotubes. The ultra-lightweight oil-resistant layer is a composite material prepared by mixing hollow microspheres, epoxy resin, and a curing agent. The oil-resistant layer is a fluoropolymer resin. In the fluorinated polyurethane PFU-X, X refers to the percentage of BTE in the total mass of the mixed chain extender, 0 ≤ X ≤ 50. The chemical formula of the fluorinated polyurethane PFU-X is [formula missing]. Figure 1 As shown.

[0006] The raw materials for preparing the anti-adhesion layer also include nano-silica, antioxidant, calcium carbonate and talc. The weight ratio of each raw material component is as follows: fluorinated polyurethane PFU-X: 88~93 parts; polypyrrole-coated halloysite nanotubes: 2~4 parts; nano-silica: 1~2 parts; antioxidant: 1~2 parts; calcium carbonate: 2~3 parts; talc: 1.5~2 parts.

[0007] The antioxidant is any one of N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine (4020), N-phenyl-2-naphthylamine (D), and N-isopropyl-N'-phenyl-p-phenylenediamine.

[0008] In the ultra-light oil-resistant layer, the amount of hollow microspheres accounts for 45-60 vol% of the total volume of the mixture. In the epoxy resin and curing agent mixture, the mass ratio is 100 parts epoxy resin and 20 parts curing agent.

[0009] Meanwhile, the present invention also provides a method for preparing an anti-adhesion lightweight underwater oil bladder material, comprising the following steps: ① corona treatment of the contact surface of the anti-adhesion layer material and the ultra-light support layer material, and uniform coating of polyurethane adhesive on the corona-treated surface of the anti-adhesion layer material; ② laminating the anti-adhesion layer material treated in step ① and the ultra-light support layer material; ③ coating the oil-resistant layer on the surface of the ultra-light support layer by spraying, scraping, or spraying.

[0010] The amount of polyurethane adhesive applied is 15 g / m³. 2 The discharge power of the corona treatment is 0.8~1.2kW, and the corona treatment time is 1.0~1.5s; the lamination temperature is 110~130℃, and the pressure is 1.3~3.0MPa.

[0011] The anti-adhesion layer material is a fluorinated polyurethane functional film, and the preparation materials include fluorinated polyurethane PFU-X, polypyrrole-coated halloysite nanotubes, nano silica, antioxidant, calcium carbonate and talc.

[0012] The preparation method includes the following steps: First, PFU-X is dissolved in a dimethylformamide (DMF) solution at 55~65℃. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc are added to the mixed solution and mechanically stirred. After completion, the mixed adhesive solution is poured into a film and dried in an oven at 0.06~0.10MPa and 55~65℃ to obtain an anti-adhesion functional layer.

[0013] The preparation method of fluorinated polyurethane PFU-X is as follows:

[0014] (1) Dehydrated polyethylene glycol and toluene-2,4-diisocyanate were mixed and the ratio of n(OH):n(NCO) was controlled to be 1:2. The mixture was reacted at 80°C for 2-3 hours under N2 atmosphere to obtain polyurethane prepolymer.

[0015] (2) The concentration of NCO% in the reaction was detected, and then the chain extender 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane and 1,4-butanediol were added. The system temperature was gradually increased to 100℃ and the reaction was stopped after 2 to 8 hours. By changing the mass fraction of 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane in the mixed chain extender, fluorinated polyurethane PFU-X was obtained, where X refers to the percentage of BTE in the total mass of the mixed chain extender, 0≦X≦50, 40000≦Mn≦80000.

[0016] The preparation method of polypyrrole-coated halloysite nanotubes is as follows: Inorganic halloysite nanoparticles are added to an acidic solution of hydrochloric acid and distilled water. After ultrasonic dispersion, pyrrole is added to the solution, and the mixture is stirred and allowed to stand to obtain solution I. Then, an acidic solution containing ammonium persulfate and hydrochloric acid is added dropwise to solution I under ice bath conditions, stirred and centrifuged, washed until neutral, and dried under vacuum conditions of 35~45℃ and 0.06~0.10MPa for 12~24h to obtain polypyrrole-coated halloysite nanotubes.

[0017] The preparation method of the ultra-light oil-resistant layer is as follows: epoxy resin and curing agent are mixed, hollow microspheres are mixed with the mixture according to the above volume fraction, and stirred under vacuum conditions of 0.06~0.10MPa for 20~40min. The stirred material is poured into a polytetrafluoroethylene mold and heated and cured under pressure of 2~5MPa. The curing temperature is 90±2℃ / 3~5h +110±2℃ / 3~5h. After natural cooling, the material is demolded. Beneficial effects

[0018] This invention prepares a polyurethane oil storage bladder material suitable for underwater oil storage by combining the aforementioned specific anti-adhesion layer, ultra-lightweight support layer, and oil-resistant layer; its structure is as follows. Figure 1 As shown. The capsule material has good anti-fouling and self-cleaning properties, and is also lightweight, high-strength, compression-resistant, wear-resistant, flexible, and easy to use.

