CN117211079A - Antifouling sustained-release tablet, preparation method and application - Google Patents
Antifouling sustained-release tablet, preparation method and application Download PDFInfo
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- CN117211079A CN117211079A CN202311256746.4A CN202311256746A CN117211079A CN 117211079 A CN117211079 A CN 117211079A CN 202311256746 A CN202311256746 A CN 202311256746A CN 117211079 A CN117211079 A CN 117211079A
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Abstract
The invention provides an anti-fouling sustained-release tablet, a preparation method and application thereof, wherein the anti-fouling sustained-release tablet comprises 3-6 parts of temperature-sensitive polymer, 2-4 parts of water-soluble resin, 12-22 parts of hydrating sustained-release resin and 55-70 parts of anti-fouling functional filler. The anti-fouling sustained release tablet can realize controllable release of an anti-fouling agent in a seawater environment with alternating temperature, particularly in seawater with alternating high temperature and normal temperature, and effectively prolongs the service life while ensuring the anti-fouling effect.
Description
Technical Field
The invention relates to the technical field of antifouling, in particular to an antifouling sustained release tablet, a preparation method and application.
Background
In the process of developing and utilizing the ocean, marine biofouling can bring great harm to ships, such as increasing ship navigation resistance, increasing ship body weight, increasing fuel consumption, accelerating ship body corrosion, increasing docking maintenance times and the like. The waste heat exchanger is an important heat exchange device in marine equipment, and is mainly used for waste heat discharge or emergency heat removal, and the working environment is a seawater environment with alternating temperature: if the highest seawater temperature in the cavity reaches more than 60 ℃ during heat exchange work, most fouling organisms cannot survive at the moment, and the device has a good antifouling function; if normal-temperature seawater is arranged in the cavity after heat exchange is suspended, fouling organisms are easy to attach to the heat exchange tube for growth, and the fouling organisms continuously grow and accumulate in the device, so that the heat exchange efficiency and the service life of the device are seriously reduced.
At present, relevant antifouling measures comprise antifouling coating, heat transfer protective coating, electrolytic chlorine production, electrolytic copper antifouling and other technologies. The anti-fouling method for coating the anti-fouling coating can reduce the heat exchange efficiency of the heat exchanger, and the temperature delay can reach more than 5 ℃, so that the anti-fouling method is not suitable for the anti-fouling design of the heat exchanger. Hydrogen is generated by the electrolytic chlorine production and electrolytic copper pollution prevention technology, so that the problem of hydrogen embrittlement of the titanium alloy substrate is easily caused, and the service life and the operation safety of the device are greatly threatened.
In view of this, the present invention has been made.
Disclosure of Invention
The invention solves the problem that the heat exchange efficiency of the heat exchange equipment in the prior ocean field can be seriously influenced after the fouling organisms are attached.
The invention provides an antifouling sustained release tablet, which comprises 3-6 parts of temperature-sensitive polymer, 2-4 parts of water-soluble resin, 12-22 parts of hydration sustained release resin and 55-70 parts of antifouling functional filler.
The temperature sensitive polymer is a polymer with low critical dissolution temperature characteristics, and is specifically expressed as follows: when the temperature is lower than the phase transition temperature, the polymer can be dissolved in water to form free flowing liquid, the temperature is increased to be higher than the phase transition temperature, the aqueous solution of the polymer is subjected to phase change to form gel which is not chemically crosslinked, the gel forming process is reversible, and the gel solution can be converted when the temperature is reduced; the low critical dissolution temperature can be adjusted by controlling the component ratio of different chain segments in the polymer, and the release rate of the anti-fouling agent in the temperature alternating environment of the anti-fouling sustained release tablet can be better realized by introducing temperature-sensitive polymers with different low critical dissolution temperatures into the anti-fouling sustained release tablet, so that the anti-fouling sustained release tablet has longer service life.
Preferably, the thermosensitive polymer is selected from at least one of polyglycolide lactide, polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide, and polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide. Preferably, the thermosensitive polymer is composed of polyglycolide lactide and polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide according to a ratio of 1:0.5-2, and the polyglycolide lactide and the polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide are purchased from Guangzhou water science and technology Co.
Preferably, the water-soluble resin is one or more selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyethyleneimine, polyethylene oxide, polyvinylamine, polyallylamine, and derivatives thereof.
Preferably, the water-soluble resin is any one of polyvinyl alcohol 1792 and polyvinyl alcohol 1788.
Preferably, the hydrated slow-release resin is at least one selected from zinc acrylate resin, silicon acrylate resin and acrylate resin.
Preferably, the antifouling functional filler comprises 35-40 parts of cuprous oxide, 10-15 parts of zinc oxide and 10-15 parts of organic antifouling agent.
