阅读说明：本技术 螺旋桨防污、防腐用两亲性高分子材料及其制备方法 (Amphiphilic polymer material for propeller antifouling and anticorrosion and preparation method thereof ) 是由 刘明光 赵茹 林伟 刘宇 刘立洁 沈凤国 于 2020-06-09 设计创作，主要内容包括：本发明公开了螺旋桨防污、防腐用两亲性高分子材料及其制备方法,包括如下步骤：S1、两亲性高分子材料的制备；S2、金属材料活化；S3、表征与测试,本发明公开一种螺旋桨用两亲性防污、防腐材料及其制备方法,提出了解决螺旋桨防污问题的新原理和新方法,在不锈钢、铜合金表面上接枝PEG刷,有望将螺旋桨的防污和防空泡腐蚀问题一并加以解决,螺旋桨特别是快艇螺旋桨体积不大,所需的表面接枝反应池也无需很大,很容易实现在其表面接入PEG刷,因此本发明易于推广应用。(The invention discloses an amphiphilic polymer material for propeller antifouling and anticorrosion and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing an amphiphilic polymer material; s2, activating a metal material; s3, characterization and test, the invention discloses an amphiphilic antifouling and anticorrosive material for a propeller and a preparation method thereof, and provides a new principle and a new method for solving the antifouling problem of the propeller.)

1. The amphiphilic polymer material for preventing fouling and corrosion of the propeller and the preparation method thereof are characterized in that: the method comprises the following steps:

s1, preparation of an amphiphilic polymer material: adding 0.2mol of TDI into a three-neck flask with a stirrer, a condenser tube and a dropping funnel, heating to 50 ℃, then dropwise adding into 0.2mol of polyethylene glycol monomethyl ether-acetone mixed solution, heating to 60 ℃, reacting for 2 hours to obtain a prepolymer, and measuring the NCO content of the prepolymer;

adding 0.2mol of polyether amine into another three-necked bottle with a stirrer, a condenser pipe and a dropping funnel, dropwise adding the prepared prepolymer into the three-necked bottle at room temperature, heating to 60 ℃, reacting for 2 hours, detecting the disappearance of NCO characteristic peak by infrared spectrum, gradually dropwise adding 0.2mol or 0.4mol KH560 through the dropping funnel, continuously reacting for a period of time at reaction temperature, extracting solvent under reduced pressure when the disappearance of epoxy characteristic peak is detected by infrared spectrum, obtaining expected products, namely amphiphilic monosilane and amphiphilic disilane, and sequentially naming the products as silane No. 1 and No. 2;

s2, activating a metal material;

and S3, characterization and testing.

2. The amphiphilic polymer material for preventing propeller fouling and corrosion and the preparation method thereof according to claim 1, wherein the activation of the metal material in S2 comprises:

1) and preparing a washing liquid:

piranha lotion treatment: taking concentrated sulfuric acid and 30% hydrogen peroxide according to a volume ratio of 4: 1, slowly adding hydrogen peroxide into concentrated sulfuric acid to prepare piranha washing liquor;

2) and a metal material activation process:

(1) grinding brass (H62 type) with the size of 20mm multiplied by 20mm for experiments by 500 and 1000 abrasive paper respectively, then ultrasonically cleaning and degreasing by acetone, putting the degreased copper sheet into a mixed solution of 2.5mol/LNaOH and 0.1mol/L ammonium persulfate, soaking for 60 minutes, taking out, sequentially cleaning by deionized water and ethanol, blow-drying by cold air, putting into an oven with the temperature of 80 ℃ for drying for 30 minutes, putting the pretreated metal sheet into a 5% (w/v) silane ethanol-water (90/10) solution, and grafting the prepared amphiphilic silane onto the surface of stainless steel;

(2) putting 500 and 1000 sandpaper-sanded AISI316L stainless steel into piranha washing solution, heating for 30min at 65 ℃ to remove dirt on the metal surface, then respectively putting into deionized water, ethanol and acetone for ultrasonic cleaning for 10min, taking out and drying with nitrogen, putting the pretreated metal sheet into 5% (w/v) silaneethanol-water (90/10) solution, and grafting the prepared amphiphilic silane onto the stainless steel surface.

3. The amphiphilic polymer material for preventing propeller fouling and corrosion and the preparation method thereof according to claim 1, wherein the characterization and test in S3 comprises:

1) and total reflection Fourier infrared spectrum (FTIR) characterization:

2) testing of metal surface X-ray photoelectron spectroscopy (XPS):

3) contact angle test:

4) and electrochemical measurement:

5) test for protein adsorption resistance

(1) Preparation of protein solution and drawing up of standard curve

(2) Preparation of buffer solution of PBS (pH = 7.4):

(3) test for protein adsorption resistance:

(4) ultraviolet spectrum (UV-Vis).

