CN114750484A - Long-acting anti-fouling fabric and preparation method thereof - Google Patents

Long-acting anti-fouling fabric and preparation method thereof Download PDF

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CN114750484A
CN114750484A CN202210541538.8A CN202210541538A CN114750484A CN 114750484 A CN114750484 A CN 114750484A CN 202210541538 A CN202210541538 A CN 202210541538A CN 114750484 A CN114750484 A CN 114750484A
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cyclodextrin
mass
carboxymethyl
rubber
fouling
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史秀龙
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/048—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0207—Materials belonging to B32B25/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Abstract

The invention discloses a long-acting anti-fouling fabric and a preparation method thereof, and relates to the technical field of fabrics. The long-acting anti-fouling fabric prepared by the invention comprises Leica cloth, foamed rubber and an anti-fouling film from inside to outside in sequence; the antifouling film is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin; the modified cyclodextrin is prepared by grafting a hydroxylamine polymer onto mercapto-carboxymethyl-cyclodextrin, so that the stability is enhanced, a large amount of hydroxyl is introduced, the hydrophilicity is enhanced, the fabric has stain resistance, the density of a stain-resistant film is enhanced, and the tear resistance of the fabric is further enhanced; the foaming rubber is prepared by blending neoprene, polyurethane rubber and fluoropolyether nitrile for vulcanization foaming; the polyurethane rubber is added and blended to accelerate the vulcanization speed and improve the tear resistance of the foamed rubber, and the lycra cloth, the foamed rubber and the stain-resistant film are tightly connected to enhance the peel strength of the fabric and prolong the service life of the fabric.

Description

Long-acting anti-fouling fabric and preparation method thereof
Technical Field
The invention relates to the technical field of fabrics, in particular to a long-acting anti-fouling fabric and a preparation method thereof.
Background
Diving is the idea of entering underwater activities with or without specialized tools for underwater exploration, salvage, repair, and underwater construction. The back diving is gradually developed into a leisure sport which takes underwater activities as main contents, thereby achieving the purposes of body exercising and leisure and entertainment, and is widely popular with the public. The diving suit is a necessity for diving, can be used for preventing the body temperature from losing too fast during diving to cause temperature loss, and can also protect divers from reef or harmful animal and plant injury.
However, when the diving suit is operated under the sea for a long time or is used for diving under the sea, the anti-fouling is particularly important, microorganisms, bacteria and the like in the sea can influence the diving suit, the service life of the diving suit is influenced if the microorganisms, the bacteria and the like can influence the diving suit, and the diving suit is broken during diving if the microorganisms, the bacteria and the like influence the diving suit, so that the divers are injured; therefore, the long-acting anti-fouling fabric which is suitable for preparing the diving suit and has good tear resistance and long service life is researched and prepared.
Disclosure of Invention
The invention aims to provide a long-acting anti-fouling fabric and a preparation method thereof, so as to solve the problems in the background technology.
The long-acting anti-fouling fabric comprises Leica cloth, foamed rubber and an anti-fouling film from inside to outside in sequence, wherein the foamed rubber is prepared by blending chloroprene rubber, polyurethane rubber and fluoropolyether nitrile and vulcanizing and foaming.
Preferably, the fluoropolyethernitrile is prepared from 2, 6-dichlorobenzonitrile, 2, 6-difluorobenzonitrile and N-methyl pyrrolidone.
Preferably, the antifouling film is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin.
Preferably, the modified cyclodextrin is prepared by grafting a hydroxylamine polymer onto a mercapto-carboxymethyl-cyclodextrin.
Preferably, the preparation method of the long-acting anti-fouling fabric comprises the following specific steps:
(1) dispersing carboxymethyl-cyclodextrin in deionized water with the mass of 8-10 times that of the carboxymethyl-cyclodextrin, and performing dispersion at 10-20 rpm, dropwise adding a sodium hydroxide solution with the mass fraction of 3-5% and 0.1-0.15 times of the mass of carboxymethyl-cyclodextrin at the rate of 3-5 ml/min, continuously stirring, dropwise adding an acetonitrile solution of p-methylbenzenesulfonyl chloride with the mass fraction of 10-20% and 0.45-0.5 times of the mass of carboxymethyl-cyclodextrin at the rate of 3-5 ml/min, stirring and reacting for 2-3 h at the temperature of 22-25 ℃ and at the speed of 800-1000 rpm after dropwise adding, centrifuging to obtain a supernatant, standing the supernatant at the temperature of 0-4 ℃ for 6-8 h to generate precipitates, recrystallizing the precipitates twice by using deionized water as a solvent, and freeze-drying at the temperature of-50-60 ℃ to obtain sulfonated-carboxymethyl-cyclodextrin; mixing sulfonated-carboxymethyl-cyclodextrin, thiourea, methanol and deionized water according to the mass ratio of 1:1:6: 3-1.2: 1.2:8:4, heating in a water bath to 80-85 ℃, performing reflux reaction for 48 hours, performing rotary evaporation to obtain white precipitate, washing the white precipitate for 3-5 times with anhydrous methanol, dissolving the white precipitate with a sodium hydroxide solution with the mass of 5-8 times that of the white precipitate and the mass fraction of 10-15%, reacting for 5-6 hours at 50-60 ℃, adjusting the pH to 2-2.5 with hydrochloric acid, adding trichloroethylene with the mass of 0.04-0.08 time that of the white precipitate, cooling to 20-25 ℃, reacting for 1-2 hours, and finally performing suction filtration and recrystallization to obtain mercapto-carboxymethyl-cyclodextrin;
(2) Dispersing a hydroxylamine polymer in absolute methanol with the mass 6.5-7.5 times that of the hydroxylamine polymer, adding dimethylolpropionic acid with the mass 0.15-0.2 time that of the hydroxylamine polymer and sulfydryl-carboxymethyl-cyclodextrin with the mass 0.8-0.9 time that of the hydroxylamine polymer, bubbling with nitrogen for 20-30 min, reacting for 10-12 h under 365nm ultraviolet light, adding dimethylolpropionic acid with the mass 2-3 times that of the hydroxylamine polymer, continuing to react for 3-5 h under the ultraviolet light, centrifuging with diethyl ether to obtain a supernatant, placing the supernatant in a vacuum drying oven with the temperature of 40-50 ℃ and drying to constant weight to obtain modified cyclodextrin;
(3) mixing hyperbranched polyglycidyl ether and modified cyclodextrin according to a mass ratio of 5: 1-8: 1, heating to 90-120 ℃, stirring at 50-100 rpm, dropwise adding concentrated sulfuric acid with a mass fraction of 98% which is 0.2-0.3 times of that of the modified cyclodextrin at a speed of 3-5 ml/min, stirring for reacting for 24-36 h, adding plasticizer dibutyl phthalate with a mass fraction of 0.03-0.05 times of that of hyperbranched polyglycidyl ether, and uniformly stirring to obtain antifouling film slurry;
(4) the preparation method comprises the following steps of putting chloroprene rubber, polyurethane rubber, carbon black, paraffin, an anti-aging agent D, fluoropolyether nitrile and a plasticizer into a mixing mill, mixing for 5-8 min at 900-1000 rpm, heating to 105-110 ℃, adding a foaming agent, namely disulfo-selenohydrazine diphenyl ether, a vulcanization accelerator TMTD and zinc oxide, continuing mixing for 3-5 min, filtering by a rubber extruder, and tabletting to obtain a film; putting the film into a flat vulcanizing agent mold, and heating at 140-145 ℃ under 130-135 kg/cm 2Then, vulcanizing and foaming, opening the mold after 15-20 min, transferring the mixture into a foaming agent, and performing pressure treatment at 130-135 ℃ and 130-135 kg/cm2Secondly, vulcanizing and foaming again, opening the mold after 10-12 min to obtain the foamed rubber with the thickness of 100-160 mu m;
(5) coating a water-based polyurethane adhesive with the thickness of 5-10 mu m on two sides of the Lycra cloth, laminating with the foamed rubber, standing for 30-50 min, scraping edges, coating an antifouling film slurry with the thickness of 50-80 mu m, and standing for 3-7 d to obtain the long-acting antifouling fabric.