Preferably, the organic anti-fouling agent is any one or more of bromopyrrocarbonitrile, copper pyrithione, zinc pyrithione, zineb and isothiazolinone. Preferably, the organic anti-fouling agent comprises 2-5 parts of copper pyrithione, 3-5 parts of zineb and 3-4 parts of isothiazolinone. Preferably, the organic anti-fouling agent further comprises 1-3 parts of bromopyrrocarbonitrile.
The invention also provides a preparation method of the antifouling sustained-release tablet, which comprises the following steps:
s1, weighing resin base materials and antifouling functional fillers according to the amount, adding the antifouling functional fillers into resin, and mixing by adopting a high-speed dispersing machine to prepare slurry;
s2, cutting fiber cotton according to the structural size of an anti-fouling sustained-release tablet die, soaking the fiber cotton in slurry for 48-72 hours, and transferring the fiber cotton into the die, wherein a polytetrafluoroethylene film is placed at the bottom of the die in advance as a substrate;
s3, placing the mixture in a baking oven at 38-45 ℃ for baking for 48-72 hours, and taking out to remove the polytetrafluoroethylene film at the bottom after baking to form the antifouling sustained-release tablet.
Preferably, the length, width and height of the fiber cotton are respectively 80-150mm, 50-100mm and 5-15mm.
The antifouling sustained release tablet is applied to marine equipment, wherein the marine equipment is a titanium alloy heat exchanger.
Compared with the prior art, the antifouling sustained-release tablet and the preparation method thereof have the following beneficial effects: the temperature-sensitive polymer changes along with the temperature of the seawater in the cavity of the waste heat exchanger, when the temperature is lower, the temperature-sensitive polymer keeps a swelling state, the water absorption of the water-soluble resin keeps a lower level, and the anti-fouling slow-release tablet anti-fouling agent exudes stably; the temperature is increased, the temperature-sensitive polymer is converted to a shrinkage state, the water absorption rate is reduced, the leaching rate of the anti-fouling agent of the anti-fouling sustained-release tablet is reduced, the controllable release of the anti-fouling agent of the anti-fouling sustained-release tablet is realized, and the service life of the anti-fouling sustained-release tablet is prolonged.
Drawings
FIG. 1 is a graph showing the results of the concentration of an antifouling agent according to the present invention as a function of time in a test case;
FIG. 2 is an external view of the antifouling sustained-release tablet prepared in example 1 after immersing in artificial seawater at 60 ℃;
FIG. 3 is an external view of the antifouling sustained-release tablet of comparative example 1 after immersing in artificial seawater at 60 ℃.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It should be noted that the technical features of the embodiments of the present invention may be combined with each other.
The waste heat exchanger is an important heat exchange device in marine equipment, is mainly used for waste heat emission or emergency heat extraction, and once marine fouling organisms adhere to the surface of the heat exchanger, the heat exchange efficiency of the marine fouling organisms is reduced. In view of the excellent corrosion resistance of titanium alloy, the novel waste heat exchanger largely adopts titanium alloy as a design base material, but the titanium alloy base material has natural biological affinity, marine organisms are more easily attached to the surface of the titanium alloy base material, and the safety of equipment operation is seriously affected.
In order to ensure the heat transfer efficiency of the surface of the heat exchanger, typical antifouling measures mainly comprise technologies such as electrolysis chlorine production, electrolysis copper antifouling and the like, but the prior art adopts a cabin penetrating external power supply to control the potential of a metal electrode so as to realize chlorine production or electrolysis copper, the electrolysis process is accompanied with the problem of serial hydrogen production, the problem of hydrogen embrittlement of a titanium alloy substrate is easily caused, and serious threat is generated to the safe operation of equipment, so that the marine antifouling measures which can be used for the titanium alloy waste heat exchanger and have higher safety are still blank, and are unfavorable for the popularization and the use of the titanium alloy waste heat exchanger.
In the previous studies, the applicant provided a seawater temperature responsive resin composition (publication No. CN 109651914A) for an antifouling paint comprising an ion exchange resin capable of releasing an antifouling agent by hydrolysis under the action of water, and a temperature sensitive copolymer mixed with the ion exchange resin, the temperature sensitive copolymer being formed by polymerizing a temperature sensitive monomer and a hydrophobic monomer additive, capable of shrinking molecular chains with an increase in temperature, forming a channel for seawater intrusion and antifouling agent exudation in the resin composition, and capable of stretching the molecular chains with a decrease in temperature to block the channel for antifouling agent exudation and seawater immersion. However, the above solution is rapidly released in the heat exchanger operating environment, resulting in a significant performance penalty. The applicant proposes the following technical scheme:
example 1
An antifouling sustained release tablet comprises the following components:
the preparation method comprises the following steps:
s1, weighing a resin base material and an antifouling functional filler according to the amount, adding the antifouling functional filler into resin, and mixing by adopting a high-speed dispersing machine to prepare slurry, wherein the critical dissolution temperature of polyglycolide lactide is 60+/-2 ℃;
s2, cutting polyester fiber cotton according to the structural size of an antifouling sustained-release tablet die, namely 110mm 80mm 10mm, soaking the polyester fiber cotton in the slurry for about 58 hours to enable the fiber cotton to absorb the slurry in a large amount, transferring the fiber cotton to the sustained-release tablet die, wherein the size of the die is 110mm 80mm 10mm, and adding a layer of polytetrafluoroethylene film at the bottom to serve as a substrate before placing so as to facilitate demolding;
and S3, placing the mixture in a baking oven at 40 ℃ for baking for 48 hours, and taking out the polytetrafluoroethylene film at the bottom after baking to form the antifouling sustained-release tablet.
