CN117327284B - Preparation method of sulfur-containing onium ion organic silicon resin with marine antifouling function - Google Patents
Preparation method of sulfur-containing onium ion organic silicon resin with marine antifouling function Download PDFInfo
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- CN117327284B CN117327284B CN202311278764.2A CN202311278764A CN117327284B CN 117327284 B CN117327284 B CN 117327284B CN 202311278764 A CN202311278764 A CN 202311278764A CN 117327284 B CN117327284 B CN 117327284B
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- sulfur
- organic silicon
- onium ion
- silicon resin
- marine antifouling
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 58
- 239000011593 sulfur Substances 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 239000011347 resin Substances 0.000 title claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 42
- 239000010703 silicon Substances 0.000 title claims abstract description 42
- 150000004010 onium ions Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 polysiloxane Polymers 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 24
- 150000003568 thioethers Chemical class 0.000 claims abstract description 19
- 239000003921 oil Substances 0.000 claims abstract description 16
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- FAYOCELKCDKZCA-UHFFFAOYSA-N 5-hydroxy-2,4-dimethylthiophen-3-one Chemical compound CC1SC(O)=C(C)C1=O FAYOCELKCDKZCA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 14
- 229920002050 silicone resin Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920013822 aminosilicone Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 239000002952 polymeric resin Substances 0.000 abstract description 3
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 35
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 24
- 230000000844 anti-bacterial effect Effects 0.000 description 21
- 239000007788 liquid Substances 0.000 description 19
- KMSNYNIWEORQDJ-UHFFFAOYSA-N Dihydro-2(3H)-thiophenone Chemical compound O=C1CCCS1 KMSNYNIWEORQDJ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003973 paint Substances 0.000 description 12
- 229920001558 organosilicon polymer Polymers 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 239000002519 antifouling agent Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000003573 thiols Chemical class 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000032770 biofilm formation Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- BAXRWZGFHHYVQE-UHFFFAOYSA-N n-(2-oxothiolan-3-yl)propanamide Chemical compound CCC(=O)NC1CCSC1=O BAXRWZGFHHYVQE-UHFFFAOYSA-N 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- IEDVQOXHVRVPIX-UHFFFAOYSA-N 2-(oxolan-2-yl)acetic acid Chemical compound OC(=O)CC1CCCO1 IEDVQOXHVRVPIX-UHFFFAOYSA-N 0.000 description 1
- 241000206761 Bacillariophyta Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RNGHAJVBYQPLAZ-UHFFFAOYSA-N Terodiline hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(CC(C)NC(C)(C)C)C1=CC=CC=C1 RNGHAJVBYQPLAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
Abstract
The application relates to the technical field of high molecular polymer resin materials, in particular to a preparation method of sulfur-containing onium ion organic silicon resin with marine antifouling function, which comprises the following steps: adding thiolactone, amine, polysiloxane containing double bonds and solvent into a flask, and putting the flask into an oil bath pot with the temperature of 20-100 ℃ to react for 1-24h to obtain thioether-containing organic silicon resin; dissolving the sulfur ether-containing organic silicon resin in an organic solvent, adding methyl iodide into the organic solvent at the temperature of between 20 ℃ below zero and 50 ℃ to react for 1 to 24 hours, and obtaining the sulfur onium ion-containing organic silicon resin. The material can be used for surface fouling protection of application scenes of underwater facilities such as ships, ocean engineering, ocean wind power, ocean pastures, underwater cables, underwater monitoring equipment and the like.
Description
Technical Field
The application relates to the technical field of high molecular polymer resins, in particular to a preparation method of sulfur-containing onium ion organic silicon resin with marine antifouling function.
Background
Preventing the adsorption and the generation of marine organisms on marine equipment is one of the most needed breakthrough technologies for developing marine resources and developing marine economy. The traditional marine antifouling paint is prepared by adding an antifouling agent with certain toxicity to algae and organisms into resin, releasing the antifouling agent into seawater at a certain speed to prevent marine organism from adhering, and gradually reducing the antifouling effect to failure along with continuous release of the antifouling agent.
In recent technology, paint containing an organic tin anti-fouling agent and an organic silicon anti-fouling paint are generally adopted, the organic tin anti-fouling agent can cause reverse change of the growth sex of marine organisms and can accumulate in organisms, so that huge damage is caused to the marine ecological environment, international Maritime Organization (IMO) 10 month passes the international convention of controlling the harmful anti-fouling bottom system of ships in 2001, and formally takes effect in 9 months 17 of 2008, and the use of the organic tin anti-fouling paint is forbidden.