Preferably, in the step (1): the preparation method of the carboxymethyl-cyclodextrin comprises the following steps: mixing cyclodextrin, sodium hydroxide and deionized water according to a mass ratio of 4.2:3.5: 18-4.5: 3.6:20, stirring until the mixture is dissolved, adding sodium chloroacetate with the mass of 1.8-2 times that of the cyclodextrin, stirring at 30-50 rpm for reaction for 3-5 h, cooling to room temperature, adjusting the pH value to 4.8-5 with hydrochloric acid, adding methanol with the mass of 5-8 times that of the cyclodextrin for precipitation, filtering after precipitation, and drying in a vacuum drying oven at 80-90 ℃ until the weight is constant to obtain the carboxymethyl-cyclodextrin.
Preferably, in the step (2): the preparation method of the hydroxylamine polymer comprises the following steps: mixing 1, 4-butanediol diglycidyl ether, 2-methylallylamine and absolute methanol according to the mass ratio of 8.4:3: 4-8.6: 3:5, stirring and reacting for 70-72 h at 300-500 rpm, continuously stirring, dropwise adding diethyl ether until the solution is clear, transferring the diethyl ether to a vacuum drying oven at 40-50 ℃ for drying for 10-12 h, and obtaining the hydroxylamine polymer.
Preferably, in the step (4): the preparation method of the fluoropolyether nitrile comprises the following steps: mixing 2, 6-dichlorobenzonitrile, resorcinol, potassium carbonate, N-methyl pyrrolidone and toluene according to a mass ratio of 1:1:1:5: 5-1: 1.1:1.1:8:8, heating to 150-180 ℃ under the argon range, reacting for 2-3 h, adding 0.1-0.15 times of 2, 6-dichlorobenzonitrile, continuing to react for 1-2 h, heating to 200-205 ℃, reacting for 0.5-1 h, adding 0.05-0.08 times of 2, 6-dichlorobenzonitrile, continuing to react for 20-30 min, precipitating with methanol, filtering, washing with methanol and hot water at 70-90 ℃ for 3-5 times, and finally drying in a drying oven at 120 ℃ to constant weight to obtain fluoropolyether nitrile.
Preferably, in the step (4): the foaming rubber comprises, by weight, 45-55 parts of chloroprene rubber, 15-20 parts of polyurethane rubber, 3-5 parts of carbon black, 3-5 parts of paraffin, 0.04-0.06 part of an anti-aging agent D, 10-20 parts of fluoropolyether nitrile, 8-12 parts of a plasticizer, 8-10 parts of a foaming agent bis (seleno-hydrazine) diphenyl ether, 0.4-0.6 part of a vulcanization accelerator TMTD and 2-4 parts of zinc oxide.
Preferably, in the step (5): the gram weight of the Lycab is 100-160 g/cm2。
Compared with the prior art, the invention has the following beneficial effects:
The long-acting anti-fouling fabric prepared by the invention sequentially comprises the Lycra cloth, the foamed rubber and the anti-fouling film from inside to outside, has excellent anti-fouling and anti-tearing properties, and is suitable for preparing diving suits;
the antifouling film is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin; the modified cyclodextrin is prepared by grafting a hydroxylamine polymer onto mercapto-carboxymethyl-cyclodextrin; sulfydryl is introduced into carboxymethyl-cyclodextrin to react with double bonds on a hydroxylamine polymer to form cyclodextrin with long chain modification, stability is enhanced, the hydroxylamine polymer is grafted to the sulfydryl-carboxymethyl-cyclodextrin, a large number of hydroxyl is introduced, hydrophilicity is enhanced, a compact hydration layer can be formed on the surface of the anti-fouling membrane, fouling substances such as protein cannot penetrate through the compact hydration layer, interaction with the surface of the fabric is reduced, and anti-fouling performance is achieved; carboxyl on the modified cyclodextrin reacts with hydroxyl on the hyperbranched polyglycidyl ether, the modified cyclodextrin with a large number of hydroxyl and long chains is introduced into the hyperbranched polyglycidyl ether, the stability of the antifouling film is enhanced by virtue of the stability of the cyclodextrin in seawater, the service life of the fabric is prolonged, meanwhile, the long chains of the modified cyclodextrin are entangled on the hyperbranched polyglycidyl ether, the density of the antifouling film is enhanced, and the tear resistance of the fabric is further enhanced;
The foaming rubber is prepared by blending chloroprene rubber, polyurethane rubber and fluoropolyether nitrile for vulcanization foaming; the vulcanization speed is accelerated after the polyurethane rubber is added and blended, and the tear resistance of the foamed rubber is improved; the fluoropolyether nitrile is used as a curing agent for vulcanization, so that the vulcanized foam rubber has nitrile groups, the nitrile groups and the waterborne polyurethane adhesive are attached, the nitrile groups are hydrolyzed into carboxyl by moisture after attachment, the attachment speed is accelerated, the generated carboxyl can also react with the waterborne polyurethane adhesive and hydroxyl on an anti-fouling membrane, and therefore the lycra cloth, the foam rubber and the anti-fouling membrane are tightly connected, the peel strength of the fabric is enhanced, meanwhile, fluorine is introduced into the foam rubber layer, and the foam rubber is hydrophobic while the anti-fouling layer is hydrophilic, so that the service life of the fabric is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for detailed description, and the method for testing each index of the long-acting anti-fouling fabric prepared in the examples and the comparative examples is as follows:
stain resistance: and (3) carrying out water contact angle test on the long-acting anti-fouling fabric prepared in the embodiment and the comparative example with the same area by using a surface contact angle tester.
