CN108822722B - Hydrophobic polyurethane marine antifouling coating material based on lotus leaf bionics and preparation method thereof - Google Patents
Hydrophobic polyurethane marine antifouling coating material based on lotus leaf bionics and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a hydrophobic polyurethane marine antifouling coating material based on lotus leaf bionics. First acylating acryloyl chloride with 2-hexyldecanol to obtain 2-hexylacrylic decyl ester, sulfhydrylating, reacting with diphenylmethane-4, 4' -diisocyanate and polypropylene glycol to obtain oligomer, using stannous isooctanoate as catalyst and nano TiO2The hydroxyl on the surface initiates L-lactide to carry out ring-opening polymerization to obtain a prepolymer, and finally, an oligomer is added to successfully prepare the hydrophobic polyurethane coating material with a micro-nano structure and a degradable main chain. Experimental research shows that the hydrophobic polyurethane coating material obtained by adopting the method of combining polycondensation and click reaction has a static contact angle of 114 degrees, is used as a novel environment-friendly marine antifouling material, achieves the antifouling purpose by reducing the adhesion of marine organisms, and does not have any toxic action on the marine organisms, thereby reducing the damage of the use of the coating to the marine ecological environment.
Description
Technical Field
The invention belongs to the field of chemical coatings, and particularly relates to a lotus leaf bionic hydrophobic polyurethane marine antifouling coating material and a preparation method thereof.
Background
Under the inspired of bionics, a hydrophobic surface has gained great attention in the past decades due to excellent self-cleaning, drag reduction, pollution resistance and freezing resistance, and the specific hydrophobicity of the hydrophobic surface can reduce the corrosion of corrosive media such as water and the like on the surface of a metal material. If the hydrophobic high-rise building exterior wall coating is used, natural rainwater can be used for cleaning and dedusting, so that the energy is saved, the environment is protected, and high maintenance cost is saved; the hydrophobic coating is used as an anti-icing coating of the wire, so that the energy utilization efficiency in the power transmission system can be improved, and the safety of materials and the system can be improved; the hydrophobic coating is used as an antifouling coating of the ship, so that the adhesion and propagation of marine fouling organisms are effectively reduced, the service life of the ship body is prolonged, and the navigation resistance is obviously reduced due to the reduction of the surface roughness of the ship body while antifouling. Therefore, the application of the hydrophobic surface technology to the corrosion protection field is an important breakthrough and has wide development prospect.
The nano material is added into the polyurethane matrix, so that a new additive effect can be given to the material, and the performance of the composite material is obviously influenced by an extremely low content. The nano material can improve the traditional comprehensive properties of polyurethane such as electricity, heat, mechanics and the like, and can also improve the barrier property of the polyurethane. Nano TiO22Has the excellent characteristics of antibiosis and sterilization, greatly reduces the attachment of fouling organisms and keeps the surface of the coating clean. The antibacterial effect lies in that the nano TiO2Quantum size effects of (a). When the energy of the electrons reaches or exceeds the band gap energy of the nano TiO2 under the irradiation of sunlight, especially ultraviolet rays, the electrons can be excited from a valence band to a conduction band, and corresponding holes are generated in the valence band, namely electron-hole pairs are generated. The generated electron-hole pairs can rapidly reach the surface of the nano-particles, and react with water and air adsorbed on the surface to generate superoxide anion radicals and hydroxyl radicals with strong chemical activity, and when encountering bacteria, the superoxide anion radicals and the hydroxyl radicals can directly attack the cells of the bacteria, so that organic matters in the cells of the bacteria are degraded, thereby killing the bacteria and decomposing the bacteria (Yang H J, Xu J B, Pispass S, Zhang G Z, Macromolecules, 2012, 45(8): 3312-3317). Nano TiO22Having photocatalytic antibacterial propertiesThe antibacterial antifouling paint has the bactericidal effect, can be used in antibacterial antifouling paint, and has antibacterial effect
The combination of the bacterial property and the hydrophobicity can effectively prevent and control fouling organisms.
The hydrophobic surface can be obtained by using a relatively short chain highly branched hydrocarbon chain, the side chain of 2-hexyl-1-decanol is used as the hydrophobicity of a long hydrocarbon chain structure to react with acryloyl chloride to generate acrylic ester, DMPA is used as a photoinitiator to perform click reaction with 1-thioglycerol to realize the preparation of a polyurethane hard segment, and the hydrophobic polyurethane with the end group of-NCO is prepared to connect the nano titanium dioxide/polylactic acid composite material by using the connection function of diphenyl diisocyanate functional group-NCO, so that the aim of modifying the hydrophobic polyurethane is fulfilled, and the self-cleaning performance and the thermal stability of the material can be enhanced by adding the nano titanium dioxide. The use of these green materials can eliminate the undesirable environmental and commercial consequences of using fluorocarbons.