The organosilicon low-surface-energy ship antifouling paint is used as the latest generation of ship antifouling paint, has the advantages of environmental protection, drag reduction and energy conservation, and the characteristic of low surface energy prevents the initial adhesion of marine organisms, and the smooth surface reduces the sailing resistance. Intersleek425 silicone anti-fouling coatings were first introduced in 1996 by International paint company in England, after which the European, heiran aged, japanese, mid-coat paint company and PPG in the U.S. also introduced silicone based anti-fouling paint products in succession. Although the special environment-friendly nontoxic property of the low-surface-energy organic silicon antifouling resin enables the low-surface-energy organic silicon antifouling resin to have incomparable advantages compared with other resins for the ship antifouling paint, the application is limited by inherent defects of the resin, and the problem of insufficient application performance exists. The organosilicon is a low-surface-energy material, the polarity is low, the adhesion force between the organosilicon and a substrate is poor, and a coating film is easy to fall off; the silane Si-O-Si bond energy of the organic silicon is low, the mechanical strength of the polymer is low, the coating is easy to scratch and damage, and the application condition that the coating cannot withstand abrasion in a marine splash zone and a shipboard landing zone can not be realized; the organic silicon resin has the antifouling performance by means of the self low surface property, and the antifouling effect of the organic silicon resin is poor in static environment application without seawater scouring, so that the application requirement cannot be met.
In a patent CN101434805a applied by the seventh, second and fifth institute of heavy industry of ships, china, a self-layering curable low-surface-energy antifouling paint is provided, wherein the paint utilizes the incompatibility principle between epoxy resin and organic silicon resin, and is automatically layered in the film forming process, the epoxy resin sinks to the bottom, and the organic silicon resin is exposed on the outer surface. The patent solves the problem of poor adhesive force of low-surface-energy organosilicon, and the resin has no antibacterial and antibacterial functional groups, and has a short antifouling period of only three months.
How to achieve efficient antifouling first requires knowledge of the attachment process of marine organisms. Early marine organism attachment is the formation of a biofilm consisting mainly of bacteria and diatoms, followed by secondary attachment of larvae or spores of large organisms to the biofilm. Thus, inhibition of biofilm formation is critical to prevent subsequent attachment of large organisms. However, due to the variety of marine organisms and the variety of sizes, it is difficult to obtain antibacterial and antiseptic broad spectrum and biofilm formation inhibiting effects with only silicone resin coatings. The quaternary ammonium salt is used as a broad-spectrum, efficient and simple-synthesis bactericide, is grafted into the organic silicon resin by a plurality of researchers for marine antifouling, and achieves a certain antifouling effect. However, quaternary ammonium salts are easily oxidized and degraded, have poor ocean durability, and after biodegradation, are subjected to water overfertilization, so that the environment is polluted. Accordingly, attention is being paid to other cationic compounds.
The sulfonium ion-containing compound means that the molecule contains-S + Radical substances, sulfonium ion compounds are widely present in animals and plants in nature. As early as 1948, challenger and Simpson have isolated this class from seaweed. Subsequently, vigneaucl v.d. and his co-workers studied its biological activity. The sulfonium ion-containing compound was found to play an extremely important role in metabolism of animals and plants. As the research is conducted, the sulfonium ion-containing compound is widely applied to the industries of textile printing and dyeing, sterilization, disinsection, rust and corrosion prevention, organic synthesis, oil extraction, detergents, cosmetics, medicines, agriculture, paper making and the like, and compared with a small molecular antimicrobial agent, the polymer containing the sulfonium ion generally has higher stability and processability. However, due to structural design defects, the performance of the sulfonium ion polymer always fails to achieve excellent antibacterial efficiency similar to that of small molecular sulfonium ions. Biomacromolecules, team Anzar Khan, published their study of sulfonium ion biocompatibilityProblems of structural stability, antibacterial activity and the like, and they found that the side-chain sulfonium ion-containing polymer does not have any remarkable antibacterial activity, so that it is seen that only the topological structure containing sulfonium ions and having no hydrophilic and hydrophobic property does not have the antifouling function of the ocean.
