Polyurethane film-pasting type antifouling material applied to marine antifouling and preparation method of polyurethane film-pasting type antifouling material

Abstract

The invention relates to a polyurethane film-sticking type antifouling material applied to marine antifouling and a preparation method of the polyurethane film-sticking type antifouling material. The high-temperature-resistant silicone oil is prepared from the following components in percentage by mass: 10%-30% of silicone oil and 10%-30% of polyether polyol; the antifouling film is prepared from the following components in percentage by weight: 5%-15% of isocyanate, 3%-10% of a chain extender, 1%-10% of an antifouling agent, 0-10% of porous filler, 1%-10% of a functional monomer, 20%-50% of a solvent and 0.05%-0.5% of a catalyst, and the antifouling agent is introduced into a polymer main chain or loaded into a cavity of the porous filler through a covalent bond, so that the antifouling film is endowed with excellent antifouling durability; the functional monomer is a disulfide compound or a ureido pyrimidone compound, and endows the antifouling film with excellent self-repairing performance. The antibacterial algal-inhibiting agent has excellent antibacterial and algal-inhibiting performance. The film material can be directly attached to the surface of equipment, the process can be completed instantly, and compared with traditional antifouling paint, the construction convenience is improved. The antifouling film material has excellent self-repairing performance, and can meet the application requirements of the antifouling film material in a complex marine environment.

Description

Technical Field

[0001] The invention relates to the technical field of new chemical materials, and in particular to a polyurethane film-type antifouling material used for marine antifouling and a preparation method thereof. Background Art

[0002] For thousands of years, human society has never stopped exploring the ocean. However, biological fouling is easy to attach to the surface of ships and equipment in the ocean. Marine biofouling will increase hull resistance and energy consumption, cause equipment corrosion, increase the frequency and cost of equipment maintenance, and also pose a risk of biological invasion.

[0003] The methods to combat biofouling mainly include manual mechanical removal, electrochemical antifouling, and antifouling coatings, and antifouling coatings are widely considered to be the most effective antifouling method to prevent biofouling.

[0004] At present, the main construction methods of antifouling coatings are spraying and brushing. Solvent-based antifouling coatings are mature and widely used in the field of marine antifouling, but the large amount of organic solvents volatilizes, causing serious harm to the environment, not in line with the country's environmental protection policies, and spraying and brushing may cause problems with uneven local thickness.

[0005] Thermoplastic polyurethane elastomer (TPU) is a green and environmentally friendly polymer material that can be plasticized by heating and dissolved by solvents. It has excellent comprehensive properties of high strength, high toughness, wear resistance and oil resistance. It is widely used in many fields such as footwear, automobiles, pipes, medical treatment, and films. TPU film has excellent flexibility and impact resistance, can effectively fit the arc surface, and prevent the fit arc surface from breaking. It can be used in the field of marine antifouling. Laminating TPU antifouling film to the surface of equipment in the ocean, on the one hand, avoids the complexity of construction and improves the convenience of operation, and on the other hand, avoids the large amount of volatilization of organic solvents, which meets the requirements of environmental protection.

[0006] Organic silicon materials have low surface energy and elastic modulus, and have broad application potential in the field of antifouling. Using organic silicon components to modify polyurethane can obtain a fouling-releasing substrate, and further introduce antifouling groups or porous materials loaded with antifouling agents to construct antifouling film materials with synergistic attack and defense, which is expected to achieve a major breakthrough in marine antifouling materials. Summary of the invention

[0007] In view of the shortcomings of existing antifouling coatings, the purpose of the present invention is to provide a polyurethane film-type antifouling material for marine antifouling and a preparation method thereof. The polymer substrate is an organosilicon-modified polyurethane, and a porous filler with antifouling groups or antifouling agents is further introduced to construct a film material, which solves the problems of long construction period, complex process and high VOC emission of traditional antifouling coatings. The antifouling film has excellent flexibility and impact resistance, can effectively fit the curved surface, prevent the fit curved surface from breaking, and can be widely used in the field of marine antifouling based on the synergistic antifouling strategy of low surface energy and low modulus and antifouling agents.

[0008] Another object of the present invention is to provide a method for preparing a polyurethane film-type antifouling material used for marine antifouling, which is scientific, reasonable, simple and easy to implement.