Tear resistance: tear strength tests are carried out on the long-acting anti-fouling fabrics prepared in the examples and the comparative examples with the same area according to GB/T529.
Service life: the long-acting anti-fouling fabric prepared in the embodiment and the comparative example with the same area is washed for 48 hours by using seawater with the same flow rate, and a water contact angle test is carried out by using a surface contact angle tester.
Peel strength: the long-lasting antifouling fabrics prepared in the same area in the examples and comparative examples were subjected to a peel strength test in accordance with DIN 53273.
Example 1
(1) The preparation method of the carboxymethyl-cyclodextrin comprises the following steps: mixing cyclodextrin, sodium hydroxide and deionized water according to a mass ratio of 4.2:3.5:18, stirring until the cyclodextrin is dissolved, adding sodium chloroacetate with a mass of 1.8 times that of the cyclodextrin, stirring at 30rpm for reaction for 3 hours, cooling to room temperature, adjusting the pH value to 4.8 by using hydrochloric acid, adding methanol with a mass of 5 times that of the cyclodextrin for precipitation, filtering after precipitation, and drying in a vacuum drying oven at 80 ℃ until the weight is constant to obtain carboxymethyl-cyclodextrin;
(2) Dispersing carboxymethyl-cyclodextrin in deionized water with the mass 8 times that of the carboxymethyl-cyclodextrin, dropwise adding a sodium hydroxide solution with the mass fraction of 3-5% and the mass fraction of 0.1 time that of the carboxymethyl-cyclodextrin at the speed of 3ml/min under the condition of 10rpm, continuously stirring, dropwise adding an acetonitrile solution of p-methylbenzenesulfonyl chloride with the mass fraction of 10% and the mass fraction of 0.45 time that of the carboxymethyl-cyclodextrin at the speed of 3-5 ml/min, stirring and reacting at the temperature of 22 ℃ and the speed of 800rpm after dropwise adding, centrifuging to obtain a supernatant, standing the supernatant at the temperature of 0 ℃ for 6 hours to generate precipitates, recrystallizing the precipitates twice by using the deionized water as a solvent, and performing freeze drying at the temperature of-50 ℃ to obtain the sulfonated-carboxymethyl-cyclodextrin; mixing sulfonation-carboxymethyl-cyclodextrin, thiourea, methanol and deionized water according to the mass ratio of 1:1:6:3, heating the mixture in a water bath to 80 ℃, carrying out reflux reaction for 48 hours, then carrying out rotary evaporation to obtain white precipitate, washing the white precipitate for 3 times by using anhydrous methanol, dissolving the white precipitate by using a sodium hydroxide solution with the mass of 10 percent accounting for 5 times of the mass of the white precipitate, reacting for 5 hours at 50 ℃, adjusting the pH to 2 by using hydrochloric acid, then adding trichloroethylene with the mass of 0.04 time of the mass of the white precipitate, cooling the mixture to 20 ℃, reacting for 1 hour, and finally carrying out suction filtration and recrystallization to obtain mercapto-carboxymethyl-cyclodextrin;
(3) Mixing 1, 4-butanediol diglycidyl ether, 2-methylallylamine and absolute methanol according to the mass ratio of 8.4:3:4, stirring and reacting for 70 hours at 300rpm, continuously stirring, dropwise adding diethyl ether until the solution is clear, transferring the diethyl ether to a vacuum drying oven at 40 ℃ after all, and drying for 10 hours to obtain a hydroxylamine polymer; dispersing a hydroxylamine polymer in anhydrous methanol with the mass 6.5 times that of the hydroxylamine polymer, adding dimethylol propionic acid with the mass 0.15 time that of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin with the mass 0.8 time that of the hydroxylamine polymer, bubbling with nitrogen for 20min, reacting for 10h under 365nm ultraviolet light, adding dimethylol propionic acid with the mass 2 times that of the hydroxylamine polymer, continuing to react for 3h under the ultraviolet light, centrifuging with diethyl ether to obtain a supernatant, and drying the supernatant in a vacuum drying oven at 40 ℃ to constant weight to obtain modified cyclodextrin;
(4) mixing hyperbranched polyglycidyl ether and modified cyclodextrin according to a mass ratio of 5:1, heating to 90 ℃, stirring at 50rpm, dropwise adding concentrated sulfuric acid with a mass fraction of 98% which is 0.2 times of that of the modified cyclodextrin at a speed of 3ml/min, stirring for reacting for 24 hours, adding plasticizer dibutyl phthalate with a mass which is 0.03 times of that of the hyperbranched polyglycidyl ether, and uniformly stirring to obtain antifouling film slurry;
(5) Mixing 2, 6-dichlorobenzonitrile, resorcinol, potassium carbonate, N-methyl pyrrolidone and toluene according to a mass ratio of 1:1:1:5:5, heating to 150 ℃ in an argon range, reacting for 2h, adding 2, 6-difluorobenzonitrile which is 0.1 time of that of the 2, 6-dichlorobenzonitrile, continuously reacting for 1h, heating to 200 ℃ after reacting for 0.5h, adding 2, 6-difluorobenzonitrile which is 0.05 time of that of the 2, 6-dichlorobenzonitrile, continuously reacting for 20min, separating out with methanol, filtering, washing with methanol and hot water at 70 ℃ for 3 times respectively, and finally drying in a 120 ℃ drying oven to constant weight to obtain fluoropolyether nitrile; the preparation method comprises the following steps of putting chloroprene rubber, polyurethane rubber, carbon black, paraffin, an anti-aging agent D, fluoropolyether nitrile and a plasticizer into a mixing mill, mixing for 5min at 900rpm, heating to 105 ℃, adding a foaming agent disulfo-selenohydrazine diphenyl ether, a vulcanization accelerator TMTD and zinc oxide, continuing mixing for 3min, filtering by a rubber extruder, and tabletting to obtain a rubber sheet; placing the film into a flat vulcanizing agent mold, and heating at 140 deg.C under 130kg/cm2Then, adding sulfur to foam, opening the mold after 15min, transferring to foaming agent at 130 deg.C under 130kg/cm2Then, the hair is vulcanized againFoaming for 10min, and then opening the die to prepare foamed rubber with the thickness of 100 microns, wherein the foamed rubber comprises 45 parts by weight of chloroprene rubber, 15 parts by weight of polyurethane rubber, 3 parts by weight of carbon black, 3 parts by weight of paraffin, 0.04 part by weight of anti-aging agent D, 10 parts by weight of fluoropolyether nitrile, 8 parts by weight of plasticizer, 8 parts by weight of foaming agent bis (seleno-hydrazine) diphenyl ether, 0.4 part by weight of vulcanization accelerator TMTD and 2 parts by weight of zinc oxide;
(6) The gram weight is 100g/cm2Coating a waterborne polyurethane adhesive with the thickness of 5 mu m on two sides of the Lycra cloth, attaching the Lycra cloth to foamed rubber, standing for 30min, scraping edges, coating antifouling film slurry with the thickness of 50 mu m, and standing for 3d to obtain the long-acting antifouling fabric.
