CN112127163B - Vertical fiber marine antifouling material modified by amphoteric ion polymer and preparation method thereof - Google Patents
Vertical fiber marine antifouling material modified by amphoteric ion polymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a vertical fiber marine antifouling material modified by a zwitterionic polymer and a preparation method thereof, and the preparation method comprises the following steps of firstly, soaking the vertical fiber material in a ferrous chloride solution for 0.5-2h; step two, taking out the vertical fiber material in the step one, controlling a ferrous chloride solution, and uniformly spraying a sodium borohydride solution on the ferrous chloride solution; step three, soaking the vertical fiber material treated by the sodium borohydride solution in the step two in a solution of a methacryloyl ethyl sulfobetaine monomer, a cross-linking agent and a free radical polymerization initiator, and reacting for 15min-1h in a room temperature environment under the protection of nitrogen; and step four, washing the vertical fiber material after the reaction in the step three, washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material. The invention has no antifouling agent and good antifouling performance, and overcomes the inherent defects of the application of common vertical fiber materials in the field of marine antifouling.
Description
Technical Field
The invention relates to a vertical fiber marine antifouling material and a preparation method thereof, in particular to a vertical fiber marine antifouling material modified by a zwitterionic polymer and a preparation method thereof, and belongs to the field of materials.
Background
The attachment and growth of marine organisms on underwater structures and ship bottoms can cause economic losses such as increased navigation resistance, increased fuel consumption, accelerated corrosion and the like, the traditional antifouling paint realizes an antifouling target by releasing an antifouling agent to drive or poison fouling organisms, but the released antifouling agent can generate negative effects on ecological systems and marine environments. In view of this, the antifouling Paint company of International Paint has proposed a biocide-free antifouling Paint based on the non-stick property of silicone-based surfaces, but the antifouling effect is not ideal.
The preparation of the antifouling material without antifouling agent release can be realized by designing a vertical fiber surface structure in the United states patent US 5618588, and the soft fiber vertical to the surface of the material can swing and bend to form a dynamic surface so that marine fouling organisms are not easy to attach or not firmly attached, thereby achieving the purpose of inhibiting fouling. However, the material of the ordinary fiber does not have the property of low surface energy or strong hydration, so the surface of the ordinary fiber still can be attached by fouling organisms. A small amount of fouling organisms attached to the surface of the fiber can prevent the fiber from swinging and bending, the fiber which originally has an antifouling effect can intercept fouling organism larvae and fouling organisms floating in the seawater from the seawater at the moment, and in addition, the surface area of the material surface with the fiber is far larger than that of a common material, so that a vicious circle is formed, and subsequent fouling organisms are attached more quickly and more than the common material. The fibers must be modified in order for the vertical fiber stain resist material to be of practical use.
Chinese patent CN 106400498A discloses a method for preparing fibers with good antifouling and fouling release properties by using polyamide fibers as raw materials and modifying the surface of the fibers with a copolymer of a hydrophilic segment with excellent hydration ability and a hydrophobic segment with low surface energy by a surface-initiated atom transfer radical polymerization method. The liquid phase environment and the chemical reaction on the surface are accompanied in the fiber modification process, so that the originally dispersed fibers are agglomerated together, particularly, the modification method of introducing hydrophilic groups with good antifouling performance on the fiber surface can further lead the fibers to absorb moisture in the air and agglomerate, and the factors can not form the special appearance of the fibers vertical to the surface, even can not flock. Patent CN 109294431A discloses that vinyltrimethoxysilane, polylactic acid and a silane coupling agent KH-560 are adopted to modify a nylon raw material, then nylon tows are prepared by electrostatic spinning and cut into fluff, and the fluff is added into a coating. The surface chemical composition introduced by the modification method of the invention has neither enough low surface energy nor excellent hydration capability, so that the improvement of the antifouling performance by modification is limited, and meanwhile, the modification means has complex process flow and is greatly limited by raw materials, and only modified nylon fluff can be produced. The fiber surface can not be effectively modified on the premise of maintaining the special surface morphology of the vertical fiber marine antifouling material regardless of the mode of carrying out polymerization grafting modification on the fiber surface or modifying the fiber and then spinning and cutting the fiber.