Example 2:
an antifouling sustained release tablet comprises the following components:
the preparation method comprises the following steps:
s1, weighing resin base materials and antifouling functional fillers according to the amount, adding the antifouling functional fillers into resin, and adopting a high-speed dispersing machine to mix to prepare slurry, wherein the critical dissolution temperatures of polyglycolide lactide and polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide are respectively 60+/-2 ℃ and 40+/-2 ℃;
s2, cutting polyester fiber cotton according to the structural size of an antifouling sustained-release tablet die, namely 110mm 80mm 10mm, soaking the polyester fiber cotton in the slurry for about 50 hours to enable the fiber cotton to absorb the slurry in a large amount, transferring the fiber cotton to the sustained-release tablet die, wherein the size of the die is 110mm 80mm 10mm, and adding a layer of polytetrafluoroethylene film at the bottom to serve as a substrate before placing so as to facilitate demolding;
and S3, placing the mixture in a baking oven at 40 ℃ for 60 hours, and taking out to remove the polytetrafluoroethylene film at the bottom after the mixture is baked, so as to form the antifouling sustained-release tablet.
Example 3
An antifouling sustained release tablet comprises the following components:
the preparation method comprises the following steps:
s1, weighing resin base materials and antifouling functional fillers according to the amount, adding the antifouling functional fillers into resin, and adopting a high-speed dispersing machine to mix to prepare slurry, wherein the critical dissolution temperatures of polyglycolide lactide and polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide are respectively 60+/-2 ℃ and 40+/-2 ℃;
s2, cutting polyester fiber cotton according to the structural size of an antifouling sustained-release tablet die, namely 110mm 80mm 10mm, soaking the polyester fiber cotton in the slurry for about 50 hours to enable the fiber cotton to absorb the slurry in a large amount, transferring the fiber cotton to the sustained-release tablet die, wherein the size of the die is 110mm 80mm 10mm, and adding a layer of polytetrafluoroethylene film at the bottom to serve as a substrate before placing so as to facilitate demolding;
and S3, placing the mixture in a baking oven at 40 ℃ for 60 hours, and taking out to remove the polytetrafluoroethylene film at the bottom after the mixture is baked, so as to form the antifouling sustained-release tablet.
Example 4:
an antifouling sustained release tablet comprises the following components:
the preparation method comprises the following steps:
the preparation method comprises the following steps:
s1, weighing a resin base material and an antifouling functional filler according to a certain amount, adding the antifouling functional filler into resin, and mixing by adopting a high-speed dispersing machine to prepare slurry, wherein the critical dissolution temperature of the polycaprolactone lactide-polyethylene glycol-polycaprolactone lactide is 40+/-2 ℃;
s2, cutting polyester fiber cotton according to the structural size of an antifouling sustained-release tablet die, namely 110mm 80mm 10mm, soaking the polyester fiber cotton in the slurry for about 50 hours to enable the fiber cotton to absorb the slurry in a large amount, transferring the fiber cotton to the sustained-release tablet die, wherein the size of the die is 110mm 80mm 10mm, and adding a layer of polytetrafluoroethylene film at the bottom to serve as a substrate before placing so as to facilitate demolding;
and S3, placing the mixture in a baking oven at 40 ℃ for 60 hours, and taking out to remove the polytetrafluoroethylene film at the bottom after the mixture is baked, so as to form the antifouling sustained-release tablet.
Comparative example 1
The antifouling sustained-release tablets were prepared by the same preparation method as in example 1, the only difference being that: the temperature sensitive polymer is not added, and the dosage of the other components is kept unchanged.
Test results
The anti-fouling sustained release tablets prepared in example 1 and comparative example 1 were respectively placed in 2L of artificial seawater at 60 ℃ and soaked for 2 hours (sampling is carried out once every 1 hour for 2 times), then respectively transferred into 2L of normal-temperature artificial seawater, soaked for 2 days (sampling is carried out once after soaking for 24 hours and seawater is replaced, and 2 times are taken out), the above process is carried out for 4 cycles in total, and the concentration change of the anti-fouling agent in the artificial seawater is detected, and the result is shown in figure 1, wherein the origin and the square represent example 1 and comparative example 1 respectively.