[0019] This invention first prepared a series of PFU resins by changing the mass fraction of 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) in a mixed chain extender, and named them PFU-X, where X refers to the percentage of BTE in the total mass of the mixed chain extender. The polyurethane resin described in this invention is a fluorinated polyurethane (PFU), and its structure is as follows: Figure 2 As shown. The soft segment of the PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a chain extender, with BTE mass fraction ranging from 0% to 50%. The PFU resin is prepared using a two-step polymerization reaction involving prepolymer synthesis and chain extension. The reaction equation is as follows: Figure 3 As shown.

[0020] Experimental results show that when the polyurethane resin is fluorinated polyurethane PFU-X, and 0≦X≦50, 40000≦Mn≦80000, the -CF3 in BTE can assemble at the interface, reduce the surface energy, prevent the adhesion of organisms to the material surface, and have better repellency to biological fluids.

[0021] Biofouling Adhesion Test: The marine diatom strain *Phaeocystis triangularis* was selected as a typical diatom for adhesion testing. The anti-fouling performance of the oil bladder material was evaluated by observing the adhesion behavior of *Phaeocystis triangularis* on its surface. The adhesion experiment was conducted in an artificial seabed using a concentration of 5 × 10⁻⁶. 6 Adhesion assays were performed using algal suspensions at a concentration of cells / mL. Three samples from each assay were immersed in the algal suspension at 22°C and cultured for 7 days (12h light / dark cycle). The samples were then washed three times with sterilized seawater to remove any unadhered diatoms. Marine fouling coverage was observed using a confocal laser scanning microscope. Diatom coverage (%) was defined as the ratio of the area of ​​diatom adhesion to the total surface area of ​​the matrix.

[0022] The areal density of the oil bladder material described in this invention is 50~65 g / m³. 2 Gasoline permeability ≤ 100g / m 2• After 24 hours, the interlayer peel strength is ≥2.0 kN / m, the bursting strength is ≥6 kN, the tensile strength is ≥1000 N / cm, the surface water contact angle is 105°~146°, the diatom coverage is ≤10%, and the tensile strength after 200 hours of salt spray corrosion is ≥700 N / cm. It can be seen that the anti-adhesion lightweight underwater oil bladder material prepared by this invention has excellent comprehensive performance and is suitable for widespread use. Attached Figure Description

[0023] Figure 1 : A simplified diagram of the composite layer structure of the anti-adhesion lightweight underwater oil bladder material of this invention.

[0024] Figure 2 The structural formula of the fluorinated polyurethane (PFU-X) in this invention.

[0025] Figure 3 The reaction equation for the preparation of fluorinated polyurethane (PFU-X) in this invention. Implementation

[0026] To further illustrate the present invention, the following describes in detail, with reference to embodiments, an anti-adhesion lightweight polyurethane oil reservoir material and its preparation method.

[0027] The two-component polyurethane adhesive was purchased from Dongguan Yantai Chemical Technology Co., Ltd. It is a general-purpose two-component polyurethane adhesive with hydroxyl-terminated polyurethane organic solution as the main agent, which is made from polyethylene adipate diol and toluene diisocyanate as the main raw materials, and trimethylolpropane-toluene diisocyanate adduct organic solution as the curing agent. Example 1

[0028] In this embodiment, the polyurethane oil bladder material structure, from the outside in, consists of an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer, as shown in the figure. Figure 1 As shown.

[0029] The anti-adhesion layer material of the polyurethane oil bladder is a hydrophobic fluorinated polyurethane functional film with an areal density of 20 g / m³. 2 Its components are as follows:

[0030] (1) PFU-10 resin: 89%;

[0031] (2) Pyrrole-coated halloysite nanotubes: 2%;

[0032] (3) Nano silica: 1%;

[0033] (4) N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine: 1.5%;

[0034] (5) Calcium carbonate: 2%;

[0035] (6) Talc: 1.5%.

[0036] The preparation method of the hydrophobic fluorinated polyurethane functional membrane is as follows:

[0037] First, PFU-10 was dissolved in a 60°C dimethylformamide (DMF) solution. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder were added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 30 minutes. After that, the mixed adhesive was poured into a polytetrafluoroethylene mold and dried in an oven at 0.06 MPa and 60°C for 10 hours to obtain the anti-adhesion functional layer.

[0038] The polyurethane resin used is a self-made PFU-10 resin, and its preparation method is as follows:

[0039] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 10%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0040] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0041] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. The reaction was stopped after 2 hours to obtain fluorinated polyurethane PFU-10.

[0042] The preparation method of the polypyrrole-coated halloysite nanotubes is as follows:

[0043] Organic nanoparticles polypyrrole (PPY) and inorganic nanoparticles halloysite nanotubes (HNTs) were used as nanomaterials for synergistic antifouling. The preparation method of polypyrrole-coated halloysite nanotubes (HNTs@PPy) is as follows: 3 g of HNTs were added to an acidic solution of 6 mL hydrochloric acid and 450 mL distilled water. After ultrasonic dispersion for 30 min, 0.5 mL of pyrrole was added to the solution, and the mixture was stirred and allowed to stand for 12 h. Then, 100 mL of acidic solution containing 2.27 g of ammonium persulfate and 1 mL of hydrochloric acid was added dropwise to the above solution under ice bath conditions and stirred for 12 h. After centrifugation, the solution was washed until neutral. The HNTs@PPy was then dried under vacuum at 40 °C for 12 h.