Example 2
(1) The preparation method of the carboxymethyl-cyclodextrin comprises the following steps: mixing cyclodextrin, sodium hydroxide and deionized water according to a mass ratio of 4.4:3.5:19, stirring until the cyclodextrin, sodium chloroacetate with a mass of 1.9 times that of the cyclodextrin is dissolved, stirring at 40rpm for reaction for 4 hours, cooling to room temperature, adjusting the pH value to 4.9 by using hydrochloric acid, adding methanol with a mass of 6 times that of the cyclodextrin for precipitation, filtering after precipitation, and drying in a vacuum drying oven with a temperature of 85 ℃ until the weight is constant to obtain carboxymethyl-cyclodextrin;
(2) dispersing carboxymethyl-cyclodextrin in deionized water with the mass of 9 times that of the carboxymethyl-cyclodextrin, dropwise adding a sodium hydroxide solution with the mass fraction of 4% and the mass fraction of 0.13 time that of the carboxymethyl-cyclodextrin at the speed of 4ml/min under the condition of 15rpm, continuously stirring, dropwise adding an acetonitrile solution of p-methylbenzenesulfonyl chloride with the mass fraction of 15% and the mass fraction of 0.48 time that of the carboxymethyl-cyclodextrin at the speed of 4ml/min, stirring and reacting for 2 hours at the temperature of 24 ℃ and 900rpm after dropwise adding, centrifuging to obtain a supernatant, standing the supernatant for 7 hours at the temperature of 2 ℃ to generate precipitates, recrystallizing the precipitates twice by taking the deionized water as a solvent, and freeze-drying at the temperature of-55 ℃ to obtain the sulfonated-carboxymethyl-cyclodextrin; mixing sulfonation-carboxymethyl-cyclodextrin, thiourea, methanol and deionized water according to the mass ratio of 1.1:1.1:7:3, heating the mixture in a water bath to 83 ℃, performing reflux reaction for 48 hours, then performing rotary evaporation to obtain white precipitate, washing the white precipitate for 4 times by using anhydrous methanol, dissolving the white precipitate by using a sodium hydroxide solution with the mass percent of 13 percent and 6 times of the mass of the white precipitate, placing the mixture at 55 ℃ for reaction for 5 hours, adjusting the pH to 2 by using hydrochloric acid, then adding trichloroethylene with the mass of 0.06 time of the mass of the white precipitate, cooling the mixture to 23 ℃, performing reaction for 1 hour, and finally performing suction filtration and recrystallization to obtain mercapto-carboxymethyl-cyclodextrin;
(3) Mixing 1, 4-butanediol diglycidyl ether, 2-methylallylamine and absolute methanol according to the mass ratio of 8.5:3:5, stirring and reacting for 71 hours at 400rpm, continuously stirring, dropwise adding diethyl ether until the solution is clear, transferring the diethyl ether to a vacuum drying oven at 45 ℃ after all, and drying for 11 hours to obtain a hydroxylamine polymer; dispersing a hydroxylamine polymer in anhydrous methanol 7 times the mass of the hydroxylamine polymer, adding dimethylolpropionic acid 0.18 times the mass of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin 0.85 times the mass of the hydroxylamine polymer, bubbling with nitrogen for 25min, reacting for 11h under 365nm ultraviolet light, adding dimethylolpropionic acid 2 times the mass of the hydroxylamine polymer, continuing to react for 4h under the ultraviolet light, centrifuging with diethyl ether to obtain a supernatant, and drying the supernatant in a vacuum drying oven at 45 ℃ to constant weight to obtain modified cyclodextrin;
(4) mixing hyperbranched polyglycidyl ether and modified cyclodextrin according to the mass ratio of 6:1, heating to 110 ℃, stirring at 80rpm, dropwise adding concentrated sulfuric acid with the mass fraction of 98% which is 0.25 times of that of the modified cyclodextrin at the speed of 4ml/min, stirring for reacting for 28 hours, adding plasticizer dibutyl phthalate with the mass of 0.04 times of that of the hyperbranched polyglycidyl ether, and uniformly stirring to obtain antifouling film slurry;
(5) Mixing 2, 6-dichlorobenzonitrile, resorcinol, potassium carbonate, N-methyl pyrrolidone and toluene according to a mass ratio of 1:1:1:8:8, heating to 160 ℃ in an argon range, reacting for 2 hours, adding 2, 6-difluorobenzonitrile which is 0.1 time of that of the 2, 6-dichlorobenzonitrile, continuously reacting for 1 hour, heating to 202 ℃ and reacting for 0.5 hour, then adding 2, 6-difluorobenzonitrile which is 0.06 time of that of the 2, 6-dichlorobenzonitrile, continuously reacting for 25 minutes, separating out and filtering with methanol, washing with methanol and hot water at 80 ℃ for 4 times respectively, and finally drying in a drying oven at 120 ℃ to constant weight to obtain fluoropolyether nitrile; adding chloroprene rubber, polyurethane rubber, carbon black, paraffin, an anti-aging agent D, fluoropolyether nitrile and a plasticizer into a mixing mill, mixing for 6min at 950rpm, heating to 108 ℃, adding a foaming agent disulfo-selenohydrazine diphenyl ether, a vulcanization accelerator TMTD and zinc oxide, continuously mixing for 4min, and extruding through a rubber extruderFiltering, and tabletting to obtain rubber sheet; placing the film into a flat vulcanizing agent mold, and heating at 143 deg.C under 133kg/cm2Then, vulcanizing and foaming, opening the mold after 16min, transferring into foaming agent at 133 deg.C and 133kg/cm under pressure2Secondly, vulcanizing and foaming again, opening the mold after 11min to prepare foamed rubber with the thickness of 120 mu m, wherein the foamed rubber comprises 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin, 0.05 part of antioxidant D, 15 parts of fluoropolyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent disulfo-selenohydrazine diphenyl ether, 0.5 part of vulcanization accelerator TMTD and 3 parts of zinc oxide in parts by weight;
(6) The gram weight is 130g/cm2Coating aqueous polyurethane adhesive with the thickness of 8 mu m on two sides of the Lycra cloth, attaching the Lycra cloth with the foaming rubber, standing for 40min, scraping edges, coating anti-fouling film slurry with the thickness of 65 mu m, and standing for 5d to obtain the long-acting anti-fouling fabric.
