阅读说明：本技术 一种仿生型石油管道涂层及其制备方法 (Bionic petroleum pipeline coating and preparation method thereof ) 是由 田丽梅 窦海旭 赵杰 范勇 于 2020-11-06 设计创作，主要内容包括：本发明涉及一种仿生型石油管道涂层及其制备方法,属于新型高分子表面涂层。该涂层以典物鲀鱼体表为基本研究模型,利用亲水性单体和低表面能含氟长链以及二苯甲酮类光引发剂聚合而成。通过紫外光引发可以将涂层固定在各种基底材料表面,基底与涂层之间附着力较强。涂层改变了基底的表面性能,实现了对基底表面的亲水改性和对低表面张力液体如多种油类的防黏附性能。这类涂层可实现动态和静态环境下的优异亲水疏油性能。此发明重点实用于解决石油管道内衬管壁结蜡的共性难题,其具有节能、高效、长寿等特点,属于防止管壁结蜡的“治本”的技术,具有良好的应用前景和经济价值,是未来输油管道防蜡技术的发展必然趋势。(The invention relates to a bionic petroleum pipeline coating and a preparation method thereof, belonging to a novel polymer surface coating. The coating is prepared by polymerizing hydrophilic monomers, fluorine-containing long chains with low surface energy and benzophenone photoinitiators by taking the surface of the fugu ocellatus as a basic research model. The coating can be fixed on the surfaces of various substrate materials through ultraviolet light initiation, and the adhesive force between the substrate and the coating is strong. The coating changes the surface properties of the substrate, achieves hydrophilic modification of the substrate surface and anti-adhesion properties to low surface tension liquids such as various oils. Such coatings can achieve excellent oleo-hydrophilic and oleophobic properties in both dynamic and static environments. The invention is mainly used for solving the common problem of wax deposition on the wall of the petroleum pipeline lining pipe, has the characteristics of energy conservation, high efficiency, long service life and the like, belongs to the technology of 'permanent cure' for preventing wax deposition on the pipe wall, has good application prospect and economic value, and is the inevitable trend of the development of the future oil pipeline wax-proofing technology.)

1. A preparation method of a bionic petroleum pipeline coating is characterized by comprising the following steps:

1) preparation of photoinitiator prepolymer with long fluorine-containing chain: dissolving benzophenone photoinitiator, hydrophilic monomer and fluorine-containing surfactant serving as raw materials in a solvent, adding azobisisobutyronitrile, and heating at the temperature of 55-90 ℃ for 3-18 h to prepare a photoinitiator prepolymer with a fluorine-containing long chain; the solvent is one or more of dimethylformamide, ethanol, acetone, isopropanol, butanol, tetrahydrofuran and toluene;

wherein, the benzophenone photoinitiator is a compound which takes benzophenone as a main body, wherein, a para-position of a phenyl group is provided with a modifying group, and the modifying group at least contains a double bond positioned at the end; the hydrophilic monomer is acrylic acid or derivatives thereof, and the hydrophilic end of the fluorine-containing surfactant is an acrylate group;

the mass ratio of the benzophenone photoinitiator to the hydrophilic monomer is 1: 5-100, and the mass ratio of the fluorine-containing surfactant to the hydrophilic monomer is 1: 2-50; the ratio of the raw material to the solvent is 5-50 g/mL.

2) Photoinitiated preparation of the coating: dispersing the prepolymer obtained in the step 1) in a solvent, coating the prepolymer on the surface of a substrate containing a carbon-hydrogen bond, carrying out ultraviolet irradiation treatment on a substrate slice, then cleaning the unreacted prepolymer on the substrate with ethanol, then placing a coating sample in a vacuum oven for drying, and volatilizing the ethanol solution.

2. The method of claim 1, wherein the benzophenone-based photoinitiator is one or more of 4-acryloxybenzophenone, 2-hydroxy-4- (methacryloxy) benzophenone, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone, 4-methacryloxybenzophenone, and 4-acryloxy-2-hydroxybenzophenone.

3. The method for preparing a biomimetic petroleum pipeline coating according to claim 1, wherein the hydrophilic monomer is one or more of acrylic acid, hydroxyethyl methacrylate, acrylamide, N-hydroxyethyl acrylamide, hydroxyethyl acrylate, and propyl methacrylate.