[0044] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0045] (1) Hollow glass microspheres: 45 vol%;

[0046] (2) Epoxy E51: 100 parts;

[0047] (3) T31 curing agent: 20 parts.

[0048] The preparation method of the ultralight support layer is as follows:

[0049] Epoxy E51 and T31 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.08 MPa for 35 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 3 MPa at a curing temperature of 90℃ / 4h + 110℃ / 4h. After natural cooling, the mixture was demolded. The density was 0.7 g / cm³. 3 It has a porosity of 2.05% and a compressive strength of 80 MPa.

[0050] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 25 g / m³. 2 .

[0051] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0052] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona time of 1.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 15 g / m. 2 ;

[0053] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s;

[0054] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 120℃ and the lamination pressure is 1.5 MPa.

[0055] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was uniformly coated on the corona surface using a coating device, and the coating surface density was 25 g / m². 2 A lightweight, anti-adhesion underwater oil bladder material was obtained. Example 2

[0056] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0057] The anti-adhesion layer material of the polyurethane oil bladder is a hydrophobic fluorinated polyurethane functional film with an areal density of 24 g / m³. 2 Its components are as follows:

[0058] (1) PFU-30 resin: 90%;

[0059] (2) Pyrrole-coated halloysite nanotubes: 4%;

[0060] (3) Nano silica: 1%;

[0061] (4) N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine: 1.5%;

[0062] (5) Calcium carbonate: 2%;

[0063] (6) Talc: 1.5%.

[0064] The preparation method of the hydrophobic fluorinated polyurethane functional membrane is as follows:

[0065] First, PFU-30 was dissolved in a dimethylformamide (DMF) solution at 55°C. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder were added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 30 minutes. After that, the mixed adhesive was poured into a polytetrafluoroethylene mold and dried in an oven at 0.1 MPa and 55°C for 10 hours to obtain the anti-adhesion functional layer.

[0066] The polyurethane resin used is a self-made PFU-30 resin, and its preparation method is as follows:

[0067] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 30%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0068] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0069] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 3 hours, the reaction was stopped, and fluorinated polyurethane PFU-30 was obtained.

[0070] The preparation method of the polypyrrole-coated halloysite nanotubes is as follows:

[0071] Organic nanoparticles polypyrrole (PPY) and inorganic nanoparticles halloysite nanotubes (HNTs) were used as nanomaterials for synergistic antifouling. The preparation method of polypyrrole-coated halloysite nanotubes (HNTs@PPy) is as follows: 3 g of HNTs were added to an acidic solution of 6 mL hydrochloric acid and 450 mL distilled water. After ultrasonic dispersion for 30 min, 0.5 mL of pyrrole was added to the solution, and the mixture was stirred and allowed to stand for 12 h. Then, 100 mL of acidic solution containing 2.27 g of ammonium persulfate and 1 mL of hydrochloric acid was added dropwise to the above solution under ice bath conditions and stirred for 12 h. After centrifugation, the solution was washed until neutral. The HNTs@PPy was then dried under vacuum at 40 °C for 12 h.

[0072] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0073] (1) Hollow glass microspheres: 50 vol%;

[0074] (2) Epoxy E51: 100 parts;

[0075] (3) 650 curing agent: 20 parts.

[0076] The preparation conditions for the ultralight support layer are as follows:

[0077] Epoxy E51 and 650 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.1 MPa for 35 minutes, and then heated and cured at 2 MPa pressure. The curing temperature was 90℃ / 4h + 110℃ / 4h. After natural cooling, the mixture was demolded. The density was 0.68 g / cm³. 3 It has a porosity of 2.45% and a compressive strength of 73 MPa.

[0078] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 25 g / m³. 2 .

[0079] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0080] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona time of 1.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 15 g / m. 2 ;

[0081] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s;

[0082] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 120℃ and the lamination pressure is 1.5 MPa.

[0083] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was sprayed onto the corona-treated surface using a spray gun, with a coating surface density of 25 g / m². 2 A lightweight, anti-adhesion underwater oil bladder material was obtained. Example 3

[0084] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0085] The anti-adhesion layer material of the polyurethane oil bladder is a hydrophobic fluorinated polyurethane functional film with an areal density of 28 g / m³. 2 Its components are as follows:

[0086] (1) PFU-50 resin: 90%;

[0087] (2) Pyrrole-coated halloysite nanotubes: 4%;

[0088] (3) Nano silica: 1%;

[0089] (4) N-Phenylacetylamine (D): 1.5%;

[0090] (5) Calcium carbonate: 2%;

[0091] (6) Talc: 1.5%.

[0092] First, PFU-50 was dissolved in a 65°C dimethylformamide (DMF) solution. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder were added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 30 minutes. After that, the mixed adhesive was poured into a polytetrafluoroethylene mold and dried in an oven at 0.08 MPa and 65°C for 8 hours to obtain the anti-adhesion functional layer.

[0093] The polyurethane resin used is a self-made PFU-50 resin, and its preparation method is as follows:

[0094] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 50%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0095] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0096] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 5 hours, the reaction was stopped, and fluorinated polyurethane PFU-50 was obtained.