Disclosure of Invention
Aiming at the defects existing in the prior art, the purpose of the application is to design the functional polymer resin so that the marine antifouling coating based on the resin has the antibacterial function and improves the resin strength and the antifouling effect, thereby solving the problems of poor static antifouling property, low mechanical strength, poor wear resistance of the coating surface and insufficient antifouling effect in the prior art.
In order to achieve the above purpose, the present application is implemented by the following technical schemes: the preparation method of the sulfur-containing onium ion organic silicon resin with the marine antifouling function comprises the following steps:
adding thiolactone, amine, polysiloxane containing double bonds and solvent into a flask, and putting the flask into an oil bath pot with the temperature of 20-100 ℃ to react for 1-24h to obtain thioether-containing organic silicon resin;
dissolving the sulfur ether-containing organic silicon resin in an organic solvent, adding methyl iodide into the organic solvent at the temperature of between 20 ℃ below zero and 50 ℃ to react for 1 to 24 hours, and obtaining the sulfur onium ion-containing organic silicon resin.
Preferably, the thiolactone is thiolactone of different substituent groups, and the thiolactone has the following structure:
。
preferably, the amine is one or more of propylamine, butylamine, hexylamine, single-end amino polyethylene glycol, double-end amino polyethylene glycol aniline, benzylamine, polyether amine and amino silicone oil.
Preferably, the double bond-containing polysiloxane is terminal double bond polysiloxane or branched double bond polysiloxane, and the structure is as follows:
。
preferably, the molar ratio of the thiolactone, amine and double bond-containing polysiloxane is 1:0.5-1.5:0.01-1.
Preferably, the molar ratio of the sulfur-containing ether organic silicon resin to methyl iodide is 1:0.01-50.
Preferably, the molecular weight of the sulfonium ion containing silicone resin is 10 3 -10 7 。
Compared with the known public technology, the technical scheme provided by the application has the following beneficial effects:
(1) The polymer prepared by introducing sulfonium ions into a polymer with hydrophobic organosilicon as a main chain on a main chain, a branched chain and a cross-linked network is designed and synthesized, so that the polymer not only has the low surface energy of the organosilicon and ensures that marine spores are difficult to attach, but also can be automatically desorbed under the scouring of seawater, and the antibacterial and bacteriostatic functions of the sulfonium ions are exerted through a hydrophilic-hydrophobic topology structure, so that a biomembrane is difficult to form, the problem that the antifouling effect of pure organosilicon resin in a static environment is poor is solved, and the problem that sulfonium ion monomers cannot be applied to film formation is solved. The antibacterial and antibacterial functions of sulfonium ions are fully utilized, a non-toxic technology which does not need to adopt a biological biocide is obtained, the polymer material with an antifouling effect in static and dynamic marine environments is obtained, the strength of the polymer is greatly improved, and the polymer material has the characteristics of high strength and wear resistance;
(2) The polymer can be singly applied to film formation, and can also be applied to the surface of an ocean underwater component together with pigment and filler, an antifouling agent, an auxiliary agent and the like to form a coating composition, so that the attachment and the tillering of marine organisms are prevented. The material can be used for protecting ships, ocean engineering, ocean wind power, ocean pastures and ocean facilities under waterline, and can also be used for preventing pollution on the surfaces of underwater cables, underwater monitoring equipment and underwater facilities.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is apparent that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a gel permeation chromatogram of the sulfur ether-containing polymer prepared in comparative examples 1 to 5 and examples 1 to 5 of the present invention and a sulfur-containing onium ion polymer;
FIG. 2 is a graph showing water contact angles of the sulfur-containing ether polymers and the sulfur-containing onium ion polymers prepared in comparative examples 1 to 5 and examples 1 to 5 of the present invention;
FIG. 3 is a graph showing the mechanical strength of the thiol-containing polymers and the sulfonium ion-containing polymers prepared in comparative examples 1 to 5 and examples 1 to 5 of the present invention;
FIG. 4 is a graph showing the abrasion resistance of the sulfur ether-containing polymers and the sulfur-containing onium ion-containing polymers prepared in comparative examples 1 to 5 and examples 1 to 5 of the present invention;
FIG. 5 is a graph showing the antibacterial properties of the thiol-containing polymers and the sulfonium ion-containing polymers prepared in comparative examples 1 to 5 and examples 1 to 5 of the present invention;
FIG. 6 is a graph showing the antibacterial efficiency of the thiol-based polymer and the sulfonium ion-containing polymer prepared in comparative examples 1 to 5 and examples 1 to 5 of the present invention;
FIG. 7 shows the antifouling effect of the thiol-containing polymers prepared in comparative examples 1 to 5 and examples 1 to 5 according to the present invention and the sulfonium ion-containing polymer in an actual sea area static test for 3 years.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the embodiments described are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
In the following examples of the invention, the reagents used were of the following purity and origin:
gamma-thiolactone, an Naiji chemistry, 98%;
propylamine, carbofuran, 98%;
polysiloxane with terminal double bonds, micllin, molecular weight of 15000g/mol,80-85%;
poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ], microphone, molecular weight 15000g/mol,80-85%;
monoamine polyethylene glycol, micturin, molecular weight 4000g/mol,99%;
double-end amino polyethylene glycol, microphone, molecular weight 4000g/mol,99%;
methyl iodide, aledine, 97%;
the solvent can be one of tetrahydrofuran acetic acid, ethyl ester, butyl acetate, xylene, petroleum ether, ethanol, water, and dimethyl sulfoxide.