4. The method for preparing a biomimetic petroleum pipeline coating according to claim 1, wherein the fluorine-containing surfactant is one or more of 1H,1H,2H, 2H-perfluorooctanol acrylate, 2,3,3, 3-pentafluoropropyl 2-fluoroacrylate, perfluorooctyl ethyl acrylate, 2-perfluorododecyl ethyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorododecyl) ethyl acrylate, N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and perfluorooctyl propyl acrylate.

5. The method for preparing the bionic petroleum pipeline coating according to claim 1, wherein the step 2) coating method can be spin coating, brush coating or dip coating.

6. The method for preparing a biomimetic petroleum pipeline coating according to claim 1, wherein the substrate is a metal and a non-metal, the metal comprises iron, copper and stainless steel materials, and the non-metal comprises: epoxy resins and polyurethane resins.

7. The method for preparing a bionic petroleum pipeline coating as claimed in claim 1, wherein the ultraviolet light irradiation treatment in step 2) has an ultraviolet light wavelength of 290-400nm and an irradiation time under the ultraviolet light of more than 0.5 h.

8. A biomimetic petroleum pipeline coating prepared according to any one of claims 1-7.

Technical Field

The invention belongs to the technical field of novel polymer surface coatings and polymer bionic materials. In particular to a bionic petroleum pipeline coating and a preparation method thereof.

Background

Bionic hydrophilic oleophobic surface: the thermoplastic glass fiber reinforced flexible pipe for ocean engineering is a light high-strength non-metal original conveying pipeline developed by Shandong Guanguan pipe industry Limited company combined with a plurality of scientific research institutions of colleges and universities in China under the support of high-technology ship scientific research projects of the national Ministry of industry, has the characteristics of corrosion resistance, fatigue resistance, degradation resistance, long service life and the like, is a high and new technology enterprise which masters the core technology of the product manufacturing technology in China after Airborne company, French Technip company and American Deepflex company in the Netherlands, breaks through monopoly in the field abroad, and fills in the blank of petroleum pipelines in China.

In the practical application process of the pipeline, the common problem of wax deposition on the lining pipe wall of the pipeline still remains unsolved. The problem is a worldwide problem. Aiming at the problems, the wax control principle and the development current situation adopted at home and abroad are as follows:

1. mechanical paraffin removal technology

Paraffin adhered to the wall of the oil pipe is removed mainly by means of a mechanical tool, and the paraffin is cleaned by means of liquid flushing. The method adopts a mechanical external force stripping method, has simple technical principle, is the most common method in the application of the wax-proofing technology, and then has the defects of high cost and low efficiency because the technology addresses the symptoms and does not address the root causes, and the transportation operation needs to be stopped.

2. Thermal insulation technology

The principle of the application method is to maintain the wax precipitation point temperature by utilizing the temperature, prevent the crystallization and keep the crude oil in a molten state. The thermal insulation technology becomes one of the most effective methods for pipeline wax prevention by heating and surface pipeline insulation methods, however, the heating or pipeline insulation requires additional power as a heat source, which greatly increases the crude oil transportation cost and also becomes an important reason for wide use.

3. Chemical agent wax-proofing technology

The principle is that the mixed chemical agent is used to change the adsorption performance of the pipe wall or wax crystals can not grow up in a regular state and can not form wax crystals, and finally the bonding strength of the paraffin crystals and the pipe wall is greatly reduced. The chemical wax-proofing technology has low cost and good effect, so that the application is very wide at present.

Although the above method can solve the problem of paraffin crystallization, there are problems that increase of petroleum transportation cost is required and long-term solution is not available to various degrees.

Disclosure of Invention

In order to solve the problems, the invention provides a bionic petroleum pipeline coating which is inspired by a special body surface structure hydrophilic and oleophobic mechanism of typical biological fugu fish, and the preparation steps of the coating are as follows:

1) preparation of photoinitiator prepolymer with long fluorine-containing chain: dissolving benzophenone photoinitiator, hydrophilic monomer and fluorine-containing surfactant serving as raw materials in a solvent, adding Azodiisobutyronitrile (AIBN) serving as an initiator, and heating at the temperature of 55-90 ℃ for 3-18 hours to prepare a photoinitiator prepolymer with a fluorine-containing long chain; the solvent is one or more of dimethylformamide, ethanol, acetone, isopropanol, butanol, tetrahydrofuran and toluene;