[0097] The preparation method of the polypyrrole-coated halloysite nanotubes is as follows:

[0098] Organic nanoparticles polypyrrole (PPY) and inorganic nanoparticles halloysite nanotubes (HNTs) were used as nanomaterials for synergistic antifouling. The preparation method of polypyrrole-coated halloysite nanotubes (HNTs@PPy) is as follows: 3 g of HNTs were added to an acidic solution of 6 mL hydrochloric acid and 450 mL distilled water. After ultrasonic dispersion for 30 min, 0.5 mL of pyrrole was added to the solution, and the mixture was stirred and allowed to stand for 12 h. Then, 100 mL of acidic solution containing 2.27 g of ammonium persulfate and 1 mL of hydrochloric acid was added dropwise to the above solution under ice bath conditions and stirred for 12 h. After centrifugation, the solution was washed until neutral. The HNTs@PPy was then dried under vacuum at 40 °C for 12 h.

[0099] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0100] (1) Hollow glass microspheres: 50 vol%;

[0101] (2) Epoxy E51: 100 parts;

[0102] (3) T31 curing agent: 20 parts.

[0103] The preparation conditions for the ultralight support layer are as follows:

[0104] Epoxy E51 and T31 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.1 MPa for 35 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 3 MPa at a curing temperature of 90℃ / 4h + 110℃ / 4h. After natural cooling, the mixture was demolded. The density was 0.68 g / cm³. 3 It has a porosity of 2.45% and a compressive strength of 73 MPa.

[0105] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 25 g / m³. 2 .

[0106] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0107] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona time of 1.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 15 g / m. 2 ;

[0108] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s;

[0109] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 120℃ and the lamination pressure is 1.5 MPa.

[0110] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was uniformly coated on the corona surface using a coating device, and the coating surface density was 25 g / m². 2 A lightweight, anti-adhesion underwater oil bladder material was obtained. Example 4

[0111] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0112] The anti-adhesion layer material of the polyurethane oil bladder is a hydrophobic fluorinated polyurethane functional film with an areal density of 31 g / m³. 2 Its components are as follows:

[0113] (1) PFU-50 resin: 91.5%;

[0114] (2) Pyrrole-coated halloysite nanotubes: 2.5%;

[0115] (3) Nano silica: 1%;

[0116] (4) N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine: 1.5%;

[0117] (5) Calcium carbonate: 2%;

[0118] (6) Talc: 1.5%.

[0119] First, PFU-50 was dissolved in a 60°C dimethylformamide (DMF) solution. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder were added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 40 minutes. After that, the mixed adhesive was poured into a polytetrafluoroethylene mold and dried in an oven at 0.08 MPa and 60°C for 12 hours to obtain the anti-adhesion functional layer.

[0120] The polyurethane resin used is a self-made PFU-50 resin, and its preparation method is as follows:

[0121] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 50%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0122] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0123] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 5 hours, the reaction was stopped, and fluorinated polyurethane PFU-50 was obtained.

[0124] The preparation method of the polypyrrole-coated halloysite nanotubes is as follows:

[0125] Organic nanoparticles polypyrrole (PPY) and inorganic nanoparticles halloysite nanotubes (HNTs) were used as nanomaterials for synergistic antifouling. The preparation method of polypyrrole-coated halloysite nanotubes (HNTs@PPy) is as follows: 3 g of HNTs were added to an acidic solution of 6 mL hydrochloric acid and 450 mL distilled water. After ultrasonic dispersion for 30 min, 0.5 mL of pyrrole was added to the solution, and the mixture was stirred and allowed to stand for 12 h. Then, 100 mL of acidic solution containing 2.27 g of ammonium persulfate and 1 mL of hydrochloric acid was added dropwise to the above solution under ice bath conditions and stirred for 12 h. After centrifugation, the solution was washed until neutral. The HNTs@PPy was then dried under vacuum at 40 °C for 12 h.

[0126] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0127] (1) Hollow glass microspheres: 55 vol%;

[0128] (2) Epoxy E51: 100 parts;

[0129] (3) 593 curing agent: 20 parts.

[0130] The preparation conditions for the ultralight support layer are as follows:

[0131] Epoxy E51 and 593 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.08 MPa for 40 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 4 MPa at a curing temperature of 88℃ / 5h + 108℃ / 5h. After natural cooling, the mixture was demolded. The density was 0.60 g / cm³. 3 It has a porosity of 3.12% and a compressive strength of 55 MPa.

[0132] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 20 g / m³. 2 .

[0133] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0134] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona time of 1.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 15 g / m. 2 ;

[0135] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s;

[0136] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 120℃ and the lamination pressure is 1.5 MPa.

[0137] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was uniformly coated on the corona surface using a coating device, and the coating surface density was 25 g / m². 2 A lightweight, anti-adhesion underwater oil bladder material was obtained. Example 5

[0138] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0139] The anti-adhesion layer material of the polyurethane oil bladder is a hydrophobic fluorinated polyurethane functional film with an areal density of 29 g / m³. 2 Its components are as follows:

[0140] (1) PFU-40 resin: 91.5%;

[0141] (2) Pyrrole-coated halloysite nanotubes: 2.5%;

[0142] (3) Nano-silica: 1.5%;

[0143] (4) N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine: 1%;

[0144] (5) Calcium carbonate: 2%;

[0145] (6) Talc: 1.5%.

