CONTROLLED-RELEASE MATERIAL FOR ANTIFOULING AGENT SENSITIVE AND RESPONSE TO FOULING ORGANISMS AND PREPARATION METHOD THEREOF

Abstract

A controlled-release material sensitive and response to fouling organisms for an antifouling agent includes an encapsulating precursor and a crosslinking agent. A hyaluronic acid/polyL-lysine nano-shell controlled-release material is prepared by an alternating layer-by-layer self-assembly of hyaluronic acid and poly-L-lysine, and a polypropylene ammonium chloride/poly-L-glycine nano-shell controlled-release material is prepared by an alternating layer-by-layer sell-assembly of polypropylene ammonium chloride and poly-L-glycine. The crosslinking agent is composed of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxythiosuccinimide. Based on the specific catalytic hydrolysis characteristic of fouling organism extracellular proteases on the controlled-release material, the purpose of adjusting the release of antifouling agents adaptively with the change of fouling organisms in off-season/peak-season can be achieved, prolonging the service life of the antifouling coatings.

Claims

1. A controlled-release material sensitive and response to fouling organisms for an antifouling agent, comprising an encapsulating precursor and a crosslinking agent, wherein the encapsulating precursor comprises a first type and a second type, the first type is a combination of hyaluronic acid and poly-L-lysine, the second type is a combination of polypropylene ammonium chloride and poly-L-glycine, and the first type and the second type are configured to prepare two different types of controlled-release materials; a hyaluronic acid/poly-L-lysine nano-shell controlled-release material is prepared by an alternating layer-by-layer self-assembly of the hyaluronic acid and the poly-L-lysine, and a polypropylene ammonium chloride/poly-L-glycine nano-shell controlled-release material is prepared by an alternating layer-by-layer self-assembly of the polypropylene ammonium chloride and the poly-L-glycine; and the crosslinking agent is composed of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxythiosuccinimide.

2. A method of preparing an antifouling agent encapsulated in a controlled-release material sensitive and response to fouling organisms, comprising: grinding water-insoluble antifouling agents or slightly water-soluble antifouling agents to particles with a diameter of 0.5-5 um, and dispersing the particles in a first buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl to obtain a first mixed solution; adding a hyaluronic acid with the a weight percentage of 1-10% to the first mixed solution to obtain a second mixed solution for stirring for 1-4 hours, and then adding the a poly-L-lysine with the a weight percentage of 1-10% to the second mixed solution for stirring for 1-2 hours; or, adding the a polypropylene ammonium chloride with the a weight percentage of 1-10% to the first mixed solution to obtain a third mixed solution for stirring for 1-4 hours, and then adding the poly-L-glycine with the weight percentage of 1-10% to the third mixed solution for stirring for 1-2 hours; performing an alternating layer-by-layer self-assembly on the hyaluronic acid and the poly-L-lysine for 2-4 times, or performing an alternating layer-by-layer self-assembly on the polypropylene ammonium chloride and the poly-L-glycine for 2-4 times; centrifuging first microspheres obtained after the alternating layer-by-layer self-assembly at 3000-4000 rpm, and taking second microspheres after the centrifugation for reserve; preparing a second buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the second buffer solution to control a concentration of the 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride between 100 and 200 mM, adding N-hydroxythiosuccinimide to the second buffer solution to control a concentration of the N-hydroxythiosuccinimide at 50 mM, dispersing the second microspheres in the second buffer solution to obtain a fourth mixed solution and stirring the fourth mixed solution for 12-24 hours, after crosslinking, centrifuging the second microspheres to obtain the antifouling agent encapsulated in the controlled-release material sensitive and response to fouling organisms.

3. (canceled)

4. The method of preparing the antifouling agent encapsulated in the controlled-release material sensitive and response to fouling organisms of claim 2, wherein the water-insoluble antifouling agents or the slightly water-soluble antifouling agents comprise cuprous oxide, cuprous thiocyanate, or copper pyrrolidine.