the benzophenone photoinitiator is a compound which takes benzophenone as a main body, wherein a para-position of a phenyl group is provided with a modifying group, and the modifying group at least contains a double bond positioned at the end; preferably 4-acryloxybenzophenone, 2-hydroxy-4- (methacryloyloxy) benzophenone, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone, 4-methacryloxybenzophenone and 4-acryloxy-2-hydroxybenzophenone;

the hydrophilic monomer is acrylic acid or its derivatives, preferably one or more of acrylic acid (AAc), hydroxyethyl methacrylate (HEMA), acrylamide (AAm), N-hydroxyethyl acrylamide (HEAA), hydroxyethyl acrylate (HEA), and propanesulfonic Acid Methacrylate (AMPS);

the hydrophilic end of the fluorine-containing surfactant is an acrylate group, preferably one or a combination of more of 1H,1H,2H, 2H-perfluorooctanol acrylate, 2,3,3, 3-pentafluoropropyl 2-fluoroacrylate, perfluorooctyl ethyl acrylate, 2-perfluorododecyl ethyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorododecyl) ethyl acrylate, N-ethyl perfluorooctyl sulfonamide ethyl acrylate and perfluorooctyl propyl acrylate.

The mass ratio of the benzophenone photoinitiator to the hydrophilic monomer is 1: 5-100, and the mass ratio of the fluorine-containing surfactant to the hydrophilic monomer is 1: 2-50; the ratio of the raw material to the solvent is 5-50 g/mL.

2) Photoinitiated preparation of the coating: dispersing the prepolymer obtained in the step 1) in a solvent, coating the prepolymer on the surface of a substrate containing a carbon-hydrogen bond, carrying out ultraviolet irradiation treatment on a substrate slice, then cleaning the unreacted prepolymer on the substrate with ethanol, then placing a coating sample in a vacuum oven for drying, and volatilizing the ethanol solution.

The step 2) coating method can adopt a spin coating, brush coating or dip coating method.

The substrate can be metal and nonmetal, the metal comprises iron, copper and stainless steel materials, and the nonmetal comprises: epoxy resin and polyurethane resin, wherein the surface of the substrate has carbon-hydrogen bond for photo initiation.

The wavelength of the ultraviolet light is 290-400nm, preferably 365nm, and the irradiation time under the ultraviolet light is more than 0.5 h.

Compared with the prior art, the invention has the following advantages:

the invention discloses a bionic paraffin-control coating material and a preparation method thereof for the first time, the coating can form a hydrophilic and oleophobic bionic functional surface, and paraffin oil is prevented from directly crystallizing on the surface of a pipe wall. The developed bionic wax-proofing technical system has the characteristics of energy conservation, high efficiency, long service life and the like, belongs to a 'permanent treatment' technology for preventing wax deposition on the pipe wall, and is a necessary trend for the development of the future wax-proofing technology of the oil pipeline.

The wax-proof principle of the invention is that the constructed hydrophilic and oleophobic bionic functional surface is utilized to adsorb water molecules in crude oil, a water film is formed on the surface of the pipe wall, paraffin oil is prevented from being directly crystallized on the surface of the solid wall of the pipeline, and simultaneously, the adhesion of oil molecules in the crude oil on the surface is prevented, so that the paraffin crystallization on the pipe wall can be effectively reduced, or even if the crystallization develops into a paraffin layer, the shearing force is very low due to the existence of the water film layer on the pipe wall surface, and the paraffin falls off under the action of the flowing shearing force of the crude oil.

Drawings

FIG. 1 is a schematic representation of a sample of the prepolymer synthesized in example 1.

FIG. 2 is a diagram of the finished product of example 1 after the prepolymer is coated on a glass sheet, a copper sheet and an iron sheet respectively and irradiated by ultraviolet light;

FIG. 3 is a sequence chart of the sliding of a hexadecane drop over the glass slide of example 1;

FIG. 4 is a photograph showing water and hexadecane contact angle measurements.

In the figure 5, paraffin droplets are dripped on the surface of the hydrophilic oleophobic coating and the surface of a common glass sheet, and after paraffin is solidified and adhered, water is used for flushing paraffin, so that paraffin is separated from the surface of the hydrophilic oleophobic coating and is not separated from the surface of the common glass sheet.

Detailed Description

The technical solution adopted by the present invention is further explained and illustrated below in the form of specific embodiments with reference to the accompanying drawings.