[0146] First, PFU-40 was dissolved in a 60°C dimethylformamide (DMF) solution. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder were added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 20 minutes. After that, the mixed adhesive was poured into a polytetrafluoroethylene mold and dried in an oven at 0.1 MPa and 60°C for 8 hours to obtain the anti-adhesion functional layer.

[0147] The polyurethane resin used is a self-made PFU-40 resin, and its preparation method is as follows:

[0148] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 40%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0149] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0150] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 4.5 hours, the reaction was stopped, and fluorinated polyurethane PFU-40 was obtained.

[0151] The preparation method of the polypyrrole-coated halloysite nanotubes is as follows:

[0152] Organic nanoparticles polypyrrole (PPY) and inorganic nanoparticles halloysite nanotubes (HNTs) were used as nanomaterials for synergistic antifouling. The preparation method of polypyrrole-coated halloysite nanotubes (HNTs@PPy) is as follows: 3 g of HNTs were added to an acidic solution of 6 mL hydrochloric acid and 450 mL distilled water. After ultrasonic dispersion for 30 min, 0.5 mL of pyrrole was added to the solution, and the mixture was stirred and allowed to stand for 12 h. Then, 100 mL of acidic solution containing 2.27 g of ammonium persulfate and 1 mL of hydrochloric acid was added dropwise to the above solution under ice bath conditions and stirred for 12 h. After centrifugation, the solution was washed until neutral. The HNTs@PPy was then dried under vacuum at 40 °C for 12 h.

[0153] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0154] (1) Hollow glass microspheres: 55 vol%;

[0155] (2) Epoxy E51: 100 parts;

[0156] (3) 650 curing agent: 20 parts.

[0157] The preparation conditions for the ultralight support layer are as follows:

[0158] Epoxy E51 and 650 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.1 MPa for 20 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 3 MPa at a curing temperature of 90℃ / 4h + 110℃ / 4h. After natural cooling, the mixture was demolded. The density was 0.60 g / cm³. 3 It has a porosity of 3.12% and a compressive strength of 55 MPa.

[0159] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 30 g / m³. 2 .

[0160] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0161] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 1.0 kW and a corona discharge time of 2.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 10 g / m. 2 ;

[0162] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.5 kW and a corona discharge time of 1.5 s;

[0163] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 130℃ and the lamination pressure is 3MPa.

[0164] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was uniformly coated on the corona surface using a coating device, and the coating surface density was 25 g / m². 2 A lightweight, anti-adhesion underwater oil bladder material was obtained. Example 6

[0165] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0166] The anti-adhesion layer material of the polyurethane oil bladder is a hydrophobic fluorinated polyurethane functional film with an areal density of 30 g / m³. 2 Its components are as follows:

[0167] (1) PFU-50 resin: 91.5%;

[0168] (2) Pyrrole-coated halloysite nanotubes: 2.5%;

[0169] (3) Nano silica: 1%;

[0170] (4) N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine: 1.5%;

[0171] (5) Calcium carbonate: 2%;

[0172] (6) Talc: 1.5%.

[0173] First, PFU-50 was dissolved in a 60°C dimethylformamide (DMF) solution. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder were added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 30 minutes. After that, the mixed adhesive was poured into a polytetrafluoroethylene mold and dried in an oven at 0.1 MPa and 60°C for 10 hours to obtain the anti-adhesion functional layer.

[0174] The polyurethane resin used is a self-made PFU-50 resin, and its preparation method is as follows:

[0175] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 50%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0176] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0177] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 5 hours, the reaction was stopped, and fluorinated polyurethane PFU-50 was obtained.

[0178] The preparation method of the polypyrrole-coated halloysite nanotubes is as follows:

[0179] Organic nanoparticles polypyrrole (PPY) and inorganic nanoparticles halloysite nanotubes (HNTs) were used as nanomaterials for synergistic antifouling. The preparation method of polypyrrole-coated halloysite nanotubes (HNTs@PPy) is as follows: 3 g of HNTs were added to an acidic solution of 6 mL hydrochloric acid and 450 mL distilled water. After ultrasonic dispersion for 30 min, 0.5 mL of pyrrole was added to the solution, and the mixture was stirred and allowed to stand for 12 h. Then, 100 mL of acidic solution containing 2.27 g of ammonium persulfate and 1 mL of hydrochloric acid was added dropwise to the above solution under ice bath conditions and stirred for 12 h. After centrifugation, the solution was washed until neutral. The HNTs@PPy was then dried under vacuum at 40 °C for 12 h.

[0180] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0181] (1) Hollow glass microspheres: 60 vol%;

[0182] (2) Epoxy E51: 100 parts;

[0183] (3) 593 curing agent: 20 parts.

[0184] The preparation conditions for the ultralight support layer are as follows:

[0185] Epoxy E51 and 593 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.1 MPa for 30 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 2 MPa at a curing temperature of 92℃ / 3h + 110℃ / 3h. After natural cooling, the mixture was demolded. The density was 0.50 g / cm³. 3 It has a porosity of 3.38% and a compressive strength of 46 MPa.