Disclosure of Invention
The invention aims to provide a vertical fiber marine antifouling material modified by a zwitterionic polymer and a preparation method thereof, which aims to realize effective chemical modification on the fiber surface on the premise of maintaining the special surface morphology of the vertical fiber marine antifouling material so as to obtain a marine antifouling material without an antifouling agent.
The purpose of the invention is realized by the following steps:
a vertical fiber marine antifouling material modified by a zwitterionic polymer is characterized in that a layer of zwitterionic polymer polymethacryloxyethyl sulfobetaine is coated on the surface of a vertical fiber on the premise of not changing the special appearance of the vertical fiber.
The invention also includes such features:
1. the vertical fibers have a diameter of 10 to 20 microns, a length of 600 to 1000 microns, and a vertical fiber basis weight of 80 to 105g/m 2 ；
2. The vertical fibers are common artificial fibers with stable properties in a seawater environment, and specifically are polyamide fibers, polyester fibers, spandex fibers, acrylic fibers or polyvinyl formal fibers;
3. the molecular structure of the zwitterionic polymer polymethacryloxyethyl sulfobetaine is as follows:
a preparation method of a vertical fiber marine antifouling material modified by a zwitterionic polymer is characterized by comprising the following steps:
step one, soaking a vertical fiber material in a ferrous chloride solution for 0.5-2h;
step two, taking out the vertical fiber material in the step one, controlling a ferrous chloride solution, and uniformly spraying a sodium borohydride solution on the ferrous chloride solution;
step three, soaking the vertical fiber material treated by the sodium borohydride solution in the step two in a solution of a methacryloyl ethyl sulfobetaine monomer, a cross-linking agent and a free radical polymerization initiator, and reacting for 15min-1h in a room-temperature environment under the protection of nitrogen;
and step four, washing the vertical fiber material after the reaction in the step three, washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material.
The concentration of the ferrous chloride solution is 0.03-0.1mol/L; the concentration of the sodium borohydride solution is 0.06mol/L-0.15mol/L;
in the third step, 5-7 parts of methacryloyl ethyl sulfobetaine monomer, 0.05-0.07 part of N, N-methylene bisacrylamide and 0.05-0.07 part of ammonium persulfate are calculated according to parts by weight;
the vertical fibers are planted on the surface of the substrate material by adopting an electrostatic flocking technology, and the method specifically comprises the following steps:
(1) polishing and cleaning the substrate material to ensure that the surface is smooth and free of dust;
(2) uniformly coating glue on the surface of a substrate;
(3) and (3) planting the fine fibers on the surface of the substrate coated with the glue in the step (2) by using an electrostatic flocking technology, and after the glue is cured, finishing the preparation of the vertical fiber material.
The glue is stable in property in a seawater environment, and specifically comprises the following components: epoxy resin glue, polyurethane glue or acrylate glue, the coating thickness is 80 to 150 microns;
the fibers have a diameter of 10 to 20 microns, a length of 600 to 1000 microns, and a basis weight of 80 to 105g/m 2 。
The fiber is common artificial fiber with stable property in a seawater environment, and specifically comprises the following components: polyamide fiber, polyester fiber, spandex fiber, acrylic fiber or polyvinyl formal fiber.
Technical description:
during the preparation process of the vertical fibers, the adhesive coating on the bottom layer is too thin, so that the fibers are not firmly bonded, and the fluff is wrapped by the adhesive due to too thick coating. Typically diatoms and other micro-fouling organisms are about 10 to 20 microns in size, with too large a diameter of the fibres increasing the surface to which the fouling organisms can attach, too short or too loose fibres being unable to effectively block the fouling organisms from contacting the substrate, and too long or too dense fibres trapping the fouling organisms.