Example 1
Gamma-thiobutyrolactone (10.1 mmol), diamido polyethylene glycol (5 mmol), double bond terminated polysiloxane (5 mmol) and solvent were added to a 50mL three-necked flask and placed in an oil bath at 70 ℃ with the open mouth. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
after natural cooling, the sulfur ether-containing organic silicon resin is dissolved in a solvent, at the temperature of minus 30 ℃, methyl iodide (10.2 mmol) is added, the reaction is finished after 12 hours, the solvent is removed by rotary evaporation, and colorless liquid is obtained, namely the sulfur onium ion-containing organic silicon polymer, and the reaction route of the reaction is as follows:
。
example 2
Gamma-thiobutyrolactone (10 mmol), propylamine (10 mmol), terminal double bond polysiloxane (5 mmol) and solvent were taken and added to a 50mL three-necked flask, which was placed in an oil bath at 70 c. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
after natural cooling, the sulfur ether-containing organic silicon resin is dissolved in a solvent, at the temperature of minus 30 ℃, methyl iodide (10 mmol) is added, the reaction is finished after 12 hours, the solvent is removed by rotary evaporation, and colorless liquid is obtained, namely the sulfur onium ion-containing organic silicon polymer, and the reaction route of the reaction is as follows:
。
example 3
Gamma-thiobutyrolactone (10.1 mmol), monoamine polyethylene glycol (10 mmol), poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ] (10 mmol) and solvent were added to a 50mL three-necked flask, and the flask was placed in an oil bath at 70 ℃. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
after natural cooling, the sulfur ether-containing organic silicon resin is dissolved in a solvent, at the temperature of minus 30 ℃, methyl iodide (10 mmol) is added, the reaction is finished after 12 hours, the solvent is removed by rotary evaporation, and colorless liquid is obtained, namely the sulfur onium ion-containing organic silicon polymer, and the reaction route of the reaction is as follows:
。
example 4
Gamma-thiobutyrolactone (10.1 mmol), diamido polyethylene glycol (5 mmol), poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ] (5 mmol) and solvent were added to a 50mL three-necked flask and placed in an oil bath at 70 c. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
after natural cooling, the sulfur ether-containing organic silicon resin is dissolved in a solvent, at the temperature of minus 30 ℃, methyl iodide (60 mmol) is added, the reaction is finished after 12 hours, the solvent is removed by rotary evaporation, colorless liquid is obtained, and the liquid is sprayed to form a film, namely the sulfur onium ion-containing organic silicon polymer, and the reaction route of the reaction is as follows:
。
example 5
N- (tetrahydro-2-oxo-3-thienyl) propanamide (10.1 mmol), propylamine (10 mmol), poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ] (1 mmol) and solvent were taken and placed in a 50mL three-necked flask with an open mouth in an oil bath at a temperature of 70 ℃. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
after natural cooling, the above-mentioned sulfur ether-containing organic silicon resin is dissolved in solvent, at the temperature of-30 deg.C (100 mmol) of methyl iodide is added, after 12h the reaction is completed, and the solvent is removed by rotary evaporation. The colorless liquid is obtained, and is sprayed to form a film, wherein the liquid is the organosilicon polymer containing the sulfonium ions, and the reaction route of the reaction is as follows:
。
comparative example 1
Gamma-thiobutyrolactone (10.1 mmol), diamido polyethylene glycol (5 mmol), double bond terminated polysiloxane (5 mmol) and solvent were added to a 50mL three-necked flask and placed in an oil bath at 70 ℃ with the open mouth. The reaction was followed by TLC and after 12h the reaction was completed, at which time the gamma-thiolactone was essentially complete.