Example 3
(1) The preparation method of the carboxymethyl-cyclodextrin comprises the following steps: mixing cyclodextrin, sodium hydroxide and deionized water according to a mass ratio of 4.5:3.6:20, stirring until the cyclodextrin, sodium chloroacetate with a mass 2 times that of cyclodextrin are dissolved, stirring at 50rpm for reaction for 5 hours, cooling to room temperature, adjusting the pH value to 5 with hydrochloric acid, adding methanol with a mass 8 times that of cyclodextrin for precipitation, filtering after precipitation, drying in a vacuum drying oven with the temperature of 90 ℃ until the weight is constant, and obtaining the carboxymethyl-cyclodextrin
(2) Dispersing carboxymethyl-cyclodextrin in deionized water with the mass 10 times that of the carboxymethyl-cyclodextrin, dropwise adding a sodium hydroxide solution with the mass fraction of 5% and the mass fraction of 0.15 times that of the carboxymethyl-cyclodextrin at the speed of 5ml/min under the rpm of 10-20, continuously stirring, dropwise adding an acetonitrile solution of p-methylbenzenesulfonyl chloride with the mass fraction of 20% and the mass fraction of 0.5 times that of the carboxymethyl-cyclodextrin at the speed of 5ml/min, stirring and reacting at 25 ℃ and 1000rpm for 3 hours after dropwise adding, centrifuging to obtain a supernatant, standing the supernatant at 4 ℃ for 8 hours to generate precipitates, recrystallizing the precipitates twice by using the deionized water as a solvent, and freeze-drying at-60 ℃ to obtain the sulfonated-carboxymethyl-cyclodextrin; mixing sulfonation-carboxymethyl-cyclodextrin, thiourea, methanol and deionized water according to a mass ratio of 1.2:1.2:8:4, heating in a water bath to 85 ℃, performing reflux reaction for 48 hours, then performing rotary evaporation to obtain white precipitate, washing the white precipitate for 5 times by using anhydrous methanol, dissolving the white precipitate by using a sodium hydroxide solution with a mass fraction of 15 percent being 8 times that of the white precipitate, placing the white precipitate at 60 ℃ for reaction for 6 hours, adjusting the pH to 2.5 by using hydrochloric acid, then adding trichloroethylene with a mass being 0.08 time that of the white precipitate, cooling to 25 ℃, reacting for 1-2 hours, and finally performing suction filtration and recrystallization to obtain mercapto-carboxymethyl-cyclodextrin;
(3) Mixing 1, 4-butanediol diglycidyl ether, 2-methylallylamine and absolute methanol according to the mass ratio of 8.6:3:5, stirring and reacting for 72 hours at 500rpm, continuously stirring, dropwise adding diethyl ether until the solution is clear, transferring the diethyl ether to a vacuum drying oven at 50 ℃ after all, and drying for 12 hours to obtain a hydroxylamine polymer; dispersing a hydroxylamine polymer in anhydrous methanol 7.5 times of the mass of the hydroxylamine polymer, adding dimethylol propionic acid 0.2 times of the mass of the hydroxylamine polymer and mercapto-carboxymethyl-cyclodextrin 0.9 times of the mass of the hydroxylamine polymer, bubbling with nitrogen for 30min, reacting for 12h under 365nm ultraviolet light, adding dimethylol propionic acid 3 times of the mass of the hydroxylamine polymer, continuing to react for 5h under the ultraviolet light, centrifuging with diethyl ether to obtain a supernatant, and drying the supernatant in a vacuum drying oven at 50 ℃ to constant weight to obtain modified cyclodextrin;
(4) mixing hyperbranched polyglycidyl ether and modified cyclodextrin according to a mass ratio of 8:1, heating to 120 ℃, stirring at 100rpm, dropwise adding concentrated sulfuric acid with a mass fraction of 98% which is 0.3 times of that of the modified cyclodextrin at a speed of 5ml/min, stirring for reacting for 36 hours, adding plasticizer dibutyl phthalate with a mass which is 0.05 times of that of the hyperbranched polyglycidyl ether, and uniformly stirring to obtain antifouling film slurry;
(5) Mixing 2, 6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methyl pyrrolidone and toluene according to the mass ratio of 1:1.1:1.1:8:8, heating to 180 ℃ in the argon range, reacting for 3h, adding 2, 6-difluorobenzonitrile 0.15 times of the 2, 6-dichlorobenzonitrile, continuing to react for 2h, heating to 205 ℃ after continuing to react for 1h, adding 2, 6-difluorobenzonitrile 0.08 times of the 2, 6-dichlorobenzonitrile, continuing to react for 30min, precipitating with methanol, filtering, washing with methanol and hot water at 90 ℃ for 5 times respectively, and finally drying in a drying box at 120 ℃ to constant weight to obtain the fluorinePolyether nitrile; the preparation method comprises the following steps of putting chloroprene rubber, polyurethane rubber, carbon black, paraffin, an anti-aging agent D, fluoropolyether nitrile and a plasticizer into a mixing mill, mixing for 8min at 1000rpm, heating to 110 ℃, adding a foaming agent disulfo-selenohydrazide, a vulcanization accelerator TMTD and zinc oxide, continuing mixing for 5min, filtering by a rubber extruder, and tabletting to obtain a film; placing the film into a flat vulcanizing agent mold, and heating at 145 deg.C under 135kg/cm2Then, adding sulfur to foam, opening the mold after 20min, transferring into foaming agent at 135 deg.C under 135kg/cm2Secondly, vulcanizing and foaming again, opening the mould after 12min to prepare foamed rubber with the thickness of 160 mu m, wherein the foamed rubber comprises 55 parts of chloroprene rubber, 20 parts of polyurethane rubber, 5 parts of carbon black, 5 parts of paraffin, 0.06 part of antioxidant D, 20 parts of fluoropolyether nitrile, 12 parts of plasticizer, 10 parts of foaming agent disulfo-selenohydrazine diphenyl ether, 0.6 part of vulcanization accelerator TMTD and 4 parts of zinc oxide in parts by weight;
(6) The gram weight is 160g/cm2Coating 10 mu m waterborne polyurethane adhesive on two sides of the Lycra cloth, attaching the Lycra cloth with the foamed rubber, standing for 50min, scraping edges, coating 80 mu m antifouling film slurry, and standing for 7d to obtain the long-acting antifouling fabric.