According to the method in the surface modification process of the fiber, trace elemental iron is deposited on the surface of the fiber through a reduction reaction, and then a free radical polymerization reaction is initiated by utilizing a trace ferrous iron catalytic initiator released by the elemental iron in a methacryloyl ethyl sulfobetaine monomer solution, so that the surface of the fiber is wrapped by the polymethacrylyl ethyl sulfobetaine. The concentration of the used ferrous chloride solution is lower than 0.03mol/L or the concentration of the used sodium borohydride solution is lower than 0.06mol/L, so that the iron content on the surface of the fiber is too low, the free radical polymerization reaction can not be effectively initiated, and the polymethacryloxyethyl sulfobetaine can not completely wrap the surface of the fiber; the concentration of ferrous chloride solution is higher than that of sodium borohydride solution or higher than 0.15mol/L, excessive iron is deposited, excessive polymethacryloxyethyl sulfobetaine is generated, and fiber adhesion is caused. Meanwhile, the monomer fraction in the aqueous solution is less than 5 parts or the initiator dosage is less than 0.05 part, which leads to insufficient polymethacryloxyethyl sulfobetaine, while the monomer fraction is more than 7 parts or the initiator dosage is more than 0.07 part, which leads to excessive polymethacryloxyethyl sulfobetaine, which leads to fiber adhesion. The amount of the crosslinking agent less than 0.05 part may result in the decrease of the stability of the polymethacryloxyethylsulfonobetaine layer in seawater, and the amount of the crosslinking agent more than 0.07 part may result in the deterioration of the hydration ability of the polymethacryloxyethylsulfonobetaine.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, amphoteric ionization modification of the vertical fiber marine antifouling material is realized, and the polymethacryloxyethyl sulfobetaine is coated on the surface of each fiber, so that the material on the surface of the fiber has very strong antifouling capability, and the inherent defect of the application of the common vertical fiber material in the marine antifouling field is overcome.
(2) The invention realizes the zwitterionization modification, and simultaneously keeps the original appearance that the vertical fiber material fibers are uniformly dispersed and are not adhered, which is beneficial to the exertion of the antifouling function.
(3) The invention can simultaneously inhibit the attachment and growth of multi-scale fouling organisms and can meet the actual antifouling value.
(4) According to the invention, no antifouling agent is added, and the finally obtained zwitterion modified vertical fiber marine antifouling material has no pollution to the environment.
(5) The electrostatic flocking technology provided by the invention is mature in development, and the surface modification method is simple in process and mild in condition, so that the production scale can be enlarged, and the electrostatic flocking technology has an actual use value.
Drawings
FIG. 1 is a cross-sectional scanning electron microscope photograph of a zwitterionic polymer modified vertical fiber marine antifouling material.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention adopts the method of firstly flocking and then depositing the free radical polymerization catalyst on the fiber surface, so that the free radical polymerization reaction can only occur on the fiber surface but not in the fiber gap, the purpose of wrapping the amphoteric ion polymer polymethacryloxyethyl sulfobetaine with good antifouling performance on the fiber surface on the premise of not filling the fiber gap is realized, the surface chemical composition essence of the vertical fiber material is changed, the vertical fiber material has good antifouling performance, the unique antifouling morphology structure of the vertical fiber material is not changed, and the vertical fiber material has practical application value in the field of marine antifouling.
The technical scheme of the invention is as follows:
the vertical fibers are prepared by planting fine fibers on the surface of a substrate material by adopting an electrostatic flocking technology. The method specifically comprises the following steps: (1) polishing and cleaning the substrate material to ensure that the surface is smooth and free of dust; (2) uniformly coating glue on the surface of a substrate; (3) and (3) planting the fine fibers on the surface of the substrate coated with the glue in the step (2) by using an electrostatic flocking technology, and after the glue is cured, finishing the preparation of the vertical fiber material.
Wherein, the glue mentioned in (2) can be epoxy resin glue, polyurethane glue, acrylate glue and other glue with stable property in seawater environment, and the coating thickness should be controlled at 80-150 μm.
Wherein, the fiber used in the step (3) can be common artificial fiber with stable property in seawater environment, such as polyamide fiber, polyester fiber, spandex fiber, acrylic fiber, polyvinyl formal fiber, etc., the fiber diameter is below 20 micrometers, the length is 600 micrometers to 1 millimeter, and the weight of the fiber in unit area is controlled at 80g/m 2 To 105g/m 2 。
The free radical polymerization surface modification steps of the fiber are as follows: (1) soaking the vertical fiber material in a ferrous chloride solution for 0.5-2h; (2) taking out the vertical fiber material in the step (1), controlling a ferrous chloride solution, and uniformly spraying a sodium borohydride solution on the ferrous chloride solution; (3) and (3) soaking the vertical fiber material treated by the sodium borohydride solution in the step (2) in a solution of a methacryloyl ethyl sulfobetaine monomer, a cross-linking agent and a free radical polymerization initiator, and reacting for 15min-1h in a room-temperature environment under the protection of nitrogen. (4) And (4) washing the vertical fiber material after the reaction in the step (3), washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material.
