WO2018188488A1 - 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 - Google Patents
一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 Download PDFInfo
- Publication number
- WO2018188488A1 WO2018188488A1 PCT/CN2018/080997 CN2018080997W WO2018188488A1 WO 2018188488 A1 WO2018188488 A1 WO 2018188488A1 CN 2018080997 W CN2018080997 W CN 2018080997W WO 2018188488 A1 WO2018188488 A1 WO 2018188488A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- polishing
- self
- methacrylate
- zwitterionic
- Prior art date
Links
- 0 CC(C*C1)*1=C Chemical compound CC(C*C1)*1=C 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy 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
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- 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
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
Definitions
- the invention belongs to the technical field of marine antifouling materials, and particularly relates to a self-polishing zwitterionic antifouling resin with main chain degradability and a preparation method and application thereof.
- the main antifouling control technologies are release antifouling coatings and low surface antifouling coatings, in which release antifouling coatings dominate. It is mainly composed of a polymer resin, an antifouling agent, a solvent, a filler, and the like.
- the antifouling agent is a biotoxin, which mainly prevents and inhibits the adsorption and growth of fouling organisms.
- the polymer resin directly affects the performance of the coating and controls the release of the antifouling agent, which determines its antifouling property, environmental protection and service life.
- Antifouling coatings can be classified into base insoluble, controlled ablation, and self-polishing depending on the resin used.
- the self-polishing antifouling coatings including copper acrylate polymer, zinc acrylate polymer and silane acrylate polymer based antifouling coating
- the basic principle is to make the polymer hydrophilic by hydrolysis of the side chain. The polymer is then dissolved under the scouring of seawater to achieve the release of the antifouling agent.
- the structure itself can only hydrolyze the side chain, it is difficult to regulate the synergy of hydrolysis and dissolution of the polymer, so that its self-polishing property depends on the movement of the ship and the erosion of the surrounding seawater, and it is difficult to meet the requirements of static antifouling. .
- the existing self-polishing polymer system itself does not have antifouling function, and can only rely on the release of the antifouling agent to inhibit fouling organisms.
- the existing antifouling agent is effective for the poisoning of fouling organisms, and the fouling is effective.
- the adhesion of biomacromolecules such as proteins and polysaccharides is powerless.
- zwitterionics in the self-polishing system will effectively enhance the inhibition of initial biofilm formation, but since the zwitterionic polymer is a polyelectrolyte, it has strong hydrophilicity, is incompatible with the coating resin, and has poor mechanical properties. Defects such as poor construction performance. More importantly, the existing self-polishing resin is a vinyl polymer that cannot degrade under natural conditions and forms a problem of “plastic waste pollution” in the ocean.
- the bio-degradation and multi-functional synergistic antifouling of the conventional self-polishing resin are expected, and a resin for long-acting, multi-functional synergistic and environmentally friendly antifouling coating is expected to be prepared.
- the primary object of the present invention is to provide a self-polishing zwitterionic antifouling resin having main chain degradability.
- Another object of the present invention is to provide a process for producing the above self-polishing zwitterionic antifouling resin having main chain degradability.
- a self-polishing zwitterionic antifouling resin having main chain degradability which is obtained by copolymerization of the following three monomers, based on the total mass of the monomers:
- the olefinic reaction monomer is 1 to 80%;
- the betaine type precursor is 1 to 80%.
- the ethylenic reactive monomer is: acrylate monomer, methacrylate monomer, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylol acrylamide, isopropyl acrylamide More than one of styrene, vinylpyrrolidone, and 4-vinylpyridine;
- the methacrylate monomer is methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid.