Comparative example 1
The formulation of comparative example 1 was the same as example 2. The preparation method of the long-acting anti-fouling fabric is only different from the preparation method of the example 2 in that the step (2) is not carried out, and the step (3) is modified as follows: mixing 1, 4-butanediol diglycidyl ether, 2-methylallylamine and absolute methanol according to the mass ratio of 8.5:3:5, stirring and reacting for 71 hours at 400rpm, continuously stirring, dropwise adding diethyl ether until the solution is clear, transferring the diethyl ether to a vacuum drying oven at 45 ℃ after all, and drying for 11 hours to obtain a hydroxylamine polymer; dispersing a hydroxylamine polymer in anhydrous methanol 7 times the mass of the hydroxylamine polymer, adding dimethylolpropionic acid 0.18 times the mass of the hydroxylamine polymer and carboxymethyl-cyclodextrin 0.85 times the mass of the hydroxylamine polymer, bubbling with nitrogen for 25min, reacting for 11h under 365nm ultraviolet light, adding dimethylolpropionic acid 2 times the mass of the hydroxylamine polymer, continuing to react for 4h under the ultraviolet light, centrifuging with diethyl ether to obtain a supernatant, and drying the supernatant in a vacuum drying oven at 45 ℃ to constant weight to obtain the modified cyclodextrin.
Comparative example 2
The formulation of comparative example 2 was the same as example 2. The preparation method of the long-acting anti-fouling fabric is only different from that of the example 2 in that the steps (1), (2) and (3) are not carried out, and the step (4) is modified as follows: and (3) mixing the hyperbranched polyglycidyl ether with plasticizer dibutyl phthalate with the mass of 0.03-0.05 times of that of the hyperbranched polyglycidyl ether, and uniformly stirring to obtain the antifouling film slurry.
Comparative example 3
The formulation of comparative example 3 was the same as example 2. The preparation method of the long-acting anti-fouling fabric is only different from that of the example 2 in that the step (3) is not carried out, and the step (4) is modified as follows: mixing hyperbranched polyglycidyl ether and mercapto-carboxymethyl-cyclodextrin according to a mass ratio of 5:1, heating to 90 ℃, stirring at 50rpm, dropwise adding concentrated sulfuric acid with a mass fraction of 98% which is 0.2 times of that of modified cyclodextrin at a rate of 3ml/min, stirring for reacting for 24 hours, adding plasticizer dibutyl phthalate with a mass which is 0.03 times of that of hyperbranched polyglycidyl ether, and uniformly stirring to obtain the antifouling film slurry.
Comparative example 4
The formulation of comparative example 4 was the same as example 2. The preparation method of the long-acting anti-fouling fabric is different from that of the example 2 only in the difference of the step (5), and the step (5) is modified as follows: mixing 2, 6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methyl pyrrolidone and toluene according to a mass ratio of 1:1:1:8:8, heating to 160 ℃ in an argon range, reacting for 2 hours, adding 2, 6-difluorobenzonitrile 0.1 time of that of the 2, 6-dichlorobenzonitrile, continuing to react for 1 hour, heating to 202 ℃ and reacting for 0.5 hour, adding 2, 6-difluorobenzonitrile 0.06 time of that of the 2, 6-dichlorobenzonitrile, continuing to react for 25 minutes, separating out with methanol, filtering, washing with methanol and hot water at 80 ℃ for 4 times respectively, and finally drying in a drying oven at 120 ℃ to constant weight to obtain fluoropolyether nitrile; adding chloroprene rubber, carbon black, paraffin, antioxidant D, fluoropolyether nitrile and plasticizer into a mixing roll, mixing at 950rpm for 6min, heating to 108 ℃, adding foaming agent disulfo-selenohydrazine diphenyl ether, vulcanization accelerator TMTD and zinc oxide, mixing for 4min, filtering by a rubber extruder, tabletting, Preparing a film; placing the rubber sheet into a flat vulcanizing agent mold, and heating at 143 deg.C under 133kg/cm2Then, vulcanizing and foaming, opening the mold after 16min, transferring into foaming agent at 133 deg.C and 133kg/cm pressure2Then, vulcanizing and foaming are carried out again, and after 11min, the mould is opened, so as to prepare the foamed rubber with the thickness of 120 mu m, wherein the foamed rubber comprises, by weight, 50 parts of chloroprene rubber, 4 parts of carbon black, 4 parts of paraffin, 0.05 part of anti-aging agent D, 15 parts of fluoropolyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent bis-sulfoseleno-hydrazine diphenyl ether, 0.5 part of vulcanization accelerator TMTD and 3 parts of zinc oxide.
Comparative example 5
Comparative example 5 was formulated as in example 2. The preparation method of the long-acting anti-fouling fabric is different from that of the example 2 only in the difference of the step (5), and the step (5) is modified into the following steps: the preparation method comprises the following steps of putting chloroprene rubber, polyurethane rubber, carbon black, paraffin, an anti-aging agent D, polyether nitrile and a plasticizer into a mixing roll, mixing for 6min at 950rpm, heating to 108 ℃, adding a foaming agent of disulfo-selenohydrazine diphenyl ether, a vulcanization accelerator TMTD and zinc oxide, continuing mixing for 4min, filtering by a rubber extruder, and tabletting to obtain a rubber sheet; placing the rubber sheet into a flat vulcanizing agent mold, and heating at 143 deg.C under 133kg/cm 2Then, vulcanizing and foaming, opening the mold after 16min, transferring into foaming agent at 133 deg.C and 133kg/cm pressure2Then, vulcanizing and foaming are carried out again, and after 11min, the mould is opened to prepare the foamed rubber with the thickness of 120 mu m, wherein the foamed rubber comprises, by weight, 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin, 0.05 part of anti-aging agent D, 15 parts of polyether nitrile, 10 parts of plasticizer, 9 parts of foaming agent disulfo-selenohydrazine diphenyl ether, 0.5 part of vulcanization accelerator TMTD and 3 parts of zinc oxide.