Wherein the concentration of the ferrous chloride solution used in the step (1) is 0.03-0.1mol/L.
Wherein the concentration of the sodium borohydride solution used in the step (2) is 0.06-0.15 mol/L.
Wherein, in the step (3), 5 to 7 parts of methacryloyl ethyl sulfobetaine monomer, 40 parts of water, 0.05 to 0.07 part of cross-linking agent N, N-methylene diacryloyl and 0.05 to 0.07 part of initiating agent ammonium persulfate are calculated according to the parts by weight.
Example 1:
the vertical fiber is prepared by planting fine fibers on the surface of a substrate material by adopting an electrostatic flocking technology. The method specifically comprises the following steps: (1) polishing and cleaning the bakelite plate to ensure that the surface is smooth and free of dust; (2) uniformly coating 100-micron-thick epoxy resin glue on the surface of a substrate; (3) planting nylon fibers with the length of 0.6 mm and the diameter of 17 micrometers on the surface of the substrate coated with the glue in the step (2) by using an electrostatic flocking technology, wherein the planting density is 105g/m 2 And after the glue is solidified, the preparation of the vertical fiber material is finished.
The surface modification of the fiber adopts a free radical polymerization method. The method comprises the following specific steps: (1) soaking the vertical fiber material in ferrous chloride solution with the concentration of 0.5mol/L for 0.5-2h; (2) taking out the vertical fiber material in the step (1), controlling a ferrous chloride solution, and uniformly spraying 0.1mol/L sodium borohydride solution on the vertical fiber material; (3) and (3) soaking the vertical fiber material treated by the sodium borohydride solution in the step (2) in a solution of 6 parts of monomer methacryloyl ethyl sulfobetaine, 0.06 part of cross-linking agent N, N-methylene-bisacrylamide, 0.05 part of free radical polymerization initiator ammonium persulfate and 40 parts of water, and reacting for 0.5 hour in a room-temperature environment under the protection of nitrogen. (4) And (4) washing the vertical fiber material after the reaction in the step (3), washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material.
Example 2:
unlike example 1, the vertical fibers were prepared by the following method: (1) polishing and cleaning the bakelite plate to ensure that the surface is smooth and free of dust; (2) uniformly coating on the surface of a substrate100 micron thick epoxy glue; (3) planting nylon fibers with the length of 0.6 mm and the diameter of 17 micrometers on the surface of the substrate coated with the glue in the step (2) by using an electrostatic flocking technology, wherein the planting density is 105g/m 2 And after the glue is solidified, the preparation of the vertical fiber material is finished.
The zwitterionic modification was not performed.
Example 3:
unlike example 1, the vertical fibers were prepared by the following method: (1) cleaning the glass to ensure that the surface is smooth and free of dust; (2) uniformly coating 100-micron-thick epoxy resin glue on the surface of a substrate; (3) planting nylon fibers with the length of 0.6 mm and the diameter of 17 microns on the surface of the substrate coated with the glue in the step (2) by utilizing an electrostatic flocking technology, wherein the planting density is 85g/m 2 And after the glue is solidified, the preparation of the vertical fiber material is finished.
The surface modification of the fiber adopts a free radical polymerization method. The method comprises the following specific steps: (1) soaking the vertical fiber material in ferrous chloride solution with the concentration of 0.5mol/L for 0.5-2h; (2) taking out the vertical fiber material in the step (1), controlling a ferrous chloride solution, and uniformly spraying 0.1mol/L sodium borohydride solution on the vertical fiber material; (3) and (3) soaking the vertical fiber material treated by the sodium borohydride solution in the step (2) in a solution of 5 parts of monomer methacryloyl ethyl sulfobetaine, 0.05 part of cross-linking agent N, N-methylene bisacrylamide, 0.05 part of free radical polymerization initiator ammonium persulfate and 40 parts of water, and reacting for 15min in a room-temperature environment under the protection of nitrogen. (4) And (4) washing the vertical fiber material after the reaction in the step (3), washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material.
Example 4:
unlike example 3, the vertical fibers were prepared by the following method: (1) cleaning the glass to ensure that the surface is smooth and free of dust; (2) uniformly coating 120-micrometer-thick epoxy resin glue on the surface of the substrate; (3) planting nylon fibers with the length of 0.6 mm and the diameter of 17 microns on the surface of the substrate coated with the glue in the step (2) by utilizing an electrostatic flocking technology, wherein the planting density is 85g/m 2 And after the glue is cured, the preparation of the vertical fiber material is finished.