5. A method of preparing an antifouling agent encapsulated in a nano-shell controlled-release material sensitive and response to fouling organisms, comprising: using porous calcium carbonate microspheres with a diameter of 0.5-5 m as templates; dispersing the porous calcium carbonate microspheres in a first buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl to obtain a first mixed soultion; using two encapsulating precursors, wherein a first encapsulating precursor is a combination of hyaluronic acid and poly-L-lysine, a second encapsulating precursor is a combination of polypropylene ammonium chloride and poly-L-glycine, and the two encapsulating precursors are configured to prepare two different types of controlled-release materials; the first encapsulating precursor is prepared by adding the hyaluronic acid with a weight percentage of 1-10% to the first mixed solution to obtain a second mixed solution for stirring for 1-4 hours, adding the poly-L-lysine with a weight percentage of 1-10% to the second mixed solution for stirring for 1-2 hours, and performing an alternating layer-by-layer self-assembly on the hyaluronic acid and the poly-L-lysine for 2-4 times; the second encapsulating precursor is prepared by adding the polypropylene ammonium chloride with a weight percentage of 1-10% to the first mixed solution to obtain a third mixed solution for stirring for 1-4 hours, adding the poly-L-glycine with a weight percentage of 1-10% to the third mixed solution for stirring for 1-2 hours, and performing an alternating layer-by-layer self-assembly on the polypropylene ammonium chloride and the poly-L-glycine for 2-4 times; centrifuging first microspheres obtained after the alternating layer-by-layer self-assembly at 3000-4000 rpm, and taking second microspheres after the centrifugation for reserve; preparing a second buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride to the second buffer solution to control a concentration of the 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride between 100 and 200 mM, adding N-hydroxythiosuccinimide to the second buffer solution to control a concentration of the N-hydroxythiosuccinimide at 50 mM, dispersing the second microspheres in the second buffer solution to obtain a fourth mixed solution and stirring the fourth mixed solution for 12-24 hours, centrifuging the second microspheres, and then dissolving the second microspheres in a gluconolactone solution to remove the porous calcium carbonate microspheres to obtain the nano-shell controlled-release material sensitive and response to fouling organisms, wherein an adding amount of the gluconolactone solution is 2-3 times a weight of the porous calcium carbonate microspheres; dissolving a water-soluble antifouling agent in a 2-(N-morpholine) ethanesulfonic acid/NaCl buffer solution to obtain a fifth mixed solution, and then dispersing the nano-shell controlled-release material sensitive and response to fouling organisms in the fifth mixed solution to load the antifouling agent into the nano-shell controlled-release material sensitive and response to fouling organisms, wherein a loading time is 0.5-5 hours; obtaining the antifouling agent encapsulated in the nano-shell controlled-release material sensitive and response to fouling organisms after a centrifugation.

6. The method of preparing the antifouling agent encapsulated in the nano-shell controlled-release material sensitive and response to fouling organisms of claim 5, wherein the water-soluble antifouling agent comprises sodium benzoate, or sodium paeonol sulfonate.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0022] The present invention will be further described below in conjunction with specific embodiments.

Embodiment 1

[0023] Encapsulation of a water-soluble antifouling agent in a controlled-release material sensitive and response to fouling organisms.

[0024] Porous calcium carbonate microspheres with a diameter of 0.5 m were dispersed in a buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl. Hyaluronic acid with a weight percentage of 1% was added, and stirred for 1 hour. Then poly-L-lysine with a weight percentage of 10% was added, and stirred for 2 hours. An alternating layer-by-layer self-assembly was performed on the two materials for two times. Microspheres after the layer-by-layer self-assembly were centrifuged at 3000 rpm for three times, and the microspheres were taken for use after centrifugation.

[0025] A buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl was prepared. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added to the buffer solution to control a concentration of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at 100 mM. N-hydroxythiosuccinimide was added to control a concentration of N-hydroxythiosuccinimide at 50 mM. The microspheres were dispersed in the buffer solution and stirred for 12 hours. The microspheres were subjected to a centrifugation and then dissolved in a gluconolactone solution to remove the calcium carbonate, and a mass ratio of the gluconolactone to the calcium carbonate is controlled at 2:1, to obtain a nano-shell controlled-release material sensitive and response to fouling organisms for antifouling agents.

[0026] The water-soluble antifouling agent such as sodium benzoate was dissolved in the 2-(N-morpholine) ethanesulfonic acid/NaCl buffer solution, and then the nano-shell material for encapsulating antifouling agents was dispersed to load the antifouling agent into the nano-shell structure. The loading time was 0.5 hours. After centrifugation, an antifouling agent was encapsulated in the controlled-release material sensitive and response to fouling organisms.

Embodiment 2

[0027] Encapsulation of a water-soluble antifouling agent in a controlled-release material sensitive and response to fouling organisms.

[0028] Porous calcium carbonate microspheres with a diameter of 5 m were dispersed in a buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl. Polypropylene ammonium chloride with a weight percentage of 10% was added and stirred for 4 hours. Then Poly-L glycine with a weight percentage of 1% was added and stirred for 1 hour. An alternating layer-by-layer self-assembly was performed on the two materials for four times. Microspheres after the layer-by-layer self-assembly were centrifuged at 4000 rpm for three times. After centrifugation, the microspheres were taken for use.

[0029] A buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl was prepared. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added to the buffer solution to control a concentration of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at 200 mM. N-hydroxythiosuccinimide was added to control a concentration of N-hydroxythiosuccinimide at 50 mM. The microspheres were dispersed in the buffer solution and stirred for 24 hours. The microspheres were subjected to a centrifugation, and then dissolved in a gluconolactone solution to remove the calcium carbonate, and a mass ratio of the gluconolactone to the calcium carbonate is controlled at 3:1, to obtain a nano-shell controlled-release material sensitive and response to fouling organisms for antifouling agents.