Naturally cooling, removing the solvent by rotary evaporation to obtain colorless liquid, and spraying the colorless liquid to form a film, wherein the liquid is the thioether-containing organosilicon polymer, and the reaction route of the above reaction is as follows:
。
comparative example 2
Gamma-thiobutyrolactone (10 mmol), propylamine (10 mmol), terminal double bond polysiloxane (5 mmol) and solvent were taken and added to a 50mL three-necked flask, which was placed in an oil bath at 70 c. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
naturally cooling, rotationally evaporating to remove the solvent to obtain colorless liquid, namely the sulfate ion-containing organosilicon polymer, and spraying the liquid to form a film, wherein the reaction route of the reaction is as follows:
。
comparative example 3
Gamma-thiobutyrolactone (10.5 mmol), monoamine polyethylene glycol (10 mmol), poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ] (10 mmol) and solvent were added to a 50mL three-necked flask, and the flask was placed in an oil bath at 70 ℃. The reaction was followed by TLC and after 12h the reaction was completed, at which time the gamma-thiolactone was essentially complete.
Naturally cooling, rotationally evaporating to remove the solvent to obtain colorless liquid, namely the thioether-containing organosilicon polymer, and spraying the liquid to form a film, wherein the reaction route of the reaction is as follows:
。
comparative example 4
Gamma-thiobutyrolactone (10.1 mmol), diamido polyethylene glycol (5 mmol), poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ] (5 mmol) and solvent were added to a 50mL three-necked flask and placed in an oil bath at 70 c. The reaction was followed by TLC and after 12h the reaction was completed, at which time the gamma-thiolactone was essentially complete.
Naturally cooling, removing the solvent by rotary evaporation to obtain colorless liquid, and spraying the colorless liquid to form a film, wherein the liquid is the thioether-containing organosilicon polymer, and the reaction route of the above reaction is as follows:
。
comparative example 5
N- (tetrahydro-2-oxo-3-thienyl) propanamide (10.1 mmol), propylamine (10 mmol), poly [ dimethylsiloxane-co- (vinyl) methylsiloxane ] (1 mmol) and solvent were taken and placed in a 50mL three-necked flask with an open mouth in an oil bath at a temperature of 70 ℃. The reaction process is tracked by TLC, and the reaction is finished after 12 hours, at the moment, the gamma-thiobutyrolactone can basically react to obtain the thioether-containing organic silicon resin;
after natural cooling, the solvent was removed by rotary evaporation. The colorless liquid is obtained, and is sprayed to form a film, wherein the liquid is the thioether-containing organosilicon polymer, and the reaction route of the reaction is as follows:
。
performance tests were carried out in the same manner as in comparative examples 1 to 5 and examples 1 to 5, wherein the molecular weight of the sulfur ether polymer of comparative example 1 was 18100 g/mol, the molecular weight of the sulfur onium ion polymer of example 1 was 21500 g/mol, the molecular weight of the sulfur ether polymer of comparative example 2 was 23500 g/mol, the molecular weight of the sulfur onium ion polymer of example 2 was 27000 g/mol, the molecular weight of the sulfur ether polymer of comparative example 3 was 30400 g/mol, the molecular weight of the sulfur onium ion polymer of example 3 was 34000 g/mol, the molecular weight of the sulfur ether polymer of comparative example 4 was 82000 g/mol, the molecular weight of the sulfur onium ion polymer of example 4 was 95000 g/mol, the molecular weight of the sulfur ether polymer of comparative example 5 was 85500 g/mol, the molecular weight of the sulfur onium ion polymer of example 5 was 98300 g/mol, indicating successful synthesis of the sulfur ether polymer of comparative example 1 to 5 (see FIG. 1).