Disclosure of Invention
The invention aims to provide a hydrophobic polyurethane marine antifouling coating material and a preparation method thereof. By adopting a method combining polycondensation and click reaction, the main chain degradable hydrophobic polyurethane is linked to the nano TiO2 in a chemical bond form to prepare the hydrophobic marine antifouling coating material with the self-cleaning function, so that a new way is provided for solving the fouling of marine fouling organisms on marine equipment such as ships and the like, reducing the navigation resistance and improving the energy efficiency of the ships.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a hydrophobic polyurethane marine antifouling coating material based on lotus leaf bionics comprises the following steps:
(1) putting 2-hexyldecanol into a container, sequentially adding triethylamine and acryloyl chloride taking tetrahydrofuran as a solvent, stirring in an ice bath, refluxing and reacting fully to obtain a 2-ethyl decyl acrylate crude product, and adding saturated NaHCO with twice volume of tetrahydrofuran3Washing the solution, performing ultrasonic treatment to fully mix the solution, standing the solution after no bubbles are generated, taking the upper layer liquid, performing rotary evaporation, controlling the temperature to be 70-80 ℃, and drying to obtain 2-decyl hexyl acrylate; sequentially taking 1-thioglycerol and a photoinitiator DMPA. Mixing 2-decyl hexyl acrylate, reacting fully under the irradiation of an ultraviolet lamp, washing the product with distilled water and saturated sodium chloride solution in sequence, drying with anhydrous magnesium sulfate, standing overnight, and rotary-steaming to obtain sulfhydrylated 2-decyl hexyl acrylate (sDHA);
(2) putting tetrahydrofuran in a container, sequentially adding nano titanium dioxide, L-lactide and a catalyst stannous isooctanoate, performing ultrasonic treatment to uniformly disperse the tetrahydrofuran, stirring and refluxing at 135 ℃ under the protection of nitrogen to react to obtain a prepolymer, naturally cooling the prepolymer to room temperature, dissolving the prepolymer with trichloromethane, precipitating with petroleum ether with the volume of three times that of the trichloromethane, repeatedly washing, and performing vacuum drying at 40 ℃ to obtain an intermediate prepolymer (TiO)2-g-PLLA）；
(3) Adding diphenylmethane-4, 4' -diisocyanate, polypropylene glycol and sDHA into a reaction device with a condenser pipe and introduced with nitrogen, adding dimethyl sulfoxide, reacting fully at 90 ℃ under stirring to obtain oligomer, and adding TiO2-g-PLLA, uniformly mixing, fully reacting to obtain a macromolecular linear polymer, cooling to room temperature after reaction, slowly dripping the solution into petroleum ether with 6 times of volume for precipitation, standing, centrifuging, and vacuum drying at 60 ℃ to obtain the hydrophobic polyurethane marine antifouling coating material (TiO)2-g -PLLA-PU-sDHA)。
And the 2-hexyldecanol, the nano titanium dioxide, the tetrahydrofuran, the normal hexane, the dimethyl sulfoxide and the polypropylene glycol need to be subjected to water removal and purification.
In the step (1), the ratio of acryloyl chloride, tetrahydrofuran, triethylamine and 2-hexyldecanol is 1.2-1.8mol: 1.2-1.6 mol:1.2 mol: 1mol, the ratio of 1-thioglycerol to 2-hexyldecyl acrylate is 1mol:1.1-1.8mol, and the amount of the photoinitiator DMPA is 5 wt%.
In the step (2), the prepolymer washing method comprises the steps of dissolving the filtered crude product in chloroform, adding methanol containing concentrated hydrochloric acid into the solution to remove Sn residues, and centrifuging; precipitating with petroleum ether, and centrifuging; finally, the product is washed by methanol, centrifugally filtered and placed in an environment at 40 ℃ for vacuum drying.
The prepolymer washing method comprises the steps of dissolving the filtered crude product in 30 mL of trichloromethane, adding the solution into 50 mL of methanol containing 1mL of concentrated hydrochloric acid to remove Sn residues, and centrifuging the solution for 3min at 5200 rad/min; precipitating with 60mL petroleum ether, and centrifuging at 6000rad/min for 5 min; finally, the product is washed by 50 mL of methanol, centrifugally filtered for 5min, and placed in an environment at 40 ℃ for vacuum drying for 48 h.
