A kind of preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material

A nano-calcium carbonate and marine antifouling technology, applied in antifouling/underwater coatings, biocide-containing paints, etc., can solve the problems of disappearing antifouling interface, poor mechanical properties of hydrogel, and increased mechanical properties, achieving Great application prospects, low surface performance, and the effect of increasing mechanical properties

Active Publication Date: 2022-07-29
SUN YAT SEN UNIV
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Problems solved by technology

Hydrogel antifouling is rated as the third-generation antifouling material, but there are many problems with hydrogel as an antifouling material, among which (1) hydrogel has poor mechanical properties and is easily damaged in marine environments
(2) The antifouling effect is not long-lasting, the surface of the hydrogel is easily polluted by sea mud, and the antifouling interface disappears, thus losing the antifouling performance
Therefore, the main defect of hydrogel antifouling is that the mechanical properties of hydrogel are not strong, but both are indispensable in practical antifouling applications.
At present, the way to improve the mechanical properties of hydrogels is usually to build a double network structure, add nanomaterials to enhance the mechanical properties, and increase the degree of crosslinking. However, while enhancing the mechanical properties, the mechanical properties of the hydrogel are increase, the elastic modulus increases, causing the hydrogel to be more like an organic antifouling coating and lose the original meaning of hydrogel antifouling
Chinese patent CN110655675A discloses a kind of in-situ doped nano-calcium carbonate chitin hydrogel and its preparation method and application. First, chitin is dissolved in Na 2 CO 3 / Ca(OH) 2 / urea aqueous solution, then carry out chemical cross-linking reaction to prepare preliminary hydrogel, then carry out physical cross-linking reaction to prepare hydrogel, finally freeze the hydrogel, and obtain in-situ doped nano-calcium carbonate chitin after freeze-drying Hydrogel, its in-situ doped nano-calcium carbonate chitin hydrogel has good mechanical properties, has good adsorption performance for heavy metal copper ions, and has a good recycling rate, and is suitable for popularization and application in heavy metal sewage treatment , but the hydrogel is mainly used for the adsorption of heavy metal ions, and its mechanical properties are not strong and do not have antibacterial properties, so it cannot be used for marine antifouling

Method used

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  • A kind of preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material
  • A kind of preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material
  • A kind of preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material

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Embodiment 1

[0036] The preparation of embodiment 1 nano calcium carbonate hydrogel sponge

[0037] 1. Quaternized chitin: 1 g of chitin powder is dispersed in 50 mL (6.38wt% Ca(OH) 2 / 8.82wt%Na 2 CO 3 / 3.39wt% urea) solution, freeze and thaw twice at -40°C within 36h to obtain a white paste mixed solution of 2wt% chitin and nano-calcium carbonate. 6.705g of 2,3-epoxypropyltrimethylammonium chloride (EPTMAC) was added to the above chitin solution, and stirred at 10°C for 24h to obtain a paste-like white mixture, which is the grafted quaternary ammonium salt functional group. Semi-finished hydrogel;

[0038] 2. Hydrogel cross-linking: add 1877 type PVA (polyvinyl alcohol), PVA accounts for 10wt% of the total, after mixing evenly, the PVA is dissolved in the casting mold, the sample is placed at -20 ° C, frozen for 12 hours, the sample is taken out, and the temperature is room temperature. After thawing for 12 h, the above freezing and thawing process was repeated three times to obtain a...

Embodiment 2

[0039] The preparation of embodiment 2 nano calcium carbonate hydrogel sponge

[0040] 1. Quaternized chitin: 1 g of chitin powder is dispersed in 50 mL (5wt% Ca(OH) 2 / 12wt%Na 2 CO 3 / 2wt% urea) solution, freeze and thaw twice at -40°C within 36h to obtain a white paste mixed solution of 2wt% chitin and nano-calcium carbonate. Add 6.705 g of dimethyl diallyl ammonium chloride to the above chitin solution, and stir at 10°C for 24 hours to obtain a paste-like white mixture, which is a semi-finished hydrogel grafted with quaternary ammonium salt functional groups;

[0041] 2. Hydrogel cross-linking: add 1877 type PVA (polyvinyl alcohol), PVA accounts for 10wt% of the total, after mixing evenly, the PVA is dissolved in the casting mold, the sample is placed at -20 ° C, frozen for 12 hours, the sample is taken out, and the temperature is room temperature. After thawing for 12 h, the above freezing and thawing process was repeated three times to obtain a hydrogel physically cros...

Embodiment 3

[0042] The preparation of embodiment 3 nanometer calcium carbonate hydrogel sponge

[0043] 1. Quaternized chitin: 1 g of chitin powder is dispersed in 50 mL (10wt% Ca(OH) 2 / 7wt%Na 2 CO 3 / 6wt% urea) solution, freeze and thaw twice at -40°C within 36h to obtain a white paste mixed solution of 2wt% chitin and nano-calcium carbonate. 6.705 g of glycidyl trimethyl ammonium chloride was added to the above chitin solution, and stirred at 10° C. for 24 hours to obtain a paste-like white mixture, which is a semi-finished hydrogel with quaternary ammonium salt functional groups grafted;

[0044] 2. Hydrogel cross-linking: add 1877 type PVA (polyvinyl alcohol), PVA accounts for 10wt% of the total, after mixing evenly, the PVA is dissolved in the casting mold, the sample is placed at -20 ° C, frozen for 12 hours, the sample is taken out, and the temperature is room temperature. After thawing for 12 h, the above freezing and thawing process was repeated three times to obtain a hydrog...

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Abstract

The invention discloses a preparation method of an in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material, comprising the following steps: S1. Dispersing chitin in Ca(OH) 2 / Na 2 CO 3 / urea solution, mix evenly, freeze and thaw 2 to 4 times to obtain a white paste-like chitin and nano-calcium carbonate mixed solution; S2. Add the quaternary ammonium salt to the mixed solution in step S1, and mix well to obtain a paste-like white mixture S3. adding polyvinyl alcohol to the mixture in step S2, after mixing uniformly, dissolving, pouring in the mold, freezing and thawing 2 to 4 times to obtain a hydrogel of polyvinyl alcohol and quaternized chitin physically cross-linked; After soaking in glutaraldehyde aqueous solution, it is obtained. The invention prepares a marine anti-fouling gel with low surface performance, anti-fouling performance, mechanical performance and low elastic modulus at the same time, and has a great application prospect in marine anti-fouling.

Description

technical field [0001] The invention relates to the technical field of marine anti-fouling materials, and more particularly, to a preparation method and application of an in-situ growth nano-calcium carbonate hydrogel sponge marine anti-fouling material. Background technique [0002] Marine biofouling not only brings huge economic losses to the marine industry, but also brings serious harm to the marine ecological environment. Marine antifouling is to use physical or chemical methods to prevent marine organisms from attaching and growing on the surface of objects, or to make them detach from the surface. Commonly used methods are mechanical removal method, electrochemical method, ultrasonic method and antifouling coating method. At present, many marine antifouling methods are used for applying antifouling coatings, which are mainly divided into two categories: a. Antifouling coatings release toxic substances to achieve antifouling effects, and such antifouling coatings caus...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08J3/075C08J9/28C08L5/08C08L29/04C08K3/26C08K5/07C09D5/16
CPCC08J3/075C08J9/28C08J9/0071C08J9/0023C08J9/0061C09D5/16C08J2305/08C08J2429/04C08K2201/011C08K2003/265C08K5/07
Inventor 李伟华魏雅男刘欢刘法谦
Owner SUN YAT SEN UNIV
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