Comparative example 1 Sulfur Ether Polymer having Water contact Angle of 107 o Example 1 Water contact Angle of the Sulfonium ion-containing Polymer was 97 o Comparative example 2 Water contact Angle of Sulfur Ether Polymer o Example 2 Water contact Angle of the Sulfonium ion containing Polymer was 103 o Comparative example 3 Water contact Angle of the thio Ether Polymer was 99 o Example 3 Water contact Angle of the Sulfonium ion containing Polymer was 71 o Comparative example 4 Water contact Angle of the thio ether Polymer was 89 o Example 4 Water contact Angle of the Sulfonium ion containing Polymer was 53 o Comparative example 5 Water contact Angle of the thiol-containing Polymer was 87 o Example 5 Water contact Angle of the Sulfonium ion containing Polymer was 58 o The water antenna was shown to decrease significantly after ionization of the sulfonium ion polymers of examples 1-5 (see FIG. 2).
The mechanical properties of comparative examples 1-5 and examples 1-5 were tested, and the test results showed that the mechanical strength of examples 1-5 corresponding to comparative examples 1-5 was significantly improved, and that the mechanical strength of the bisaminopolyethylene glycol prepared sulfonium ion polymer was the highest (as shown in FIG. 3).
The abrasion resistance of the comparative examples 1-5 and examples 1-5 is tested, and the test results show that the abrasion resistance of the comparative examples 1-5 corresponding to examples 1-5 is also improved significantly, meanwhile, the abrasion resistance of the sulfonium ion polymer prepared by the bisaminopolyethylene glycol is best, and the mass loss is less than 30mg after 10000 revolutions of abrasion (as shown in figure 4).
The antibacterial properties of comparative examples 1 to 5 and examples 1 to 5 were tested, and the test results showed that comparative example 2 had almost no antibacterial property, the antibacterial efficiency was close to 0, and the antibacterial efficiency was 5% for comparative example 5. The antibacterial efficiency of comparative examples 1 and 3-4 is improved to a certain extent along with the introduction of polyethylene glycol, the antibacterial efficiency is greatly improved to more than 90% along with the formation of sulfonium ions after ionization of the thioether polymer, and the antibacterial efficiency of example 3 is up to more than 99%. (as in figures 5-6).
The sulfur ether-containing polymers and the sulfur onium ion-containing polymers prepared in comparative examples 1 to 5 and examples 1 to 5 were evaluated for antifouling property in an actual sea area static test for 3 years, and the test results showed that comparative examples 2, 5 were completely covered by marine organisms, and the coverage area was close to 100%. In comparative examples 1 and 3-4, the introduction of polyethylene glycol has certain antifouling performance, sulfonium ions are generated after ionization of the thioether polymer, the antifouling performance is greatly improved, the coverage area is smaller than 10%, the antifouling effect of example 4 is best, and the coverage area is smaller than 5%, so that the antifouling coverage area in 5 years is ensured to be not more than 10%. (see FIG. 7).
In the application, according to the difference of the numerical values of m and n in the structural formula of the double-bond polysiloxane which is terminal double-bond polysiloxane or branched double-bond polysiloxane, the following double-bond polysiloxane reacts with different amine compounds to obtain sulfur ether-containing organic silicon resins with different structures, then reacts with methyl iodide to obtain sulfur-containing onium ion organic silicon polymers, and according to the difference of the numerical values of m and n, the molecular weights of the obtained sulfur-containing onium ion organic silicon resins are different; the molar ratio of the thiolactone, the amine and the polysiloxane containing double bonds is different; the molar ratio of the thioether-containing silicone resin to methyl iodide is also different. After a number of experiments by the applicant, the molecular weight of the sulfonium ion silicone resin is 10 3 -10 7 The molar ratio of the thiolactone, the amine and the polysiloxane containing double bonds is 1:0.5-1.5:0.01-1, when the molar ratio of the sulfur ether-containing organic silicon resin to the methyl iodide is within the range of 1:0.01-50, the mechanical strength of a coating film prepared from the prepared sulfur-containing onium ion-containing organic silicon resin body with different topological structures is 0.5MPa-5MPa, the antibacterial efficiency of the prepared sulfur-containing onium ions with different topological structures can reach 80-99%, and the static real sea protection period of the prepared sulfur-containing onium ions with different topological structures can reach 3-8 years; in this application, the described embodiments are some, but not all, of the embodiments of the present application.