- the acrylate monomer is methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, More than one of octyl acrylate, isooctyl acrylate, lauryl acrylate, acrylate stearate, and hydroxyethyl acrylate;
- the cycloketene acetal monomer is: (1) 2-methylene-1,3-dioxocyclopentane, (2) 2,4-dimethylene-1,3-dioxolane Alkane, (3) 2-methylene-4-alkyl-1,3 dioxoperane, (4) 2-methylene-4-phenyl-1,3-dioxolane, ( 5) 2-methylene-1,3-dioxo-4,5-benzocyclopentane, (6) 2-methylene-1,3-dioxane, (7) 2,5 - dimethylene-1,3-dioxane, (8) 2-methylene-4-alkyl-1,3-dioxane, (9) 2-methylene-5 -phenyl-1,3-dioxane, (10) 2-ethylidene-1,3-dioxane, (11) 2-methylene-1,3-dioxepane (12) 2-methylene-5-alkyl-1,3-dioxocycl
- n is an integer from 1 to 12.
- R 1 represents H or CH 3
- R 2 represents an alkyl group having 2 to 10 carbon atoms (linear, branched, cyclic), an organic antifouling group, a copper-containing group, a zinc-containing group, and a silicon-containing group.
- the organic antifouling group is N-methylene isothiazolinone (26), N-methylene benzisothiazolinone (27) methylene paeonol (28), N-(2, 4, 6-trichlorophenyl)maleamide (29), and one or more of N-substituted anthracene (30) and N-(4-hydroxy-3-methylene)benzylpropanamide (31).
- the zinc group-containing structure is *-Zn-OC(O)-R 3 , and R 3 is a benzene ring or a saturated or unsaturated alkyl chain having a carbon number of 1 to 10, a saturated or unsaturated cycloalkyl group. "*" indicates a linkage; -OC(O)- indicates an ester group;
- the copper group-containing structure is *-Cu-OC(O)-R 4 , and R 4 is a benzene ring or a saturated or unsaturated alkyl chain having a carbon number of 1 to 10, a saturated or unsaturated naphthenic chain.
- the structural formula of the silicon-containing group is: Wherein C is an alkyl group having a carbon number of 3 or 4, and "*" indicates a joint;
- the preparation method of the above self-polishing zwitterionic antifouling resin having main chain degradability includes the following steps:
- a betaine-type precursor an addition reaction of an acrylate containing R 2 with 2-(methylamino)ethanol at 0 to 50 ° C to obtain an addition product; an addition product and a (methyl group)
- the acryloyl chloride is acylated at 0 to 30 ° C to obtain a betaine type precursor;
- the (meth)acryloyl chloride means methacryloyl chloride or acryloyl chloride;
- the structure of the R 2 -containing acrylate in the step (1) is: Same as R 2 and betaine-type structure in the precursor wherein R 2.
- the addition reaction time in the step (1) is 6 to 12 hours, and the acylation reaction time is 6 to 12 hours.
- the molar ratio of the R 2 -containing acrylate, 2-(methylamino)ethanol to (meth)acryloyl chloride in the step (1) is 1: (1 to 1.5): (1 to 2).
- the organic solvent in the step (2) is one or more of tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, n-butanol, toluene, and xylene.
- the initiator in the step (2) is azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide or t-butyl hydroperoxide.
- the initiator is used in the step (2) in an amount of from 0.1 to 5% by mass based on the total mass of the ethylenic reactive monomer, the cycloketene acetal monomer and the betaine type precursor.
- the present invention has the following advantages and beneficial effects:
- the present invention is prepared by radical ring-opening polymerization of an ethylenic reactive monomer, a cycloketene acetal monomer, and a hydrophobic betaine-type precursor capable of hydrolyzing and releasing an antifouling agent, in addition to main chain degradability
- a hydrophobic betaine-type precursor capable of hydrolyzing and releasing an antifouling agent
- main chain degradability In addition to (hydrocyclyl acetal monomer imparted) and side chain hydrolyzability (given by a hydrophobic betaine-type precursor that hydrolytically releases the antifouling agent), the conversion of the zwitterion can also be achieved by the release of the antifouling agent, ie by The hydrolysis of the surface achieves a transition from hydrophobic to hydrophilic, resulting in a super-hydrophilic zwitterionic surface that further enhances the antifouling ability of the system.