Comparative example 6
Comparative example 6 was formulated as in example 2. The preparation method of the long-acting anti-fouling fabric is different from that of the example 2 only in the difference of the step (5), and the step (5) is modified into the following steps: adding chloroprene rubber, polyurethane rubber, carbon black, paraffin, antioxidant D and plasticizer into a mixing roll, mixing at 950rpm for 6min, heating to 108 ℃, adding foaming agent disulfo-selenohydrazine diphenyl ether, vulcanization accelerator TMTD and zinc oxide, and continuously mixingRefining for 4min, filtering with rubber extruder, and tabletting to obtain rubber sheet; placing the rubber sheet into a flat vulcanizing agent mold, and heating at 143 deg.C under 133kg/cm2Then, vulcanizing and foaming, opening the mold after 16min, transferring into foaming agent at 133 deg.C and 133kg/cm pressure 2And then, vulcanizing and foaming are carried out again, and after 11min, the die is opened to prepare the foamed rubber with the thickness of 120 mu m, wherein the foamed rubber comprises, by weight, 50 parts of chloroprene rubber, 18 parts of polyurethane rubber, 4 parts of carbon black, 4 parts of paraffin, 0.05 part of anti-aging agent D, 10 parts of plasticizer, 9 parts of foaming agent bis-sulfoseleno-hydrazine diphenyl ether, 0.5 part of vulcanization accelerator TMTD and 3 parts of zinc oxide.
Effects of the invention
Table 1 below gives the results of performance analysis of the long-acting antifouling fabrics according to examples 1, 2 and 3 of the present invention and comparative examples 1, 2, 3, 4, 5 and 6.
TABLE 1
Figure BDA0003648532180000141
Compared with the experimental data of the comparative example in the table 1, it can be obviously found that the long-acting anti-fouling fabrics prepared in the examples 1, 2 and 3 have good anti-fouling and anti-tearing peel strength and long service life;
compared with the experimental data of examples 1, 2 and 3 and comparative examples 1, 2 and 3, the hyperbranched polyglycidyl ether is used for reacting with the modified cyclodextrin to prepare the antifouling film, the sulfydryl is introduced to the carboxymethyl-cyclodextrin to react with the double bond on the hydroxylamine polymer to form the modified cyclodextrin with a long chain, the stability is enhanced, the hydroxylamine polymer is grafted to the sulfydryl-carboxymethyl-cyclodextrin, a large amount of hydroxyl is introduced to enhance the hydrophilicity, so that a compact hydration layer can be formed on the surface of the antifouling film, fouling substances such as protein cannot pass through the compact hydration layer, the interaction with the surface of the fabric is reduced, and the antifouling property is achieved; the modified cyclodextrin is introduced into the hyperbranched polyglycidyl ether, the stability of the antifouling film is enhanced and the service life of the fabric is enhanced by virtue of the stability of the cyclodextrin in seawater, and meanwhile, the long chain of the modified cyclodextrin is entangled on the hyperbranched polyglycidyl ether, so that the density of the antifouling film is enhanced, and further the impact resistance of the fabric is enhanced, and compared with the experimental data of examples 1, 2 and 3 and comparative examples 4, 5 and 6, the foamed rubber is prepared by blending chloroprene rubber, polyurethane rubber and fluoropolyether nitrile for vulcanization foaming; the addition of the polyurethane rubber improves the impact resistance of the foamed rubber; the fluoropolyether nitrile is used as a curing agent for vulcanization, and can react with hydroxyl on a water-based polyurethane adhesive and an anti-fouling membrane to tightly connect the lycra cloth, the foamed rubber and the anti-fouling membrane, so that the peel strength of the fabric is enhanced, and meanwhile, fluorine elements are introduced into the foamed rubber layer, so that the foamed rubber is hydrophobic while the anti-fouling layer is hydrophilic, and the service life of the fabric is prolonged.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The long-acting anti-fouling fabric comprises Leica cloth, foamed rubber and an anti-fouling film from inside to outside in sequence, and is characterized in that the foamed rubber is prepared by blending chloroprene rubber, polyurethane rubber and fluoropolyether nitrile for vulcanization foaming.
2. The fabric according to claim 1, wherein said fluoropolyethernitrile is obtained from 2, 6-dichlorobenzonitrile, 2, 6-difluorobenzonitrile and N-methyl-pyrrolidone.
3. The long-acting anti-fouling fabric according to claim 1, wherein the anti-fouling film is prepared by reacting hyperbranched polyglycidyl ether with modified cyclodextrin.
4. The long-acting antifouling fabric according to claim 3, wherein the modified cyclodextrin is obtained by grafting a hydroxylamine polymer onto mercapto-carboxymethyl-cyclodextrin.
5. The preparation method of the long-acting anti-fouling fabric is characterized by comprising the following specific steps of:
(1) dispersing carboxymethyl-cyclodextrin in deionized water with the mass of 8-10 times that of the carboxymethyl-cyclodextrin, and performing dispersion at 10-20 rpm, dropwise adding a sodium hydroxide solution with the mass fraction of 3-5% and 0.1-0.15 times of the mass of carboxymethyl-cyclodextrin at the speed of 3-5 ml/min, continuously stirring, dropwise adding an acetonitrile solution of p-methylbenzenesulfonyl chloride with the mass fraction of 10-20% and 0.45-0.5 times of the mass of carboxymethyl-cyclodextrin at the speed of 3-5 ml/min, stirring and reacting for 2-3 hours at the temperature of 22-25 ℃ and at the speed of 800-1000 rpm after dropwise adding, centrifuging to obtain a supernatant, standing the supernatant at the temperature of 0-4 ℃ for 6-8 hours to generate precipitates, recrystallizing the precipitates twice by using deionized water as a solvent, and performing freeze drying at the temperature of-50-60 ℃ to obtain the sulfonated-carboxymethyl-cyclodextrin; mixing sulfonation-carboxymethyl-cyclodextrin, thiourea, methanol and deionized water according to a mass ratio of 1:1:6: 3-1.2: 1.2:8:4, heating in a water bath to 80-85 ℃, performing reflux reaction for 48 hours, performing rotary evaporation to obtain white precipitate, washing the white precipitate for 3-5 times by using anhydrous methanol, dissolving the white precipitate by using a sodium hydroxide solution with a mass fraction of 10-15% which is 5-8 times that of the white precipitate, reacting for 5-6 hours at 50-60 ℃, adjusting the pH to 2-2.5 by using hydrochloric acid, adding trichloroethylene with a mass of 0.04-0.08 times that of the white precipitate, cooling to 20-25 ℃, reacting for 1-2 hours, and finally performing suction filtration and recrystallization to obtain mercapto-carboxymethyl-cyclodextrin;