No zwitterionic modification was performed.
Example 5:
unlike example 1, the vertical fibers were prepared by the following method: (1) polishing and cleaning the bakelite plate to ensure that the surface is smooth and free of dust; (2) uniformly coating epoxy resin glue with the thickness of 90 microns on the surface of a substrate; (3) planting nylon fibers with the length of 0.6 mm and the diameter of 17 microns on the surface of the substrate coated with the glue in the step (2) by utilizing an electrostatic flocking technology, wherein the planting density is 65g/m 2 And after the glue is solidified, the preparation of the vertical fiber material is finished.
The surface modification of the fiber adopts a free radical polymerization method. The method comprises the following specific steps: (1) soaking the vertical fiber material in ferrous chloride solution with the concentration of 0.5mol/L for 0.5-2h; (2) taking out the vertical fiber material obtained in the step (1), controlling a ferrous chloride solution, and uniformly spraying a 0.1mol/L sodium borohydride solution on the vertical fiber material; (3) and (3) soaking the vertical fiber material treated by the sodium borohydride solution in the step (2) in a solution of 5 parts of monomer methacryloyl ethyl sulfobetaine, 0.05 part of cross-linking agent N, N-methylene-bisacrylamide, 0.05 part of free radical polymerization initiator ammonium persulfate and 40 parts of water, and reacting for 15min in a room-temperature environment under the protection of nitrogen. (4) And (4) washing the vertical fiber material after the reaction in the step (3), washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material.
Example 6:
unlike example 5, the vertical fibers were prepared by the following method: (1) polishing and cleaning the bakelite plate to ensure that the surface is smooth and free of dust; (2) uniformly coating 100-micrometer-thick epoxy resin glue on the surface of a substrate; (3) planting nylon fibers with the length of 0.6 mm and the diameter of 17 microns on the surface of the substrate coated with the glue in the step (2) by utilizing an electrostatic flocking technology, wherein the planting density is 65g/m 2 And after the glue is solidified, the preparation of the vertical fiber material is finished.
The zwitterionic modification was not performed.
Antifouling test:
(1) Anti-diatom test: the samples were soaked in artificial seawater for 24h and then transferred to an exponential growth phase with approximately 1X 10 numbers of diatoms (Nitzschia closterium) 6 Soaking in per mL of seaweed culture solution for two days. After the reaction is finished, the sample is soaked in clean artificial seawater and slightly shaken to wash off diatom which is not attached to the surface, then the sample is placed in 2.5% glutaraldehyde aqueous solution for fixing for two hours, then freeze drying is carried out, under the condition that a scanning electron microscope is adopted to amplify the solution by 500 times, 3 different positions are selected, the diatom attachment condition on the surface of the material is observed, and the diatom attachment condition is counted.
(2) Mussel adhesion test:
examples 1 to 6 were cut into 2.5 cm. Times.7.5 cm pieces, 3 pieces of each example were used as samples, and 36 pieces of the same size glass and 9 pieces of polydimethylsiloxane were cut as controls. And randomly placing all the sample positions to be spliced into a mosaic sample test board. The test board is soaked in artificial seawater for 24h, then 19 mussels with the size of about 5cm are placed on the test board on average, and the quantity of the sufficient silk discs secreted by the mussels on the surface of each sample is counted after 4 days.
And (3) testing results:
TABLE 1 anti-Diatom test results
Table 1 shows that in the anti-diatom test, there was no diatom attachment on the vertical fiber surface modified by zwitterion, there was only a small amount of diatom on the unmodified fiber surface, and there was a large amount of diatom on the surfaces of the polydimethylsiloxane and nylon plates as the control. Polydimethylsiloxane is the most widely used of nontoxic antifouling materials, and the antifouling effect of vertical fibers is obviously superior to that of the vertical fibers. Considering that the nylon plate and the fiber are made of the same material, the small fiber diameter is the key to prevent the adhesion of diatom.
From Table 2, it can be seen that the zwitterionic modified vertical fiber marine antifouling material can greatly reduce adhesion of mussel byssus, and particularly, the fiber density is 80g/m 2 The above zwitterionThe modified vertical fiber marine antifouling material completely inhibits mussels from secreting byssus on the surface of the mussels in the test.