Example 1

The synthetic route adopted in this example is as follows:

preparation of photoinitiator prepolymers with long fluorine-containing chains

4-Acryloxybenzophenone (0.60g, 2.4mmol), acrylic acid (8.40g, 116.6mmol), 1H,2H, 2H-perfluorooctanol acrylate (1g, 2.4mmol), initiator azobisisobutyronitrile (16.4mg,0.10mmol) were dissolved in a round bottom flask containing ethanol (30mL) and reacted for 8H in a 75 ℃ oil bath.

Photo-initiation of the preparation of coatings

The glass slides were washed with water and alcohol, air dried for ten minutes and placed on glass slides. The glass flakes were coated with a coating of a photoinitiator prepolymer by brushing. The glass flakes were exposed to UV light (365nm) for 0.5h and the unreacted prepolymer on the substrate was washed with an ethanol solution. The coated sample was then dried in a vacuum oven and the ethanol solution was evaporated.

Example 2

Preparation of photoinitiator prepolymers with long fluorine-containing chains

4-Acryloxy-2-hydroxybenzophenone (0.60g, 2.4mmol), acrylamide (7.68g, 108.2mmol), 2- (perfluorododecyl) ethacrylate (1.72g, 2.4mmol), initiator azobisisobutyronitrile (16.4mg,0.10mmol) were dissolved in a round bottom flask with dimethylformamide (30mL) and reacted for 15h in an oil bath at 80 ℃.

Photo-initiation of the preparation of coatings

The glass slides were washed with water and alcohol, air dried for ten minutes and placed on glass slides. The glass flakes were coated with a coating of a photoinitiator prepolymer by spray coating. The glass flakes were exposed to ultraviolet light (365nm) for 0.5h, after which the unreacted prepolymer on the substrate was washed with an ethanol solution. The coated sample was then dried in a vacuum oven and the ethanol solution was evaporated.

Example 3

Preparation of photoinitiator prepolymers with long fluorine-containing chains

4-methacryloyloxybenzophenone (0.64g, 2.4mmol), hydroxyethyl acrylate (8.08g, 69.6mmol), perfluorooctylpropyl acrylate (1.28g, 2.4mmol), initiator azobisisobutyronitrile (16.4mg,0.10mmol) were dissolved in a round bottom flask containing dimethylformamide (30mL) and reacted for 10h in a 75 ℃ oil bath.

Photo-initiation of the preparation of coatings

The glass slides were washed with water and alcohol, air dried for ten minutes and placed on glass slides. The glass flakes were coated with a coating of a photoinitiator prepolymer by brushing. The glass flakes were exposed to ultraviolet light (365nm) for 0.5h, after which the unreacted prepolymer on the substrate was washed with an ethanol solution. The coated sample was then dried in a vacuum oven and the ethanol solution was evaporated.

As shown in fig. 5, after dropping water, the paraffin on the surface of the glass sheet drops due to the existence of the water film layer on the surface of the pipe wall, the shearing force is very low, and the paraffin falls off under the action of the flowing shearing force of crude oil, so that the paraffin control effect is realized.

The solvent used in the invention is one or a combination of more of dimethylformamide, ethanol, acetone, isopropanol, butanol, tetrahydrofuran and toluene;

the benzophenone photoinitiator is a compound which takes benzophenone as a main body, wherein a para-position of a phenyl group is provided with a modifying group, and the modifying group at least contains a double bond positioned at the end; preferably 4-acryloxybenzophenone, 2-hydroxy-4- (methacryloyloxy) benzophenone, 4' -bis [2- (1-propenyl) phenoxy ] benzophenone, 4-methacryloxybenzophenone and 4-acryloxy-2-hydroxybenzophenone;

the hydrophilic monomer is acrylic acid or its derivatives, such as acrylate, acrylamide, preferably one or more of acrylic acid (AAc), hydroxyethyl methacrylate (HEMA), acrylamide (AAm), N-hydroxyethyl acrylamide (HEAA), hydroxyethyl acrylate (HEA), and methyl acrylic acid propane sulfonic Acid (AMPS);

the hydrophilic end of the fluorine-containing surfactant is an acrylate group, preferably one or a combination of more of 1H,1H,2H, 2H-perfluorooctanol acrylate, 2,3,3, 3-pentafluoropropyl 2-fluoroacrylate, perfluorooctyl ethyl acrylate, 2-perfluorododecyl ethyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorododecyl) ethyl acrylate, N-ethyl perfluorooctyl sulfonamide ethyl acrylate and perfluorooctyl propyl acrylate.