In the step (3), the ratio of the diphenylmethane-4, 4' -diisocyanate to the polypropylene glycol to the sDHA to the dimethyl sulfoxide is 2.5-2.7g, 4.0-4.3g, 2.2-2.4g and 50-70 ml.
The hydrophobic polyurethane marine antifouling coating material prepared by the method.
The invention has the beneficial effects that:
(1) the raw materials for synthesizing the material are environment-friendly and low in price, and the synthesis method is simple, so that the material has a very broad popularization prospect.
(2) The invention successfully prepares the hydrophobic polyurethane marine antifouling coating material, and tests show that TiO2The static contact angle of the PLLA-PU-sDHA is 114 degrees, which shows that the material has good hydrophobicity, so that marine fouling organisms are difficult to attach to the ship body, and the purposes of preventing fouling and reducing drag are achieved.
(3) In the composite material prepared by the invention, nano TiO is added2The photocatalytic antibacterial bactericidal effect, the biodegradability of the polylactic acid and the structural hydrophobicity of the sulfhydrylation 2-hexyl decyl acrylate are combined, so that the comprehensive performance of the coating material is excellent.
Drawings
FIG. 1 is a general reaction scheme of example 1;
FIG. 2 is an infrared spectrum of DHA (a) and sDHA (b);
FIG. 3 shows sDHA (b) and TiO2-ir spectrum of g-PLLA-PU-sdha (c);
FIG. 4 is a NMR spectrum of DHA;
fig. 5 is a nuclear magnetic resonance hydrogen spectrum of sDHA;
FIG. 6 is TiO2g-PLLA-PU-sDHA coating Material (a)) And (b) testing contact angle with common polyurethane coating material.
Detailed Description
Examples of the present invention are given below. It should be noted that the following examples are several specific implementation methods of the present invention, and the scope of the present invention is not limited thereto.
Example 1:
(1) purification of reagents
1) Water removal of 2-hexyldecanol: refluxing 200ml 2-hexyldecanol and CaH for 4 hours, centrifuging to remove precipitate, taking supernatant, putting into activated molecular sieve, sealing and storing.
2) Drying the nano TiO 2: and (3) placing the nano TiO2 in a vacuum oven, controlling the temperature to be 70-80 ℃, and drying for 12 h.
3) Water removal of tetrahydrofuran/hexane/dimethylsulfoxide: weighing a certain volume of tetrahydrofuran/n-hexane/dimethyl sulfoxide into a 500 mL round-bottom flask, taking a proper amount of metal sodium, cutting into sodium particles, adding the sodium particles into the tetrahydrofuran/n-hexane/dimethyl sulfoxide, condensing and refluxing for 3-7 days at about 100 ℃ by using a heat collection type constant temperature heating magnetic stirrer, adding an indicator benzophenone at a proper time until the solution turns blue, distilling and collecting fractions at about 67 ℃, and removing water.
4) Dehydration of polypropylene glycol: the polypropylene glycol was placed in a vacuum oven and dehydrated for 6 h at 110 ℃.
(2) Preparation of sulfhydrylated decyl 2-hexyl acrylate
And (2) putting 2-hexyldecanol into a three-neck flask, sequentially adding triethylamine and acryloyl chloride using tetrahydrofuran as a solvent, wherein the ratio of the acryloyl chloride to the tetrahydrofuran to the triethylamine to the 2-hexyldecanol is 1.5 mol:1.2 mol:1.2 mol: 1mol, and stirring in an ice bath for reflux reaction for 6-8h to obtain a 2-decyl ethacrylate crude product. Saturated NaHCO in twice the volume amount with tetrahydrofuran3Washing the crude product with the solution, performing ultrasonic treatment for 20 min to fully mix the crude product, pouring the mixture into a separating funnel after no bubbles are generated, standing for 2-3h, taking the upper-layer liquid, performing rotary evaporation, putting the upper-layer liquid into a vacuum drying oven, controlling the temperature to be about 70-80 ℃, and drying for 12h to obtain 2-decyl hexyl acrylate; sequentially taking 1-thioglycerol and light guidePlacing a hair agent DMPA and 2-decyl hexyl acrylate in a beaker, wherein the proportion of 1mol to 1.2mol of 1-thioglycerol and 2-decyl hexyl acrylate is adopted, the using amount of a photoinitiator DMPA is 5 percent by weight, reacting for 5 hours under the irradiation of an ultraviolet lamp, washing the product for 3 times by using distilled water and a saturated sodium chloride solution in sequence, finally drying by using anhydrous magnesium sulfate, standing overnight, and carrying out rotary evaporation to obtain the sulfhydrylated 2-decyl hexyl acrylate (sDHA).