[0009] The technical solution adopted by the present invention is as follows:

[0010] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0011] Silicone oil: 25%-50%;

[0012] Polyether polyol: 25%-50%;

[0013] Isocyanate: 15%-30%;

[0014] Chain extender: 3%-10%;

[0015] Antifouling agent: 1%-10%;

[0016] Porous filler: 0-10%;

[0017] Functional monomer: 1%-10%;

[0018] Solvent: 20%-50%;

[0019] Catalyst: 0.05%-0.5%;

[0020] After the above raw materials react, the solvent is evaporated to obtain a solid product. After granulation, heating and melting, and extrusion into a film, the final product solid film material is obtained. The solid film material is directly applied to the surface of the protective device.

[0021] The silicone oil is one of hydroxypropyl silicone oil or aminopropyl silicone oil, and has a molecular weight of 2000-4000;

[0022] The polyether polyol is polytetramethylene ether diol with a molecular weight of 1000-2000;

[0023] The isocyanate is one or more of isophorone diisocyanate, hexamethylene isocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate;

[0024] The chain extender is one of propylene glycol and 1,4-butanediol;

[0025] The antifouling agent is one or more of capsaicin, allicin, eugenol, rosmarinic acid, furoate, bromopyrrole nitrile, DCOIT, zinc pyrithione, copper pyrithione, and cuprous oxide;

[0026] The functional monomer is a disulfide compound (such as 2,2'-diaminodiphenyl disulfide) or a ureido-pyrimidone compound (such as 2-ureido-4[1H]-pyrimidone);

[0027] The solvent is one or more of tetrahydrofuran, 1,4-dioxane, and N,N-dimethylformamide;

[0028] The catalyst is an organotin catalyst;

[0029] In the antifouling agent, capsaicin, allicin, eugenol, rosmarinic acid, and furoate are introduced into the polymer main chain through covalent bonds to achieve antifouling effect, and bromopyrrole nitrile, DCOIT, zinc pyrithione, copper pyrithione, and cuprous oxide are loaded with porous fillers and then mixed into the polymer resin;

[0030] The porous filler is one or more of hollow glass microspheres, mesoporous silica, ZIF-8, and UiO-66;

[0031] Furthermore, the preparation method of the polyurethane film-type antifouling material used for marine antifouling comprises the following steps:

[0032] (1) Coumarin, eugenol, capsaicin, allicin, rosmarinic acid, furoate and other substances are modified by 3-chloroglycerol to obtain bactericidal substances containing dihydroxyl groups. Antifouling agents such as bromopyrrole nitrile, DCOIT, zinc pyrithione, copper pyrithione, cuprous oxide and other antifouling agents are mixed with porous materials and loaded under ultrasonic environment;

[0033] (2) Disulfide compounds (such as 2,2'-diaminodiphenyl disulfide) or ureidopyrimidone compounds (such as 2-ureido-4[1H]-pyrimidone) are modified with dihydroxy groups;

[0034] (3) dissolving silicone oil and polytetrahydrofuran in a solvent, adding isocyanate and an organotin catalyst, and reacting at 60-90° C. for 4-8 hours;

[0035] (4) adding a functional monomer, a dihydroxy modified fungicide or a porous material loaded with an antifouling agent to the reaction product of (3), continuing the reaction at 60-90° C. for 2-4 hours, and obtaining pellets after gelation, aging and crushing;

[0036] (5) The pellets obtained in (4) are injection molded and extruded into films to obtain a polyurethane film material for marine antifouling.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The present invention first introduces the organosilicon chain segment into the TPU molecular chain system, which reduces the surface energy and elastic modulus of the antifouling film, which is conducive to the desorption of biological fouling on the surface of the antifouling film. The antifouling agent is introduced into the TPU molecular chain segment or a porous filler loaded with the antifouling agent is added to the polymer to extend the antifouling service life of the antifouling film, which is conducive to killing biological fouling on the surface of the antifouling film. The antifouling film is highly efficient and durable in antifouling by adopting an offensive and defensive strategy and synergistic antifouling, and exhibits excellent antifouling performance against inorganic pollutants, proteins, bacteria, and algae.

[0039] At the same time, the present invention not only has excellent mechanical properties and antifouling durability, but also has excellent self-repairing properties, which can meet its application requirements in complex marine environments and has broad application prospects in the field of marine antifouling.