TABLE 2 Mytilus resistant adhesion test results
Claims (8)
1. A preparation method of a vertical fiber marine antifouling material modified by a zwitterionic polymer is characterized by comprising the following steps:
the method comprises the following steps: soaking a vertical fiber material which adopts an electrostatic flocking technology to plant fine fibers on the surface of a substrate material in a ferrous chloride solution for 0.5-2h;
step two: taking out the vertical fiber material obtained in the first step, controlling a ferrous chloride solution out, and uniformly spraying a sodium borohydride solution on the vertical fiber material;
step three: soaking the vertical fiber material treated by the sodium borohydride solution in the step two in a solution of methacryloyl ethyl sulfobetaine monomer, N-methylene bisacrylamide and ammonium persulfate, and reacting for 15min-1h in a room-temperature environment under the protection of nitrogen;
step four: and (3) washing the vertical fiber material after the reaction in the third step, washing off redundant polymethacryloxyethyl sulfobetaine on the surface, and exposing fibers to obtain the zwitterion modified vertical fiber marine antifouling material.
2. The preparation method of the zwitterionic polymer modified vertical fiber marine antifouling material as claimed in claim 1, wherein the concentration of the ferrous chloride solution is 0.03-0.1mol/L; the concentration of the sodium borohydride solution is 0.06mol/L-0.15mol/L.
3. The preparation method of the zwitterionic polymer modified vertical fiber marine antifouling material as claimed in claim 1, wherein in the third step, 5-7 parts by weight of methacryloyl ethyl sulfobetaine monomer, 0.05-0.07 part by weight of N, N-methylene bisacrylamide and 0.05-0.07 part by weight of ammonium persulfate are adopted.
4. The method for preparing the zwitterionic polymer-modified vertical fiber marine antifouling material as claimed in claim 1, wherein the vertical fibers are 10-20 microns in diameter, 600-1000 microns in length and 80-105 g/m in weight per unit area 2 。
5. The method for preparing the zwitterionic polymer modified vertical fiber marine antifouling material as claimed in claim 1, wherein the vertical fibers are polyamide fibers, polyester fibers, spandex fibers, acrylic fibers or polyvinyl formal fibers.
6. The preparation method of the zwitterionic polymer modified vertical fiber marine antifouling material as claimed in claim 1, wherein the step of planting the fine fibers on the surface of the substrate material by adopting the electrostatic flocking technology specifically comprises the following steps:
(1) polishing and cleaning the substrate material to ensure that the surface is flat and free of dust;
(2) uniformly coating glue on the surface of a substrate;
(3) and (3) planting the fine fibers on the surface of the substrate coated with the glue in the step (2) by using an electrostatic flocking technology, and after the glue is cured, finishing the preparation of the vertical fiber material.
7. The method for preparing the vertical fiber marine antifouling material modified by the zwitterionic polymer as claimed in claim 6, wherein the glue is epoxy resin glue, polyurethane glue or acrylate glue, and the coating thickness of the glue is 80-150 microns.
8. A vertical fiber marine antifouling material modified by a zwitterionic polymer prepared by the method according to any one of claims 1 to 7, wherein the vertical fiber surface is coated with a layer of the zwitterionic polymer polymethacryloxyethyl sulfobetaine.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618588A (en) * | 1992-06-05 | 1997-04-08 | Sealflock Aktiebolag | Coating on marine constructions |
| CN106400498A (en) * | 2016-11-04 | 2017-02-15 | 青岛理工大学 | Multi-element synergistic antifouling copolymer modified polyimide fiber and preparation method thereof |
| CN106521945A (en) * | 2016-11-04 | 2017-03-22 | 青岛理工大学 | Multi-element synergistic antifouling copolymer modified spandex fiber and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618588A (en) * | 1992-06-05 | 1997-04-08 | Sealflock Aktiebolag | Coating on marine constructions |
| CN106400498A (en) * | 2016-11-04 | 2017-02-15 | 青岛理工大学 | Multi-element synergistic antifouling copolymer modified polyimide fiber and preparation method thereof |
| CN106521945A (en) * | 2016-11-04 | 2017-03-22 | 青岛理工大学 | Multi-element synergistic antifouling copolymer modified spandex fiber and preparation method thereof |
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