Technical Field

The invention relates to the technical field of amphiphilic polymer materials, in particular to an amphiphilic polymer material for propeller antifouling and anticorrosion and a preparation method thereof.

Background

In the marine environment, particularly for long-time berthing, marine organisms are easy to parasitize at the part below a hull waterline, after the marine organisms are attached to the surface of the hull, the speed of the ship is reduced, the fuel consumption is increased, organic acid is also generated by the attachment of the marine organisms, the corrosion degree of the hull is aggravated, the service life is obviously shortened, the average speed of the ship polluted by the marine organisms is reported to be reduced by more than about 5 percent, the most serious reduction can reach 25 percent, and in order to reduce the parasitism of the marine organisms at the part of the hull, the antifouling paint is the cheapest, most effective and most convenient way for solving the problem of the parasitism of the marine organisms, but the antifouling paint can quickly fall off at the part which is frequently abraded and washed, such as a propeller, so the antifouling problem cannot be;

the propeller is a propeller for ship navigation, when the ship navigates, the propeller rotates at a high speed, scouring of high-speed water flow and friction of mud and sand are caused, marine organisms are difficult to attach to the surface of the propeller, but during ship berthing, the marine organisms often attach to the surface of the propeller, the attachment is often combined firmly and is difficult to strip by means of rotation shearing force, water flow scouring or mud and sand friction, the attachment of the marine organisms to the surface of the propeller increases the surface roughness of the propeller, the propulsion efficiency is reduced, the navigation speed is reduced, and the fuel consumption is increased;

the antifouling of the propeller is a difficult problem to be solved, so far, people mainly start from the angle of material composition design and prepare the copper alloy propeller with better antifouling performance by adjusting the components of the copper alloy, but the copper alloy is required to have a certain corrosion rate to ensure that a certain amount of copper ions are separated out to play an antifouling role and also can lose the antifouling function due to the shielding effect of corrosion products, so the parasitic problem of marine organisms cannot be thoroughly eradicated, the propellers of large ships and speedboats are generally made of stainless steel materials, the rest of the propellers are generally made of common copper alloy materials, and the problem of how to improve the antifouling performance of the propellers is urgently needed to be solved, the invention develops a new method, the hydrophilic polymer-polyethylene glycol (PEG) is grafted on the surfaces of the stainless steel and the copper alloy to obtain a polymer brush with the nanometer thickness for preventing the marine organisms from attaching on the metal surface, the PEG brush grafted on the surface of the propeller has important theoretical and practical significance for solving the problems of fouling prevention and cavitation corrosion prevention of the propeller, can improve the fouling prevention and cavitation corrosion prevention performance of the existing marine propeller, prolongs the maintenance period and the service life of the propeller, and generates obvious economic benefit.

Disclosure of Invention

The invention provides an amphiphilic polymer material for propeller antifouling and anticorrosion and a preparation method thereof, which can effectively solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the amphiphilic polymer material for preventing fouling and corrosion of propeller and its preparation process includes the following steps:

s1, preparation of an amphiphilic polymer material: adding 0.2mol of TDI into a three-neck flask with a stirrer, a condenser tube and a dropping funnel, heating to 50 ℃, then dropwise adding into 0.2mol of polyethylene glycol monomethyl ether-acetone mixed solution, heating to 60 ℃, reacting for 2 hours to obtain a prepolymer, and measuring the NCO content of the prepolymer;

adding 0.2mol of polyether amine into another three-necked bottle with a stirrer, a condenser pipe and a dropping funnel, dropwise adding the prepared prepolymer into the three-necked bottle at room temperature, heating to 60 ℃, reacting for 2 hours, detecting the disappearance of NCO characteristic peak by infrared spectrum, gradually dropwise adding 0.2mol or 0.4mol KH560 through the dropping funnel, continuously reacting for a period of time at reaction temperature, extracting solvent under reduced pressure when the disappearance of epoxy characteristic peak is detected by infrared spectrum, obtaining expected products, namely amphiphilic monosilane and amphiphilic disilane, and sequentially naming the products as silane No. 1 and No. 2;

s2, activating a metal material;

and S3, characterization and testing.