[0186] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 25 g / m³. 2 .

[0187] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0188] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 30 g / m. 2 ;

[0189] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona discharge time of 1.0 s;

[0190] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 110℃ and the lamination pressure is 1.3MPa.

[0191] (4) The corona discharge power on the back of the ultralight support was 1.2 kW and the corona time was 1.5 s; then, a polyvinyl fluoride layer was uniformly coated on the corona-coated surface using a spray coating equipment, and the coating surface density was 25 g / m². 2 A lightweight, anti-adhesion underwater oil bladder material was obtained.

[0192] To verify the beneficial effects of fluorinated polyurethane on the present invention, we replaced the PFU resin in the polyurethane functional film with fluorine-free polyurethane resin, while keeping the rest of the formulation and process parameters the same as in Example 4, and conducted a comparative experiment. Comparative Example 1

[0193] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0194] The anti-adhesion layer of the polyurethane oil bladder material is a polyurethane film with a surface density of 28 g / m³. 2 Its components are as follows:

[0195] (1) PU resin: 91.5%;

[0196] (2) Pyrrole-coated halloysite nanotubes: 2.5%;

[0197] (3) Nano silica: 1%;

[0198] (4) N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine: 1.5%;

[0199] (5) Calcium carbonate: 2%;

[0200] (6) Talc: 1.5%.

[0201] First, PU resin is dissolved in a 60°C dimethylformamide (DMF) solution. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc powder are added to the mixed solution according to the above proportions. The mixture is mechanically stirred for 30 minutes. After that, the mixed adhesive is poured into a polytetrafluoroethylene mold and dried in an oven at 0.1 MPa and 60°C for 8 hours to obtain an anti-adhesion functional layer.

[0202] The polyurethane resin used is a self-made fluorine-free polyurethane resin, and its preparation method is as follows:

[0203] The soft segment of the PU resin is made of polyethylene glycol (PEG), the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer, and the only chain extender is 1,4-butanediol (BDO). The BTE mass fraction is 0%. The PU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0204] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0205] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 5 hours, the reaction was stopped, and fluorine-free polyurethane (PU) was obtained.

[0206] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0207] (1) Hollow glass microspheres: 55 vol%;

[0208] (2) Epoxy E51: 100 parts;

[0209] (3) T31 curing agent: 20 parts.

[0210] The preparation conditions for the ultralight support layer are as follows:

[0211] Epoxy E51 and T31 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.1 MPa for 30 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 3 MPa at a curing temperature of 90℃ / 4h + 110℃ / 4h. After natural cooling, the mixture was demolded. The density was 0.60 g / cm³. 3 It has a porosity of 3.12% and a compressive strength of 55 MPa.

[0212] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 25 g / m³. 2 .

[0213] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0214] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona time of 1.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 15 g / m. 2 ;

[0215] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s;

[0216] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 120℃ and the lamination pressure is 1.5 MPa.

[0217] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was uniformly coated on the corona surface using a coating device, and the coating surface density was 25 g / m². 2 .

[0218] To verify the beneficial effects of adding pyrrole-coated halloysite nanotubes on the present invention, we prepared an anti-adhesion layer material without pyrrole-coated halloysite nanotubes, with the remaining formulations and process parameters being the same as in Example 4, and conducted comparative experiments. Comparative Example 2

[0219] In this embodiment, the polyurethane oil bladder material structure consists of, from the outside in, an anti-adhesion layer → an ultra-lightweight support layer → an oil-resistant layer.

[0220] The anti-adhesion layer of the polyurethane oil bladder material is a polyurethane film with a surface density of 28 g / m³. 2 Its components are as follows:

[0221] (1) PFU-50 resin: 91.5%;

[0222] (2) Nano-silica: 2%;

[0223] (3) N-Isopropyl-N'-Phenylene-p-phenylenediamine (4010NA): 2%;

[0224] (4) Calcium carbonate: 2.5%;

[0225] (5) Talc: 2%.

[0226] First, PFU-50 resin was dissolved in a 60°C dimethylformamide (DMF) solution. Nano-silica, antioxidant, calcium carbonate, and talc were then added to the mixed solution according to the above proportions. The mixture was mechanically stirred for 30 minutes. After stirring, the mixed solution was poured into a polytetrafluoroethylene mold and dried in an oven at 0.1 MPa and 60°C for 8 hours to obtain an anti-adhesion functional layer.

[0227] The polyurethane resin used is a self-made PFU-50 resin, and its preparation method is as follows:

[0228] The soft segment of PFU resin is made of polyethylene glycol (PEG), and the hard segment is made of toluene-2,4-diisocyanate (TDI) monomer. 1,4-Butanediol (BDO) and 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane (BTE) are mixed in different proportions as a mixed chain extender, with BTE having a mass fraction of 50%. PFU resin is prepared by a two-step polymerization reaction of prepolymer synthesis and chain extension. The specific reaction process is shown below:

[0229] (1) Place the pre-dehydrated PEG and TDI in a three-necked flask equipped with mechanical stirring, nitrogen protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 80℃ for 2 hours under N2 atmosphere protection to obtain polyurethane prepolymer.