(2) Dispersing a hydroxylamine polymer in absolute methanol with the mass 6.5-7.5 times that of the hydroxylamine polymer, adding dimethylolpropionic acid with the mass 0.15-0.2 time that of the hydroxylamine polymer and sulfydryl-carboxymethyl-cyclodextrin with the mass 0.8-0.9 time that of the hydroxylamine polymer, bubbling with nitrogen for 20-30 min, reacting for 10-12 h under 365nm ultraviolet light, adding dimethylolpropionic acid with the mass 2-3 times that of the hydroxylamine polymer, continuing to react for 3-5 h under the ultraviolet light, centrifuging with diethyl ether to obtain a supernatant, placing the supernatant in a vacuum drying oven with the temperature of 40-50 ℃ and drying to constant weight to obtain modified cyclodextrin;
(3) mixing hyperbranched polyglycidyl ether and modified cyclodextrin according to a mass ratio of 5: 1-8: 1, heating to 90-120 ℃, stirring at 50-100 rpm, dropwise adding concentrated sulfuric acid with a mass fraction of 98% which is 0.2-0.3 times of that of the modified cyclodextrin at a speed of 3-5 ml/min, stirring for reacting for 24-36 h, adding plasticizer dibutyl phthalate with a mass fraction of 0.03-0.05 times of that of hyperbranched polyglycidyl ether, and uniformly stirring to obtain antifouling film slurry;
(4) the preparation method comprises the following steps of putting chloroprene rubber, polyurethane rubber, carbon black, paraffin, an anti-aging agent D, fluoropolyether nitrile and a plasticizer into a mixing mill, mixing for 5-8 min at 900-1000 rpm, heating to 105-110 ℃, adding a foaming agent, namely disulfo-selenohydrazine diphenyl ether, a vulcanization accelerator TMTD and zinc oxide, continuing mixing for 3-5 min, filtering by a rubber extruder, and tabletting to obtain a film; putting the film into a flat vulcanizing agent mold, and heating at 140-145 ℃ under 130-135 kg/cm 2Then, vulcanizing and foaming, opening the mold after 15-20 min, transferring the mixture into a foaming agent, and performing pressure treatment at 130-135 ℃ and 130-135 kg/cm2Secondly, vulcanizing and foaming again, opening the mold after 10-12 min to obtain the foamed rubber with the thickness of 100-160 mu m;
(5) coating a waterborne polyurethane adhesive with the thickness of 5-10 mu m on two sides of the Lycra cloth, attaching the Lycra cloth to foamed rubber, standing for 30-50 min, scraping edges, coating an antifouling film slurry with the thickness of 50-80 mu m, and standing for 3-7 d to obtain the long-acting antifouling fabric.
6. The method for preparing a long-acting anti-fouling fabric according to claim 5, wherein in the step (1): the preparation method of the carboxymethyl-cyclodextrin comprises the following steps: mixing cyclodextrin, sodium hydroxide and deionized water according to a mass ratio of 4.2:3.5: 18-4.5: 3.6:20, stirring until the mixture is dissolved, adding sodium chloroacetate with a mass of 1.8-2 times that of the cyclodextrin, stirring at 30-50 rpm for reaction for 3-5 hours, cooling to room temperature, adjusting the pH value to 4.8-5 with hydrochloric acid, adding methanol with a mass of 5-8 times that of the cyclodextrin for precipitation, precipitating, filtering, and drying in a vacuum drying oven at 80-90 ℃ until the weight is constant to obtain the carboxymethyl-cyclodextrin.
7. The method for preparing a long-acting anti-fouling fabric according to claim 5, wherein in the step (2): the preparation method of the hydroxylamine polymer comprises the following steps: mixing 1, 4-butanediol diglycidyl ether, 2-methylallylamine and absolute methanol according to the mass ratio of 8.4:3: 4-8.6: 3:5, stirring and reacting for 70-72 h at 300-500 rpm, continuously stirring, dropwise adding diethyl ether until the solution is clear, and transferring the diethyl ether to a vacuum drying oven at 40-50 ℃ for drying for 10-12 h to obtain the hydroxylamine polymer.
8. The method for preparing a long-acting anti-fouling fabric according to claim 5, wherein in the step (4): the preparation method of the fluoropolyether nitrile comprises the following steps: mixing 2, 6-dichlorobenzonitrile, m-diphenol, potassium carbonate, N-methyl pyrrolidone and toluene according to a mass ratio of 1:1:1:5: 5-1: 1.1:1.1:8:8, heating to 150-180 ℃ under the argon atmosphere, reacting for 2-3 h, adding 0.1-0.15 times of 2, 6-dichlorobenzonitrile, continuing to react for 1-2 h, heating to 200-205 ℃, reacting for 0.5-1 h, adding 0.05-0.08 times of 2, 6-difluorobenzonitrile, continuing to react for 20-30 min, precipitating with methanol, filtering, washing with methanol and hot water at 70-90 ℃ for 3-5 times, and finally drying in a drying box at 120 ℃ to constant weight to obtain the fluoropolyether nitrile.
9. The method for preparing a long-acting anti-fouling fabric according to claim 5, wherein in the step (4): the foaming rubber comprises, by weight, 45-55 parts of chloroprene rubber, 15-20 parts of polyurethane rubber, 3-5 parts of carbon black, 3-5 parts of paraffin, 0.04-0.06 part of an anti-aging agent D, 10-20 parts of fluoropolyether nitrile, 8-12 parts of a plasticizer, 8-10 parts of a foaming agent bis (seleno-hydrazine) diphenyl ether, 0.4-0.6 part of a vulcanization accelerator TMTD and 2-4 parts of zinc oxide.
10. The method for preparing a long-acting anti-fouling fabric according to claim 5, wherein in the step (5): the gram weight of the Lycab is 100-160 g/cm2。
CN202210541538.8A 2022-05-17 2022-05-17 Long-acting anti-fouling fabric and preparation method thereof Pending CN114750484A (en)

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CN106674664A (en) * 2016-12-12 2017-05-17 天长市康宁塑胶科技有限公司 Tear-resistant high-wear-resistance chloroprene rubber material
CN214395789U (en) * 2020-08-25 2021-10-15 苏州市芳洲纺织有限公司 Dacron cloth with hydrophobic material for diving suit
CN113667485A (en) * 2021-07-12 2021-11-19 同济大学 Composite soil eluting agent containing modified beta cyclodextrin and method for eluting and repairing composite contaminated soil by adopting same

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CN106674664A (en) * 2016-12-12 2017-05-17 天长市康宁塑胶科技有限公司 Tear-resistant high-wear-resistance chloroprene rubber material
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