(3) Preparation of polyurethane prepolymers
Taking 25 mL tetrahydrofuran, adding nano titanium dioxide, L-lactide and stannous isooctanoate serving as a catalyst into a flask in sequence, carrying out ultrasonic treatment for 30 min to ensure that the nano titanium dioxide, the L-lactide and the stannous isooctanoate are uniformly dispersed, and carrying out stirring reflux reaction for 24 h at 120 ℃ under the protection of nitrogen to obtain a prepolymer. Naturally cooling the prepolymer to room temperature, and carrying out centrifugal filtration for 5 min; dissolving the filtered crude product in 30 mL of methanol, adding 50 mL of methanol containing 1mL of concentrated hydrochloric acid into the solution to remove Sn residues, and carrying out centrifugal filtration for 5 min; washing with 20mL of dichloromethane, and carrying out centrifugal filtration for 5 min; finally, the mixture is washed by 50 mL of methanol and centrifugally filtered for 5 min. The product is placed in an environment with the temperature of 30 ℃ for vacuum drying for 24 h to obtain an intermediate prepolymer (TiO)2-g-PLLA）。
(4) Preparation of hydrophobic polyurethanes
Adding 2.5g of diphenylmethane-4, 4' -diisocyanate, 4.0g of polypropylene glycol and 2.2g of sDHA into a three-neck flask reaction device with a condenser tube and introduced with nitrogen, adding 50 mL of dimethyl sulfoxide, reacting for 16 h at 90 ℃ under a stirring state to obtain an oligomer, and adding TiO2-g-PLLA 0.2 g, and reacting for 10 hours after uniformly mixing to obtain the macromolecular linear polymer. After the reaction is finished, when the temperature is reduced to room temperature, dropwise adding the solution into n-hexane with the volume of 8 times, precipitating, centrifugally filtering for 5min, and putting the product into a vacuum drying oven at 50 ℃ for 12h to obtain the hydrophobic polyurethane coating material (TiO)2-g-PLLA-PU-sDHA). The best static contact angle result was found to be 114 °.
Example 2:
2.5g of diphenylmethane-4, 4' -diisocyanate, 4.2g of polypropylene glycol and 2.4g of sDHA were charged into a three-necked flask reaction apparatus equipped with a condenser and charged with nitrogen, and 60mL of dimethyl sulfoxide was added thereto, and the other steps and methods were the same as those of example 1, and the result of measuring a static contact angle was 100 °.
Example 3:
2.8g of diphenylmethane-4, 4' -diisocyanate, 4.4g of polypropylene glycol and 2.6g of sDHA were charged into a three-necked flask reaction apparatus equipped with a condenser and charged with nitrogen, 70mL of dimethyl sulfoxide was charged, and the other steps and methods were the same as those of example 1, and the result of detecting a static contact angle was 103 °.
Example 4:
3g of diphenylmethane-4, 4' -diisocyanate, 4g of polypropylene glycol and 2.5g of sDHA were put into a three-necked flask reaction device with a condenser and a nitrogen gas inlet, 80 mL of dimethyl sulfoxide was added, and the other steps and methods were the same as in example 1, and the result of the static contact angle was 107 degrees.
