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Main chain degradation type metal ion complexation poly-Schiff base antifouling resin, preparation method and application

A technology of metal ions and poly-Schiff bases, applied in antifouling/underwater coatings, coatings, paints containing biocides, etc., can solve the problem of low mechanical strength, difficult control of hydrolysis rate, and limitations of intrinsic antifouling resins Application and other issues, to achieve high mechanical strength and property stability, improve the effect of regulating the hydrolysis rate of the resin, uniform and stable hydrolysis rate

Pending Publication Date: 2021-11-26
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the reversibility of the main chain degradable poly-Schiff base resin, the molecular weight is usually not high, the mechanical strength is low, and the hydrolysis rate is not easy to control, which seriously affects the promotion of poly-Schiff base antifouling resins.
However, there is currently a lack of such main chain degradable metal ion complexed poly-Schiff base antifouling resins and their preparation methods, which greatly limits the application of this type of intrinsic antifouling resins.

Method used

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  • Main chain degradation type metal ion complexation poly-Schiff base antifouling resin, preparation method and application
  • Main chain degradation type metal ion complexation poly-Schiff base antifouling resin, preparation method and application
  • Main chain degradation type metal ion complexation poly-Schiff base antifouling resin, preparation method and application

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preparation example Construction

[0043] Another aspect of the embodiments of the present invention also provides a method for preparing the aforementioned main chain degradable metal ion complexed poly-Schiff base antifouling resin, which includes:

[0044] In a protective atmosphere, the first homogeneously mixed reaction system comprising dialdehyde, diamine and the first solvent is reacted to prepare a poly-Schiff base polymer;

[0045] And, reacting the second homogeneously mixed reaction system comprising the poly-Schiff base polymer, metal ions and a second solvent to prepare the main chain degradable metal ion complexed poly-Schiff base antifouling resin.

[0046] Further, the protective atmosphere includes a nitrogen atmosphere, but is not limited thereto.

[0047] In some more specific embodiments, the preparation method specifically includes:

[0048] dissolving dialdehyde and diamine in the first solvent at -10-25°C to form the first uniformly mixed reaction system, and then reacting at 40-120°C f...

Embodiment 1

[0090] (1) Dissolve terephthalaldehyde and laurylamine dipropylenediamine in dichloromethane at -10 to 5°C, then add them to the reaction kettle, and gradually heat up to 60°C under nitrogen atmosphere. ℃, constant temperature reaction for 24 hours and use a water separator to remove the water generated in the reaction, remove most of the solvent by rotary evaporation, purify with methanol for 3 to 5 times, put it into a vacuum oven at 80 ℃ for drying and further After reacting for 24 hours, poly-Schiff-base macromolecules were obtained after being cooled to room temperature. The structure of the prepared poly-Schiff-base macromolecules is shown in the following formula:

[0091]

[0092] (2) At room temperature, dissolve the poly-Schiff base macromolecule and ferric chloride into tetrahydrofuran completely respectively to form a poly-Schiff base macromolecule solution and ferric chloride solution, and then fully stir the trichloride The iron solution was slowly added dropw...

Embodiment 2

[0102] The preparation method of this example is basically the same as that of Example 1, except that divalent copper ions are used to replace ferric ions to coordinate the Schiff base resin, and the molar ratio of metal ions to Schiff base groups is increased, respectively A group of samples of 1:10 (such as Figure 5 shown), four kinds of main chain degraded Cu prepared by this method 2+ The shear strength of ion complexed poly-Schiff base antifouling resin is about 0.3MPa, 1.3MPa, 2.4MPa, 4.0MPa respectively;

[0103] Four kinds of coatings (Cu 2+ The molar ratios of ions and Schiff base groups are 1:1250, 1:250, 1:50, and 1:10) placed in water for 24 hours, and the concentration of dialdehyde release per unit area on each coating is about 0.5 mg / L, 0.8mg / L, 1.1mg / L and 10.3mg / L;

[0104] Four coatings (Cu 2+ The molar ratios of ions and Schiff base groups are 1:1250, 1:250, 1:50, 1:10) and the average contact angles with water are about 134°, 123°, 98°, 101° (such as ...

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Abstract

The invention discloses main chain degradation type metal ion complexation poly-Schiff base antifouling resin as well as a preparation method and application thereof. The main chain degradation type metal ion complexation poly-Schiff base antifouling resin has a structure as shown in the following formula shown in the specification, wherein Me comprises any one or a combination of more than two of Ag, Cu, Fe, Zn and Cr; and n is selected from 10 to 500. The preparation method provided by the invention has the advantages of easily available raw materials, simple method and convenience in use; meanwhile, the main chain degradation type metal ion complexation poly-Schiff base antifouling resin prepared by the method integrates two antifouling materials, namely a metal ion antifouling material and a Schiff base antifouling material, the mechanical strength and degradation rate of the resin and a coating can be adjusted in a large range by changing the metal ion complexing degree, and the main chain degradation type metal ion complexation poly-Schiff base antifouling resin is excellent in antifouling effect and has a good application prospect.

Description

technical field [0001] The invention belongs to the field of antifouling technology, and in particular relates to a main chain degradable metal ion complexed poly-Schiff base antifouling resin, a preparation method and application. Background technique [0002] The sea area accounts for about 70% of the earth's surface, and there are immeasurable resources in the vast ocean. However, marine activities will inevitably be plagued by the problem of marine biofouling. Marine biofouling refers to the biofouling formed by the attachment, growth and accumulation of marine organisms on the surface of marine facilities, which seriously affects the development and utilization of marine resources by humans. For example, the firm attachment of organisms to the hull will cause a significant increase in navigation resistance and fuel consumption, and increase greenhouse gas emissions; biofouling will block the cages of mariculture, making it difficult to fully exchange oxygen and nutrient...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G12/06C08G12/40C09D161/32C09D5/16
CPCC08G12/06C08G12/40C09D161/32C09D5/1662
Inventor 赵文杰严明龙王立平卢光明蓝席建
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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