[0040] In addition, the membrane material prepared by the present invention has the advantages of convenient construction, controllable cost, and green environmental protection. Specifically, the membrane material prepared by the present invention is different from the traditional antifouling coating. The construction method of the traditional antifouling coating is brushing, spraying, rolling, etc. The construction method of the antifouling membrane material prepared by the present invention is film pasting, which avoids the volatilization of solvents in the film forming process and the problems existing in the construction process. DETAILED DESCRIPTION

[0041] In order to better understand the above technical scheme, exemplary embodiments of the present invention will be described in more detail below. Although exemplary embodiments of the present invention are shown below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a clearer and more thorough understanding of the present invention, and to be able to fully convey the scope of the present invention to those skilled in the art.

[0042] Example 1

[0043] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0044] Hydroxypropyl silicone oil: 17.2%;

[0045] Polytetramethylene glycol: 16.1%;

[0046] Isophorone diisocyanate: 16.65%;

[0047] 1,4-Butanediol: 5.5%;

[0048] Coumarin: 2.25%;

[0049] Ureapyrimidone: 2.25%;

[0050] Tetrahydrofuran: 40%;

[0051] Dibutyltin dilaurate: 0.05%;

[0052] The preparation method of the polyurethane film-type antifouling material used for marine antifouling comprises the following steps:

[0053] (1) Hydroxypropyl silicone oil (molecular weight 2000) and polytetramethylene glycol (molecular weight 2000) were heated at 80°C to remove water, and then dissolved in tetrahydrofuran. Isophorone diisocyanate and an organotin catalyst were added, stirred evenly, and reacted at 75°C for 4 hours to obtain a mixed solution;

[0054] (2) Adding hydroxy-modified coumarin and dihydroxyureido pyrimidone to the mixed solution, continuing the reaction at 75° C. for 4 h, pouring the material into a drying tray after gelation, and curing it in an oven at 120° C. for 8 h, and then crushing the product to obtain pellets;

[0055] (3) The pellets are injection molded by an injection molding machine and extruded into films by a film drawing machine, thereby obtaining a polyurethane film material for marine antifouling.

[0056] Example 2

[0057] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0058] Hydroxypropyl silicone oil: 14%;

[0059] Polytetramethylene glycol: 14%;

[0060] Isophorone diisocyanate: 13.5%;

[0061] 1,4-Butanediol: 3.5%;

[0062] Capsaicin: 1.5%;

[0063] Uridine: 1.5%;

[0064] Tetrahydrofuran: 35%;

[0065] Dibutyltin dilaurate: 0.05%;

[0066] The preparation method of the polyurethane film-type antifouling material used for marine antifouling has the same steps as the preparation method of Example 1.

[0067] Example 3

[0068] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0069] Hydroxypropyl silicone oil: 15%;

[0070] Polytetramethylene glycol: 10%;

[0071] 1,4-cyclohexane diisocyanate: 15%;

[0072] 1,4-Butanediol: 5%;

[0073] Mesoporous SiO2: 5%;

[0074] Bromopyrrolecarbonitrile: 2.5%;

[0075] Ureapyrimidone: 2.5%;

[0076] Tetrahydrofuran: 45%;

[0077] Dibutyltin dilaurate: 0.05%;

[0078] The preparation method of the polyurethane film-type antifouling material used for marine antifouling comprises the following steps:

[0079] (1) Dispersing mesoporous silica and bromopyrrole nitrile in tetrahydrofuran, stirring evenly, and ultrasonically dispersing the load for 12 h;

[0080] (2) Hydroxypropyl silicone oil (molecular weight 2000) and polytetramethylene glycol (molecular weight 2000) were heated at 80°C to remove water, and then dissolved in tetrahydrofuran. 1,4-cyclohexane diisocyanate and dibutyltin dilaurate were added, stirred evenly, and reacted at 75°C for 4 hours to obtain a mixed solution;

[0081] (3) adding mesoporous silica loaded with bromopyrrolecarbonitrile and bishydroxyureidopyrimidone to the mixed solution, continuing the reaction at 75° C. for 4 h, pouring the material into a drying tray after gelation, and aging in an oven at 120° C. for 8 h, and then crushing the product to obtain pellets;

[0082] (4) The pellets are injection molded by an injection molding machine and extruded into films by a film drawing machine, thereby obtaining a polyurethane film material for marine antifouling.