[0030] The water-soluble antifouling agent such as sodium paeonol sulfonate was dissolved in the 2-(N-morpholine) ethanesulfonic acid/NaCl buffer solution, and then the nano-shell material for encapsulating antifouling agents was dispersed therein to load the antifouling agent into the nano-shell structure. The loading time was 5 hours. After centrifugation, an antifouling agent was encapsulated in the controlled-release material sensitive and response to fouling organisms.

Embodiment 3

[0031] Encapsulation of a water-insoluble antifouling agent in a controlled-release material sensitive and response to fouling organisms.

[0032] Cuprous oxide with a diameter of about 0.5 m was dispersed in a buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl. Polypropylene ammonium chloride with a weight percentage of 5% was added and stirred for 2 hours, then poly-L-glycine with a weight percentage of 5% was added and stirred for 1.5 hours. An alternating layer-by-layer self-assembly was performed on the two materials for three times. Microspheres after the layer-by-layer self-assembly were centrifuged at 3500 rpm for three times. After centrifugation, the microspheres were taken for use.

[0033] A buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl was prepared. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added to the buffer solution to control a concentration of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at 150 mM. N-hydroxythiosuccinimide was added to control a concentration of N-hydroxythiosuccinimide at 50 mM. The microspheres were dispersed in the buffer solution and stirred for 18 hours. After crosslinking, the microspheres were subjected to a centrifugation to obtain cuprous oxide directly encapsulated in the controlled-release material sensitive and response to fouling organisms.

Embodiment 4

[0034] Cuprous thiocyanate with a diameter of about 5 m was dispersed in a buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl. Polypropylene ammonium chloride with a weight percentage of 10% was added and stirred for 4 hours, then poly-L-glycine with a weight percentage of 1% was added and stirred for 2 hours. An alternating layer-by-layer self-assembly was performed on the two materials for four times. Microspheres after the layer-by-layer self-assembly were centrifuged at 4000 rpm for three times. After centrifugation, the microspheres were taken for use.

[0035] A buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl was prepared. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added to the buffer solution to control a concentration of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at 200 mM. N-hydroxythiosuccinimide was added to control a concentration of N-hydroxythiosuccinimide at 50 mM. The microspheres were dispersed in the buffer solution and stirred for 24 hours. After crosslinking, the microspheres were subjected to a centrifugation to obtain cuprous thiocyanate directly encapsulated in the controlled-release material sensitive and response to fouling organisms.

Embodiment 5

[0036] Copper pyrrolidine with a diameter of about 2 m was dispersed in a buffer solution consisting of 0.1 mM Tris-HCl and 0.15 M NaCl. Hyaluronic acid with a weight percentage of 1% was added and stirred for 1 hour, then poly-L-glycine with a weight percentage of 10% was added and stirred for 1 hour. An alternating layer-by-layer self-assembly was performed on the two materials for two times. Microspheres after the layer-by-layer self-assembly were centrifuged at 3500 rpm for three times. After centrifugation, the microspheres were taken for use.

[0037] A buffer solution consisting of 0.02 M 2-(N-morpholine) ethylsulfonic acid and 0.15 M NaCl was prepared. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added to the buffer solution to control a concentration of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride at 100 mM. N-hydroxythiosuccinimide was added to control a concentration of N-hydroxythiosuccinimide at 50 mM. The microspheres were dispersed in the buffer solution and stirred for 12 hours. After crosslinking, the microspheres were subjected to a centrifugation to obtain copper pyrrolidine directly encapsulated in the controlled-release material sensitive and response to fouling organisms.

Embodiment 6

[0038] Release performance test of cuprous oxide encapsulated in the controlled-release material sensitive and response to fouling organisms.

[0039] 0.5 g of particles of the cuprous oxide-encapsulated controlled-release material sensitive and response to fouling organisms were dispersed in 20 ml protease solution. After 12 hours, the dispersed solution was centrifuged. The encapsulating layer was observed to be significantly hydrolyzed, and the cuprous oxide particles were observed to be exposed by SEM scanning electron microscopy.

Embodiment 7

[0040] Release performance test of sodium paeonol sulfonate encapsulated in the controlled-release material sensitive and response to fouling organisms. [0041] 0.5 g of particles of the sodium paeonol sulfonate-encapsulated controlled-release material sensitive and response to fouling organisms were dispersed in 20 ml protease solution, and benthic diatoms were added to the dispersed solution, concentration of the benthic diatoms was controlled to 1.010.sup.5. After 4 hours, the dispersed solution was centrifuged. The encapsulating layer was observed to be hydrolyzed by SEM scanning electron microscopy; and the concentration of the benthic diatoms was reduced to 0.8810.sup.5 by microscopic counting.