Further, the metal material activation in S2 includes:

1) and preparing a washing liquid:

piranha lotion treatment: taking concentrated sulfuric acid and 30% hydrogen peroxide according to a volume ratio of 4: 1, slowly adding hydrogen peroxide into concentrated sulfuric acid to prepare piranha washing liquor;

2) and a metal material activation process:

(1) grinding brass (H62 type) with the size of 20mm multiplied by 20mm for experiments by 500 and 1000 abrasive paper respectively, then ultrasonically cleaning and degreasing by acetone, putting the degreased copper sheet into a mixed solution of 2.5mol/LNaOH and 0.1mol/L ammonium persulfate, soaking for 60 minutes, taking out, sequentially cleaning by deionized water and ethanol, blow-drying by cold air, putting into an oven with the temperature of 80 ℃ for drying for 30 minutes, putting the pretreated metal sheet into a 5% (w/v) silane ethanol-water (90/10) solution, and grafting the prepared amphiphilic silane onto the surface of stainless steel;

(2) putting 500 and 1000 sandpaper-sanded AISI316L stainless steel into piranha washing solution, heating for 30min at 65 ℃ to remove dirt on the metal surface, then respectively putting into deionized water, ethanol and acetone for ultrasonic cleaning for 10min, taking out and drying with nitrogen, putting the pretreated metal sheet into 5% (w/v) silaneethanol-water (90/10) solution, and grafting the prepared amphiphilic silane onto the stainless steel surface.

Further, the characterization and testing in S3 includes:

1) and total reflection Fourier infrared spectrum (FTIR) characterization:

the total reflection (ATR) Fourier infrared spectrum (FTIR) of the metal surface modified by the silane is measured by a Spectrum BXII Fourier infrared spectrometer produced by Perkin-Elemer instruments, and the test wave number range is 400-4000 cm^-1Resolution of 0.8cm^-1；

2) Testing of metal surface X-ray photoelectron spectroscopy (XPS):

x-ray photoelectron spectroscopy (XPS) employs a PHI-5300 multifunctional electron spectrometer manufactured by Perkin-Elmer, USA, and uses Mg target as a radiation emission source, and the following energy is applied: the full scan was 89.45eV, the narrow scan was 35.75eV, and the scale was C1s284.6eV;

3) contact angle test:

the contact angle between the metal surface and water is tested by an JGW-360a type contact angle tester produced by Shenghui tester Co., Ltd, the testing temperature is 25 ℃, water drops are dropped on the metal surface in a hanging drop mode, after the water drops are stabilized, the included angle between the water drops and the material surface is observed by a JGW-360a type contact angle tester, the obtained angle value is the static water contact angle, three points on the diagonal line are taken from the surface of each sample for measurement, and the average value is taken;

4) and electrochemical measurement:

the electrochemical measurement adopts a three-electrode system, a platinum mesh is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a NaCl solution with the concentration of 4% is prepared as a dielectric solution, the measurement of an Electrochemical Impedance Spectroscopy (EIS) is carried out on a CS350 electrochemical workstation, the amplitude of a sine wave is 10mV, the frequency range of the sine wave is 10 mHz-100 kHz, the scanning stepping rate of a polarization curve is 2mV/s, and all potentials are relative to the potential of the saturated calomel electrode;

5) test for protein adsorption resistance

(1) Preparation of protein solution and drawing up of standard curve

a, preparing a protein solution:

standard protein solution, prepared with G-Bovine Serum Albumin (BSA) to 1.0mg/mL standard protein solution, configuration of coomassie brilliant blue G-250 dye reagent: weighing 100mg of Coomassie brilliant blue G-250, dissolving in 50mL of 95% ethanol, adding 120mL of 85% phosphoric acid, and diluting with water to 1L to obtain a Coomassie brilliant blue reagent;

b determination of standard curve:

taking 7 test tubes, taking 1 test tube as a blank, respectively adding water and a reagent into the other test tubes, diluting a bovine serum albumin standard solution into solutions of 0, 0.01, 0.02, 0.04, 0.06, 0.08 and 0.1mg/mL, respectively and accurately transferring 1.0mL into the test tubes, respectively adding 4.0mL of Coomassie brilliant blue G-250 solution into each test tube, shaking uniformly, reacting for 5min at room temperature, measuring light absorption at 595nm wavelength, and obtaining a standard curve by taking the concentration of the bovine serum albumin standard solution as an abscissa and the light absorption as an ordinate;

