A kind of low surface energy self-polishing type polyurethane marine antifouling coating and preparation method thereof

Abstract

The invention provides low-surface-energy self-polishing polyurethane marine antifouling paint and a preparation method thereof. The preparation method combines ring-opening polymerization, polycondensation and hydrophobization; stannous octoate is taken as a catalyst; nanometer silicon dioxide is taken as an initiating agent; a certain quantity of hydroxyl groups and other groups contained in the surface of nanometer silicon dioxide are utilized for triggering ring-opening pre-polymerization of L-lactic acid monomers; a reaction is conducted between the obtained pre-polymer and 4,4-diphenyl-methane-diisocyanate; 1,4-butylene glycol is utilized for chain extension of the obtained oligomer, so that a crude product is synthesized; through hydrophobization treatment of the crude product, the low-surface-energy self-polishing polyurethane marine antifouling paint is obtained. Experiment research shows that the static water contact angle of the low-surface-energy self-polishing polyurethane marine antifouling paint is 108 degrees; the surface energy is relatively low; the self-polishing capability is excellent; the degradation period is 6 months; moreover, the low-surface-energy self-polishing polyurethane marine antifouling paint has a certain antibacterial property; the application prospect is broad, a novel way is provided to solve the vessel and marine biofouling problem, and the marine development construction and the national defense construction are facilitated.

Description

technical field [0001] The invention belongs to the field of chemical coatings, and in particular relates to a low surface energy self-polishing polyurethane marine antifouling coating and a preparation method thereof. Background technique [0002] In the process of human beings' continuous development and utilization of the ocean, how to solve the problem of marine biofouling has always been a difficult problem. Marine biofouling refers to the biological fouling formed by the adhesion of various microorganisms, plants, animals, etc. living in the ocean to the surface of the equipment submerged in seawater, and the continuous growth and reproduction. Marine biofouling has caused a certain negative impact on human beings' use of the ocean for development. Whether it is marine transportation, or the exploration and development of marine resources, it has been hindered. For example, marine biofouling will increase the roughness of the surface of marine equipment and navigation....

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Problems solved by technology

Isocyanates can be combined with hydroxyl resins, and can also be combined with hydroxyl groups in the substrate to promote the formation of hydrogen bonds and other chemical bonds, thereby enhancing the adhesion to the substrate. It is precisely because of these properties that isocyanates are synthetic The main raw material of polyurethane has advantages that other substances do not have. For example, Ma Chunfeng et al. have prepared a kind of main chain degradable polyurethane material by combining ring-opening polymerization and polycondensation reaction. This material has high degradation performance and excellent Adhesion, this research has greatly promoted the research and development of marine antifouling coatings, but due to the high surface energy of this polyurethane material, the hull is easy to be adhered to by fouling organisms during navigation, which increases navigation resistance and cannot be used for In actual voyage (Ma Chunfeng, Wu Bo, Xu Wentao, Zhang Guangzhao, Development of Marine Antifouling Polymer Materials, Polymer Bulletin, 2013, 9, 87–95.)

nano-SiO 2 There are certain active silicon hydroxyl groups on the surface, which makes nano-SiO 2 The surface of the surface exhibits certain hydrophilic and oleophobic properties, and is easy to agglomerate and condense. The study found that the modified nano-SiO 2 It has good hydrophobicity and low surface energy. For example, Majumdar P et al. have synthesized nano-silica polyurethane copolymers. Due to the incompatibility of the two, a layered coating is formed. The upper layer is low surface energy polydimethylene Silicone-based elastomer, the bottom layer is polyurethane with high surface energy, which solves the problem of weak adhesion of traditional low-surface-energy materials while improving the mechanical properties, but the copolymer has poor degradability, that is, self- The polishing ability is weak, and the fouling organisms adhere to the hull surface for a long time and corrode the hull surface (Majumdar P, Webster D C. Preparation of siloxane-urethane coatings having spontaneously formed stable biphasicmicrotophopical surfaces[J]. Macromolecules, 2005, 38(14) : 5857-5859), KeefeA J et al. grafted quaternary ammonium salt, triclosan grafted silicone resin, and zwitterionic polymers onto polydimethylsiloxane elastomers to prepare anti-fouling and anti-fouling Antifouling material with adsorption effect. Although the antifouling material has certain antibacterial properties, it does not have the two important properties of low surface energy and degradability. Bacteriostasis, which also limits the scope of application of this type of antifouling material (Keefe A J, Brault N D, Jiang SY. Suppressing surface reconstruction of superhydrophobic PDMS using asuperhydrophilic zwitterionic polymer[J]. Biomacromolecules, 2012, 13(5):1683- 1687.)

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