In addition, the sulfonium ion organic silicon resin can be singly applied to film formation, and can also be applied to the surface of a marine underwater component together with pigment and filler, an antifouling agent, an auxiliary agent and the like to form a coating composition, so that attachment and generation of marine organisms are prevented.
The material can be used for protecting ships, ocean engineering, ocean wind power, ocean pastures and ocean facilities under waterline, and can also be used for preventing pollution on the surfaces of underwater cables, underwater monitoring equipment and underwater facilities.
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting thereof; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; these modifications or substitutions do not depart from the essence of the corresponding technical solutions from the protection scope of the technical solutions of the embodiments of the present application.
Claims (7)
1. The preparation method of the sulfur-containing onium ion organic silicon resin with the marine antifouling function is characterized by comprising the following steps of:
adding thiolactone, amine, polysiloxane containing double bonds and solvent into a flask, and putting the flask into an oil bath pot with the temperature of 20-100 ℃ to react for 1-24h to obtain thioether-containing organic silicon resin;
dissolving the sulfur ether-containing organic silicon resin in an organic solvent, adding methyl iodide into the organic solvent at the temperature of between 20 ℃ below zero and 50 ℃ to react for 1 to 24 hours, and obtaining the sulfur onium ion-containing organic silicon resin.
2. The method for preparing the sulfur-containing onium ion silicone resin with the marine antifouling function according to claim 1, wherein the thiolactone is thiolactone with different substituent groups, and the thiolactone has the following structure:
。
3. the method for preparing the sulfur-containing onium ion silicone resin with marine antifouling function according to claim 1, wherein the amine is one or more of propylamine, butylamine, hexylamine, single-end amino polyethylene glycol, double-end amino polyethylene glycol aniline, benzylamine, polyether amine and amino silicone oil.
4. The method for preparing a sulfur-containing onium ion silicone resin with marine antifouling function according to claim 1, wherein the double bond-containing polysiloxane is a terminal double bond polysiloxane or a branched double bond polysiloxane, and has the following structure:
。
5. the method for preparing the sulfur-containing onium ion silicone resin with marine antifouling function according to claim 1, wherein the molar ratio of the thiolactone, the amine and the double bond-containing polysiloxane is 1:0.5-1.5:0.01-1.
6. The method for producing a sulfur-containing onium ion silicone resin with marine antifouling function according to claim 5, wherein the molar ratio of the sulfur-containing ether silicone resin to methyl iodide is 1:0.01-50.
7. The method for producing a sulfur-containing onium ion silicone resin having marine antifouling function according to claim 1, wherein the molecular weight of the sulfur-containing onium ion silicone resin is 10 3 -10 7 。
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| JP2001072869A (en) * | 1999-09-06 | 2001-03-21 | Chugoku Marine Paints Ltd | Polysiloxane-acrylic resin block copolymer composition, antifouling agent composition, antifouling coated film, antifouling treatment base, and antifouling treatment of base |
| KR20130027374A (en) * | 2011-09-07 | 2013-03-15 | 순천향대학교 산학협력단 | Antifoul agent and antifouling paint composition comprising hexadecyl methacylate |
| CN103304762A (en) * | 2013-07-01 | 2013-09-18 | 浙江大学 | Method for preparing organosilicon quaternary ammonium salt modified polyurethane resin for marine antifouling coating |
| CN115785803A (en) * | 2021-09-09 | 2023-03-14 | 涂创时代(苏州)科技开发有限公司 | Nontoxic amphiphilic organic silicon polymer-based marine antifouling paint and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072869A (en) * | 1999-09-06 | 2001-03-21 | Chugoku Marine Paints Ltd | Polysiloxane-acrylic resin block copolymer composition, antifouling agent composition, antifouling coated film, antifouling treatment base, and antifouling treatment of base |
| KR20130027374A (en) * | 2011-09-07 | 2013-03-15 | 순천향대학교 산학협력단 | Antifoul agent and antifouling paint composition comprising hexadecyl methacylate |
| CN103304762A (en) * | 2013-07-01 | 2013-09-18 | 浙江大学 | Method for preparing organosilicon quaternary ammonium salt modified polyurethane resin for marine antifouling coating |
| CN115785803A (en) * | 2021-09-09 | 2023-03-14 | 涂创时代(苏州)科技开发有限公司 | Nontoxic amphiphilic organic silicon polymer-based marine antifouling paint and preparation method and application thereof |
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