The release rate of the anti-fouling sustained release tablet prepared in example 1 is basically maintained unchanged in the whole experimental period, the state is good, the anti-fouling sustained release tablet does not generate water absorption expansion, as shown in fig. 2, while the release rate of the anti-fouling agent in high-temperature artificial seawater is obviously accelerated, the release rate of the anti-fouling agent transferred to the normal-temperature artificial seawater environment is obviously reduced, the anti-fouling sustained release tablet obviously expands after 4 periods, part of the anti-fouling material overflows a titanium alloy packaging net box, as shown in fig. 3, and the release rate of the anti-fouling agent is obviously accelerated along with the expansion of the anti-fouling sustained release tablet.
The temperature sensitive polymer has temperature stimulus responsiveness, and keeps a swelling state in a seawater environment when the temperature is lower than the critical dissolution temperature, so that the normal release rate of the anti-fouling agent of the anti-fouling sustained release tablet is maintained; when the temperature is higher than the critical dissolution temperature, the temperature-sensitive polymer is converted from a swelling state to a shrinkage state, the water absorption rate of the anti-fouling sustained-release tablet is reduced, the leaching rate of the anti-fouling agent of the anti-fouling sustained-release tablet is reduced, but the high-temperature seawater environment is not suitable for the growth of marine fouling organisms, and the good anti-fouling effect in the cavity of the heat exchanger can be realized; as the heat exchanger finishes working, the temperature in the cavity of the heat exchanger is reduced, the temperature gradually tends to natural sea water temperature, the temperature-sensitive polymer is converted into a swelling state again, the release concentration of the anti-fouling slow-release tablet anti-fouling agent is increased, and the good anti-fouling effect in the cavity of the heat exchanger can be ensured. The preparation method not only realizes the controllable release of the anti-fouling sustained-release tablet anti-fouling agent, but also effectively prolongs the service life of the anti-fouling sustained-release tablet.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.
Claims (10)
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| JP2000303002A (en) * | 1999-04-16 | 2000-10-31 | Nitta Ind Corp | Antifouling coating composition |
| CN102083925A (en) * | 2008-06-11 | 2011-06-01 | 佐敦集团 | Binder for antifouling coating composition and antifouling coating composition comprising binder |
| CN109651914A (en) * | 2018-11-27 | 2019-04-19 | 中国船舶重工集团公司第七二五研究所 | A kind of antifouling paint ocean temperature response type resin combination and preparation method thereof |
| CN109985236A (en) * | 2019-04-17 | 2019-07-09 | 烟台大学 | Multivesicular liposome gel capable of overcoming burst release and maintaining antibody activity and preparation method thereof |
| CN110818827A (en) * | 2019-09-12 | 2020-02-21 | 中国船舶重工集团公司第七二五研究所 | A kind of antifouling paint with seawater temperature response function and preparation method thereof |
| CN115521700A (en) * | 2022-09-19 | 2022-12-27 | 江苏科技大学 | A kind of controllable degradation polyurethane antifouling coating based on PLGA and preparation method thereof |
| CN116772645A (en) * | 2023-06-20 | 2023-09-19 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Ocean anti-fouling method for titanium alloy waste heat exchanger cavity |
-
2023
- 2023-09-27 CN CN202311256746.4A patent/CN117211079A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000303002A (en) * | 1999-04-16 | 2000-10-31 | Nitta Ind Corp | Antifouling coating composition |
| CN102083925A (en) * | 2008-06-11 | 2011-06-01 | 佐敦集团 | Binder for antifouling coating composition and antifouling coating composition comprising binder |
| CN109651914A (en) * | 2018-11-27 | 2019-04-19 | 中国船舶重工集团公司第七二五研究所 | A kind of antifouling paint ocean temperature response type resin combination and preparation method thereof |
| CN109985236A (en) * | 2019-04-17 | 2019-07-09 | 烟台大学 | Multivesicular liposome gel capable of overcoming burst release and maintaining antibody activity and preparation method thereof |
| CN110818827A (en) * | 2019-09-12 | 2020-02-21 | 中国船舶重工集团公司第七二五研究所 | A kind of antifouling paint with seawater temperature response function and preparation method thereof |
| CN115521700A (en) * | 2022-09-19 | 2022-12-27 | 江苏科技大学 | A kind of controllable degradation polyurethane antifouling coating based on PLGA and preparation method thereof |
| CN116772645A (en) * | 2023-06-20 | 2023-09-19 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Ocean anti-fouling method for titanium alloy waste heat exchanger cavity |
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