[0083] Example 4

[0084] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0085] Aminopropyl silicone oil: 10%;

[0086] Polytetramethylene glycol: 25%;

[0087] Isophorone diisocyanate: 18%;

[0088] 1,4-Butanediol: 4.5%;

[0089] ZIF-8: 3.5%;

[0090] Bromopyrrole carbonitrile: 1.5%

[0091] Ureapyrimidone: 3.5%;

[0092] Tetrahydrofuran: 34%;

[0093] Dibutyltin dilaurate: 0.05%;

[0094] The preparation method of the polyurethane film-type antifouling material used for marine antifouling has the same steps as Example 3.

[0095] Example 5

[0096] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0097] Aminopropyl silicone oil: 25%;

[0098] Polytetramethylene glycol: 10%;

[0099] Isophorone diisocyanate: 18%;

[0100] 1,4-Butanediol: 4.5%;

[0101] Uio-66: 3.5%;

[0102] Bromopyrrole carbonitrile: 1.5%

[0103] Ureapyrimidone: 3.5%;

[0104] Tetrahydrofuran: 34%;

[0105] Dibutyltin dilaurate: 0.05%;

[0106] The preparation method of the polyurethane film-type antifouling material used for marine antifouling has the same steps as Example 3.

[0107] Example 6

[0108] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0109] Aminopropyl silicone oil: 12%;

[0110] Polytetramethylene glycol: 23%;

[0111] Isophorone diisocyanate: 18%;

[0112] 1,4-Butanediol: 4.5%;

[0113] Uio-66: 3.5%;

[0114] Copper pyrithione: 1.5%

[0115] Ureapyrimidone: 3.5%;

[0116] Tetrahydrofuran: 34%;

[0117] Dibutyltin dilaurate: 0.05%;

[0118] The preparation method of the polyurethane film-type antifouling material used for marine antifouling has the same steps as Example 3.

[0119] Comparative Example 1

[0120] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0121] Aminopropyl silicone oil: 13%;

[0122] Polytetramethylene glycol: 25%;

[0123] Isophorone diisocyanate: 18%;

[0124] 1,4-Butanediol: 4.5%;

[0125] Ureapyrimidone: 3.5%;

[0126] Tetrahydrofuran: 34%;

[0127] Dibutyltin dilaurate: 0.05%;

[0128] The preparation method of the polyurethane film-type antifouling material used for marine antifouling has the same steps as Example 3.

[0129] Comparative Example 2

[0130] The polyurethane film-type antifouling material used for marine antifouling is made of the following raw materials in percentage by mass:

[0131] Main agent: 35%;

[0132] Catalyst: 3.5%;

[0133] Xylene: 61.5%

[0134] The construction process is brush coating, mix the above mixture evenly and then brush it on the surface of the protective equipment;

[0135] Comparative Example 3

[0136] The material used for comparison is commercial Dow Corning 184 with antifouling agent added, which is composed of the following raw materials in percentage by mass:

[0137] Main agent: 35%;

[0138] Catalyst: 3.5%;

[0139] Bromopyrrolecarbonitrile: 1%;

[0140] Xylene: 60.5%

[0141] The construction process is brushing. Mix the above mixture evenly and then brush it on the surface of the protective equipment.

[0142] The experimental results are shown in the following table:

[0143]

[0144] From the experimental results of the embodiments and comparative examples, the embodiments described can effectively inhibit bacteria and algae from settling on their surfaces, and the antibacterial rates of all embodiments are greater than 85%. Among all the embodiments, the antibacterial and anti-algae conditions of Example 5 are the best, which is attributed to the lowest surface energy and elastic modulus, which is conducive to the desorption of fouling organisms on its surface. The comparison between Example 3 and Example 1 shows that although the product surface energy and elastic modulus of Example 1 are lower, the addition of more commercial antifouling agents in Example 3 leads to its more intentional antibacterial and anti-algae performance. In all the embodiments, the membrane material can be directly attached to the surface of the protective equipment, while Comparative Examples 2 and 3 require surface drying solvents at room temperature for 48 hours, indicating that the construction of the present invention is more convenient.

[0145] Compared with commercial PDMS, the present invention can also perform self-repair in a shorter time.