[0230] (2) The concentration of NCO% in the reaction was detected by di-n-butylamine hydrochloride titration. Then, a stoichiometric mixture of BTE and BDO chain extender was added, and the system temperature was gradually increased to 100℃. After 5 hours, the reaction was stopped, and fluorinated polyurethane PFU-50 was obtained.

[0231] The ultralight support layer of the polyurethane oil bladder material is a composite material of hollow glass microspheres and epoxy resin, and its composition is as follows:

[0232] (1) Hollow glass microspheres: 55 vol%;

[0233] (2) Epoxy E51: 100 parts;

[0234] (3) 593 curing agent: 20 parts.

[0235] The preparation conditions for the ultralight support layer are as follows:

[0236] Epoxy E51 and 593 curing agent were mixed according to the above mass ratio. Hollow glass microspheres were then mixed with the mixture according to the above volume fraction. The mixture was stirred under a vacuum of 0.1 MPa for 30 minutes. The stirred material was poured into a PTFE mold and cured under a pressure of 2 MPa at a curing temperature of 90℃ / 4h + 110℃ / 4h. After natural cooling, the mixture was demolded. The density was 0.60 g / cm³. 3 It has a porosity of 3.12% and a compressive strength of 55 MPa.

[0237] The oil-resistant layer is a commercially available polyvinyl fluoride coating; the areal density of the oil-resistant layer is 25 g / m³. 2 .

[0238] The anti-adhesion layer material and the ultralight support layer material are prepared by lamination composite method, and the specific steps are as follows:

[0239] (1) The anti-adhesion layer material is placed at the first unwinding position of the laminating machine. First, it is passed through a single-sided corona discharge device with a corona discharge power of 0.8 kW and a corona time of 1.0 s. Then, a two-component polyurethane adhesive is uniformly coated on the corona-treated surface with an adhesive amount of 15 g / m. 2 ;

[0240] (2) The ultralight support layer material is placed at the second unwinding position of the laminating machine and first passes through a single-sided corona discharge device with a corona discharge power of 1.2 kW and a corona discharge time of 1.5 s;

[0241] (3) The anti-adhesion layer material and the ultra-light support layer material are laminated together using a lamination composite device. The lamination temperature is 120℃ and the lamination pressure is 1.5 MPa.

[0242] (4) The corona discharge power on the back of the ultralight support was 0.8 kW and the corona time was 1.0 s; then, a polyvinyl fluoride layer was uniformly coated on the corona surface using a coating device, and the coating surface density was 25 g / m². 2 .

[0243] To verify the technical effects of the present invention, the anti-adhesion lightweight oil bladder materials prepared in Examples 1 to 6 were subjected to various performance tests, including areal density, oil and gas permeability, interlayer peel strength, bursting strength, tensile strength, surface water contact angle, and seaweed coverage. Comparative Examples 1 and 2 were also subjected to the same tests, and the results are shown in Table 1.

[0244] Table 1. Test results of the anti-adhesion lightweight oil bladder materials obtained in Examples 1-6 and the oil bladder materials in Comparative Examples 1-2

[0245] Group <![CDATA[Areal density (g / m 2 )]]> <![CDATA[Gas and oil permeation amount (g / m 2 ·24h)]]> Interlayer peel strength (kN / m) Bursting strength (kN) Tensile strength (N / cm) <![CDATA[Surface water contact angle ( o )]]> Diatom coverage (%) Tensile strength (N / cm) after 200 hours of salt spray test Example 1 55 89.4 2.88 6.4 1185 105 9.8 942 Example 2 54 77.9 2.97 6.8 1296 123 8.6 1130 Example 3 58 95.4 3.43 7.5 1137 146 6.9 1014 Example 4 61 72.6 4.84 6.5 1215 139 4.6 1103 Example 5 58 86.5 3.15 6.1 1032 135 5.8 841 Example 6 47 80.2 4.55 6.3 1141 140 7.7 956 Comparative Example 1 80 92.4 5.32 7.2 1236 67 78.1 652 Comparative Example 2 58 124.5 2.53 6.1 1157 142 67.3 884

Claims

1. A lightweight, anti-adhesion underwater oil bladder material, characterized in that: The anti-adhesion lightweight underwater oil bladder material consists of an anti-adhesion layer, an ultra-lightweight support layer, and an oil-resistant layer from the outside in. The anti-adhesion layer and the ultra-lightweight support layer are laminated together. The oil-resistant layer is coated onto the ultra-lightweight support layer. The anti-adhesion layer is a fluorinated polyurethane functional film, prepared from fluorinated polyurethane PFU-X and polypyrrole-coated halloysite nanotubes. The ultra-lightweight oil-resistant layer is a composite material prepared from hollow microspheres, epoxy resin, and a curing agent. The oil-resistant layer is a fluoropolymer resin. In the fluorinated polyurethane PFU-X, X refers to the percentage of BTE in the total mass of the mixed chain extender, 0 < X ​​≤ 50. The chemical formula of the fluorinated polyurethane PFU-X is: 。 2. The anti-adhesion lightweight underwater oil bladder material according to claim 1, characterized in that: The raw materials for preparing the anti-adhesion layer also include nano-silica, antioxidant, calcium carbonate and talc. The weight ratio of each raw material component is as follows: fluorinated polyurethane PFU-X: 88~93 parts; polypyrrole-coated halloysite nanotubes: 2~4 parts; nano-silica: 1~2 parts; antioxidant: 1~2 parts; calcium carbonate: 2~3 parts; talc: 1.5~2 parts.