Claims (7)
1. A preparation method of a hydrophobic polyurethane marine antifouling coating material based on lotus leaf bionics is characterized by comprising the following steps
(1) Putting 2-hexyldecanol into a container, sequentially adding triethylamine and acryloyl chloride taking tetrahydrofuran as a solvent, stirring in an ice bath, refluxing and reacting fully to obtain a 2-ethyl decyl acrylate crude product, and adding saturated NaHCO with twice volume of tetrahydrofuran3Washing the solution, performing ultrasonic treatment to fully mix the solution, standing the solution after no bubbles are generated, taking the upper layer liquid, performing rotary evaporation, controlling the temperature to be 70-80 ℃, and drying to obtain 2-decyl hexyl acrylate; mixing 1-thioglycerol, a photoinitiator DMPA and 2-decyl hexyl acrylate in sequence, reacting fully under the irradiation of an ultraviolet lamp, washing a product with distilled water and a saturated sodium chloride solution in sequence, drying with anhydrous magnesium sulfate, standing overnight, and performing rotary evaporation to obtain sulfhydrylated 2-decyl hexyl acrylate sDHA;
(2) putting tetrahydrofuran in a container, sequentially adding nano titanium dioxide, L-lactide and a catalyst stannous isooctanoate, performing ultrasonic treatment to uniformly disperse the tetrahydrofuran, stirring and refluxing at 135 ℃ under the protection of nitrogen to react to obtain a prepolymer, naturally cooling the prepolymer to room temperature, dissolving the prepolymer with trichloromethane, and dissolving the prepolymer with trichloromethanePetroleum ether precipitation with the volume of three times of methane, repeated washing and vacuum drying at 40 ℃ to obtain intermediate prepolymer TiO2-g-PLLA；
(3) Adding diphenylmethane-4, 4' -diisocyanate, polypropylene glycol and sDHA into a reaction device with a condenser pipe and introduced with nitrogen, adding dimethyl sulfoxide, reacting fully at 90 ℃ under stirring to obtain oligomer, and adding TiO2-g-PLLA, uniformly mixing, fully reacting to obtain a macromolecular linear polymer, cooling to room temperature after reaction, slowly dripping the solution into petroleum ether with 6 times of volume for precipitation, standing, centrifuging, and vacuum drying at 60 ℃ to obtain the hydrophobic polyurethane marine antifouling coating material TiO2-g -PLLA-PU-sDHA。
2. The preparation method of the hydrophobic polyurethane marine antifouling coating material as claimed in claim 1, wherein the 2-hexyldecanol, the nano titanium dioxide, the tetrahydrofuran, the n-hexane, the dimethyl sulfoxide and the polypropylene glycol need to be purified by water.
3. The preparation method of the hydrophobic polyurethane marine antifouling coating material as claimed in claim 1, wherein in the step (1), the ratio of the acryloyl chloride to the tetrahydrofuran to the triethylamine to the 2-hexyldecanol is 1.2-1.8mol: 1.2-1.6 mol:1.2 mol: 1mol, the ratio of the 1-thioglycerol to the 2-hexyldecanoate is 1mol:1.1-1.8mol, and the amount of the photoinitiator DMPA is 5 wt%.
4. The method for preparing the hydrophobic polyurethane marine antifouling coating material according to the claim 1, wherein in the step (2), the prepolymer is washed by dissolving the filtered crude product in chloroform, adding methanol containing concentrated hydrochloric acid into the solution to remove Sn residues, and centrifuging; precipitating with petroleum ether, and centrifuging; finally, the product is washed by methanol, centrifugally filtered and placed in an environment at 40 ℃ for vacuum drying.
5. The method for preparing hydrophobic polyurethane marine antifouling coating material according to claim 4, wherein the prepolymer washing method comprises dissolving the filtered crude product in 30 mL of chloroform, adding 1mL of concentrated hydrochloric acid in 50 mL of methanol to remove Sn residues, and centrifuging at 5200rad/min for 3 min; precipitating with 60mL petroleum ether, and centrifuging at 6000rad/min for 5 min; finally, the product is washed by 50 mL of methanol, centrifugally filtered for 5min, and placed in an environment at 40 ℃ for vacuum drying for 48 h.
6. The preparation method of the hydrophobic polyurethane marine antifouling coating material as claimed in claim 1, wherein in the step (3), the ratio of the diphenylmethane-4, 4' -diisocyanate, the polypropylene glycol, the sDHA and the dimethyl sulfoxide is 2.5-2.7g, 4.0-4.3g, 2.2-2.4g and 50-70 ml.
7. A hydrophobic polyurethane marine antifouling coating material prepared by the method of any one of claims 1 to 6.
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| DE10120989A1 (en) * | 2001-04-25 | 2002-11-07 | Inst Polymerforschung Dresden | Hydrophobic permanent coatings on substrates and processes for their production |
| CN103694839B (en) * | 2013-12-16 | 2015-09-16 | 浙江大学 | The preparation method of a kind of antimicrobial form low surface energy modified polyurethane antifouling coating agent |
| CN104910779B (en) * | 2015-06-04 | 2017-06-27 | 西安交通大学 | A kind of super-hydrophobic Acrylic Polyurethane Coating and preparation method thereof |
| CN107189669B (en) * | 2017-07-01 | 2019-01-29 | 湖南科技大学 | A kind of low-surface-energy aqueous polyurethane/nano SiO2Marine anti-pollution coating material and preparation method |
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| KR20110035356A (en) * | 2009-09-30 | 2011-04-06 | 재단법인 구미전자정보기술원 | Multi-functional hard coating composition and hard coating structure |
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