(2) preparation of buffer solution of PBS (pH = 7.4):

weighing 71.6g of Na2HPO4 & 12H2O, dissolving the mixture in 1000mL of water to prepare a 0.2mol/LNa2HPO4 solution, weighing 31.2g of NaH2PO4 & 2H2O, dissolving the mixture in 1000mL of water to prepare a 0.2mol/LNaH2PO4 solution, taking 81mL of 0.2mol/L Na2HPO4 solution and 19mL of 0.2mol/LNaH2PO4 solution, mixing the solutions uniformly, adding deionized water to dilute the solution to 1000mL, adding 0.9% (g/100 mL) of NaCl, and preparing a buffer solution of 0.02mol/L PBS (pH = 7.4) for later use;

(3) test for protein adsorption resistance:

the metal plate is grafted and modified by silane, and then is soaked in PBS buffer solution, the surface under the environment similar to the organism is obtained under the condition of room temperature, then the metal sheet is soaked in protein solution for a certain time, and is taken out, and after each sample adsorbs protein, the absorbance of the protein solution is measured by the following method.

Taking a plurality of test tubes, taking 1 test tube as a blank, respectively adding 1.0mL of protein solution after protein adsorption into the other test tubes, then adding 4.0mL of Coomassie brilliant blue reagent, after finishing adding the reagent for 2-5 minutes, starting to use a cuvette, measuring the light absorption value A595 of each sample at 595nm on a spectrophotometer, taking a blank control as a No. 1 test tube, namely 1.0mLH2O and 4.0mL of Coomassie brilliant blue solution, measuring the value of each protein solution after protein adsorption at A595, and finding out the protein content of an unknown sample according to a standard curve;

(4) ultraviolet spectrum (UV-Vis) characterization:

and (3) after the protein is adsorbed on the sample by adopting a UV-3000 ultraviolet-visible spectrometer, measuring the absorbance of the protein solution.

Compared with the prior art, the invention has the beneficial effects that: the invention discloses an amphiphilic antifouling and anticorrosive material for propellers and a preparation method thereof, wherein a suspension polymerization method is adopted, Toluene Diisocyanate (TDI) is taken as a raw material, the toluene diisocyanate is sequentially reacted with hydrophilic methoxy polyethylene glycol (MPEG) and hydrophobic polyether amine, the synthesized prepolymer containing terminal amino groups is reacted with glycidyl ether oxypropyl trimethoxy silane (KH 560), finally, amphiphilic silane is synthesized, the amphiphilic silane is grafted onto an activated metal surface by a sol-gel method, and the characteristics of the modified metal surface are characterized;

(1) provides a new principle and a new method for solving the problem of the fouling prevention of the propeller, grafts the PEG brush on the surface of the stainless steel and the copper alloy, is expected to solve the problems of the fouling prevention and the cavitation erosion prevention of the propeller together,

aiming at the antifouling problem of the existing propeller, the invention provides a self-assembled monolayer PEG brush grafted with a water-soluble polymer on a stainless steel and copper alloy propeller to prevent marine organisms from attaching to the surface of the propeller and achieve the antifouling effect, and meanwhile, the PEG brush can also buffer the impact effect of cavitation bubble breakage on the surface of the propeller and improve the cavitation bubble corrosion resistance of the propeller, so that the PEG brush assembled on the surface of the propeller with a specific structure and composition is expected to simultaneously solve the antifouling and cavitation bubble corrosion resistance problems of the propeller, prolong the maintenance period of the propeller and prolong the service life of the propeller;

(2) the popularization and application prospect is clear:

the invention has definite application prospect, the volume of the propeller, particularly the propeller of a speed boat is not large, the required surface grafting reaction tank does not need to be large, and the PEG brush is easily connected to the surface of the propeller, so the invention is easy to popularize and apply.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.

In the drawings:

FIG. 1 is a schematic diagram of the preparation of the amphiphilic polymeric material of the present invention;

FIG. 2 is a schematic diagram of a standard curve for BSA determination by the constant method of the present invention;

FIG. 3 is an ATR-FTIR spectrum of a metal surface of the present invention;

FIG. 4 is an XPS spectrum of a stainless steel surface of the present invention;

FIG. 5 is a schematic representation of XPS spectra of untreated and No. 2 amphiphilic silane modified copper plate surfaces of the present invention;

FIG. 6 is a schematic diagram of the electrochemical impedance spectroscopy of the surface of a silane-modified copper sheet of the present invention;

FIG. 7 is a schematic diagram of the electrochemical impedance spectrum of the graft-modified steel plate of the present invention;

FIG. 8 is a graph showing the absorbance of A595 in the same concentration of BSA over time for the metal plates of the present invention.

Detailed Description

The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.