[0146] As can be seen from the above description, the present invention has the following advantages: it has excellent antibacterial and anti-algae properties. The membrane material can be directly attached to the surface of the equipment, and the process can be completed instantly, which improves the construction convenience compared with traditional antifouling coatings. The antifouling membrane material has excellent self-repairing properties and can meet its application requirements in complex marine environments.

[0147] The technical scope of the present invention is not limited to the contents in the above description. Those skilled in the art can make various deformations and modifications to the above embodiments without departing from the technical idea of ​​the present invention, and these deformations and modifications should all fall within the protection scope of the present invention.

Claims

1. A polyurethane film-type antifouling material for marine antifouling, characterized in that: The invention comprises the following raw materials in mass fraction: silicone oil: 25%-50%, polyether polyol: 25%-50%, isocyanate: 15%-30%, chain extender: 3%-10%, antifouling agent: 1%-10%, porous filler: 0-10%, functional monomer: 1%-10%, solvent: 20%-50%, catalyst: 0.05%-0.5%.

2. The polyurethane film-type antifouling material for marine antifouling according to claim 1, characterized in that: After the raw materials react, the solvent is evaporated to obtain a solid product. After granulation, heating and melting, and extrusion into a film, the final product is a solid film material. The solid film material is directly applied to the surface of the protective device.

3. The polyurethane film-type antifouling material for marine antifouling according to claim 2, characterized in that: The silicone oil is one of hydroxypropyl silicone oil and aminopropyl silicone oil, and the molecular weight is 2000-4000; the polyether polyol is polytetramethylene glycol, and the molecular weight is 1000-2000.

4. The polyurethane film-type antifouling material for marine antifouling according to claim 2, characterized in that: The isocyanate is one or more of isophorone diisocyanate, hexamethylene isocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; and the chain extender is one of propylene glycol and 1,4-butanediol.

5. The polyurethane film-type antifouling material for marine antifouling according to claim 2, characterized in that: The antifouling agent is one or more of capsaicin, allicin, eugenol, rosmarinic acid, furoate, bromopyrrole nitrile, 4,5-dichloro-N-octyl-4-isothiazoline-3-one (DCOIT), zinc pyrithione, copper pyrithione, and cuprous oxide.

6. The polyurethane film-type antifouling material for marine antifouling according to claim 2, characterized in that: The functional monomer is a disulfide compound or a ureido-pyrimidone compound.

7. The polyurethane film-type antifouling material for marine antifouling according to claim 2, characterized in that: The solvent is one or more of tetrahydrofuran, 1,4-dioxane and N,N-dimethylformamide; and the catalyst is an organic tin catalyst.

8. The polyurethane film-type antifouling material for marine antifouling according to claim 5, characterized in that: Capsaicin, allicin, eugenol, rosmarinic acid, and furoate were introduced into the polymer backbone through covalent bonds to achieve antifouling effects. Bromopyrrole nitrile, DCOIT, zinc pyrithione, copper pyrithione, and cuprous oxide were loaded on porous fillers and then blended into polymer resins.

9. The polyurethane film-type antifouling material for marine antifouling according to claim 1 or 8, characterized in that: The porous filler is one or more of hollow glass microspheres, mesoporous silica, ZIF-8, and UiO-66.

10. The method for preparing the polyurethane film-type antifouling material for marine antifouling according to claim 9, It is characterized in that The steps include: (1) For coumarin, eugenol, capsaicin, allicin, rosmarinic acid, and furoate, 3-chloroglycerol was used to modify them to obtain bactericidal substances containing dihydroxyl groups; for bromopyrrole nitrile, DCOIT, zinc pyrithione, copper pyrithione, and cuprous oxide, porous fillers were used to mix them and then placed under ultrasonic environment for loading; (2) dihydroxy modification of disulfide compounds or ureidopyrimidone compounds; (3) dissolving silicone oil and polytetrahydrofuran in a solvent, adding isocyanate and an organotin catalyst, 60-90℃ for 4-8h; (4) adding a functional monomer, a dihydroxy fungicide or a porous filler loaded with an antifouling agent to the reaction product of step (3), continuing the reaction at 60-90° C. for 2-4 hours, and obtaining pellets after gelation, aging and crushing; (5) The obtained pellets are injection molded and extruded into films, thereby obtaining a polyurethane film-type antifouling material used for marine antifouling.

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