3. The anti-adhesion lightweight underwater oil bladder material according to claim 2, characterized in that: The antioxidant is any one of N-(1,3-dimethyl)butyl-N'-phenyl-p-phenylenediamine (4020), N-phenyl-2-naphthylamine (D), and N-isopropyl-N'-phenyl-p-phenylenediamine.

4. The anti-adhesion lightweight underwater oil bladder material according to claim 1, characterized in that: In the ultra-light oil-resistant layer, the amount of hollow microspheres accounts for 45-60 vol% of the total volume of the mixture. In the epoxy resin and curing agent mixture, the mass ratio is 100 parts epoxy resin and 20 parts curing agent.

5. A method for preparing the anti-adhesion lightweight underwater oil bladder material according to claim 1, characterized in that: The process includes the following steps: ① Corona treatment of the contact surfaces of the anti-adhesion layer material and the ultralight support layer material, and uniform coating of polyurethane adhesive on the corona-treated surface of the anti-adhesion layer material; ② Lamination of the anti-adhesion layer material treated in step ① and the ultralight support layer material; ③ Coating of the oil-resistant layer onto the surface of the ultralight support layer by spraying, scraping, or spraying.

6. A method for preparing the anti-adhesion lightweight underwater oil bladder material according to claim 5, characterized in that: The amount of polyurethane adhesive applied is 15 g / m³. 2 The discharge power of the corona treatment is 0.8~1.2kW, and the corona treatment time is 1.0~1.5s; the lamination temperature is 110~130℃, and the pressure is 1.3~3.0MPa.

7. A method for preparing the anti-adhesion lightweight underwater oil bladder material according to claim 5, characterized in that: The anti-adhesion layer material is a fluorinated polyurethane functional film, and the preparation materials include fluorinated polyurethane PFU-X, polypyrrole-coated halloysite nanotubes, nano silica, antioxidant, calcium carbonate and talc. The preparation method includes the following steps: First, PFU-X is dissolved in a dimethylformamide (DMF) solution at 55~65℃. Then, pyrrole-coated halloysite nanotubes, nano-silica, antioxidant, calcium carbonate, and talc are added to the mixed solution and mechanically stirred. After completion, the mixed adhesive is poured into a mold and dried in an oven at 0.06~0.10MPa and 55~65℃ to obtain an anti-adhesion functional layer.

8. A method for preparing the anti-adhesion lightweight underwater oil bladder material according to claim 7, characterized in that: The preparation method of the fluorinated polyurethane PFU-X is as follows: (1) Dehydrated polyethylene glycol and toluene-2,4-diisocyanate were mixed and the ratio of n(OH):n(NCO) was controlled to be 1:

2. The mixture was reacted at 80°C for 2-3 hours under N2 atmosphere to obtain polyurethane prepolymer. (2) The concentration of NCO% in the reaction was detected, and then the chain extender 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane and 1,4-butanediol were added. The system temperature was gradually increased to 100℃ and the reaction was stopped after 2 to 8 hours. By changing the mass fraction of 2,2-bis[4-(4-aminophenoxy)benzene]hexafluoropropane in the mixed chain extender, fluorinated polyurethane PFU-X was obtained, where X refers to the percentage of BTE in the total mass of the mixed chain extender, 0 < X ​​≦ 50, 40000 ≦ Mn ≦ 80000.

9. A method for preparing the anti-adhesion lightweight underwater oil bladder material according to claim 7, characterized in that: The method for preparing the polypyrrole-coated halloysite nanotubes is as follows: adding inorganic halloysite nanoparticles into an acidic solution of hydrochloric acid and distilled water; After ultrasonic dispersion, pyrrole was added to the solution, stirred and allowed to stand to obtain solution I; Then, an acidic solution containing ammonium persulfate and hydrochloric acid was added dropwise to solution I under ice bath conditions, stirred and centrifuged, washed until neutral, and dried under vacuum conditions of 35~45℃ and 0.06~0.10MPa for 12~24h to obtain polypyrrole-coated halloysite nanotubes.

10. A method for preparing the anti-adhesion lightweight underwater oil bladder material according to claim 5, characterized in that: The preparation method of the ultra-light oil-resistant layer is as follows: epoxy resin and curing agent are mixed, and hollow microspheres are mixed with the mixture at a volume ratio of 45~60 vol% of hollow microspheres to the total volume of the mixture. The mixture is stirred under vacuum conditions of 0.06~0.10 MPa for 20~40 min. The stirred material is poured into a mold and heated and cured under a pressure of 2~5 MPa. The curing temperature is 90±2℃ / 3~5h + 110±2℃ / 3~5h. The material is demolded after natural cooling.

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