- the material not only overcomes the shortcomings of poor mechanical properties of zwitterionic materials and poor solubility in organic solvents, but also combines the advantages of traditional self-polishing resins to effectively control the long-term stable release of antifouling agents to achieve antifouling agents and anti-fouling agents. Protein synergistic anti-fouling effect.
- the resin is biodegradable in the marine environment and is an environmentally friendly material.
- the method is simple in process and low in cost, and is suitable for industrial production.
- the material has a good application prospect in the field of preparing marine antifouling coating.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- Ethyl acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1 at 30 ° C for 6 hours to obtain an addition product; the addition product was reacted with acryloyl chloride at 0 ° C for 12 hours to obtain an R 2 group.
- the antifouling resin of the present embodiment has no marine fouling bioadhesive for 6 months.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- N-methylenebenzisothiazolinone acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.5 at 0 ° C for 12 hours to obtain an addition product;
- the addition product and acryloyl chloride were wherein the molar ratio of ethylene acrylic acid N- methyl-benzo isothiazolin-ketoester with acryloyl chloride;
- reaction 10 °C 12 hours to obtain N- R 2 is a methylene group benzisothiazol betaine precursor oxazoline-one Is 1:2;
- the antifouling resin of the present embodiment can effectively delay the formation of microbial biofilm, and the solid sea hanging plate can effectively prevent marine fouling bioadhesion for 8 months.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- the methylene paeonol acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.2 at 30 ° C for 6 hours to obtain an addition product; the addition product was reacted with acryloyl chloride at 10 ° C. 12 Hours, a betaine-type precursor having a R 2 group of methylene paeonol; wherein the molar ratio of methylene paeonol acrylate to acryloyl chloride is 1:1.1;
- the antifouling resin of the present embodiment has complete resistance to protein adsorption and greatly reduces the adhesion of marine bacteria.
- the resin solid sea plate can effectively prevent marine fouling adhesion for 12 months.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- 3-((4-Hydroxy-3-methoxybenzyl)amino)-3-oxopropyl acrylate was reacted with 2-(methylamino)ethanol at a molar ratio of 1:1.3 at 50 ° C for 10 hours. , an addition product is obtained; the addition product is reacted with acryloyl chloride at 15 ° C for 12 hours to obtain a betaine-type precursor having an R 2 group of N-(4-hydroxy-3-methylene)benzylpropanamide Wherein the molar ratio of 3-((4-hydroxy-3-methoxybenzyl)amino)-3-oxopropyl acrylate to acryloyl chloride is 1:1.8;
- the polymerization tube was added 10ml of xylene, was added 1g of styrene, 1g of the R 2 group is N- (4- hydroxy-3-methyl) benzyl propionamide betaine precursor, 1 g of 2-methylene-1,3-dioxane and 0.02 g of t-butyl hydroperoxide, three times of removal of oxygen after freezing, placed in a 150 ° C oil bath for 24 h, taken out and concentrated The solvent was precipitated again with diethyl ether and dried in vacuo at 50 ° C for 24 hours to give a product, self-polishing, amphoteric anti-fouling resin.
- the resulting self-polishing zwitterionic antifouling resin has the following structure:
- the antifouling resin solid sea plate of the present embodiment can effectively prevent marine fouling bioadhesion for 12 months.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- the zinc acetate acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1.2 at 40 ° C for 10 hours to obtain an addition product; the addition product was reacted with acryloyl chloride at 5 ° C for 10 hours to obtain R 2 .
- the group is a betaine type precursor of zinc acetate; wherein the molar ratio of zinc acetate acrylate to acryloyl chloride is 1:1.5;
- the antifouling resin solid sea plate of the present embodiment can effectively prevent marine fouling bioadhesion for 14 months.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- the triisopropylsilane acrylate and 2-(methylamino)ethanol were reacted at a molar ratio of 1:1 at 50 ° C for 10 hours to obtain an addition product; the addition product was reacted with acryloyl chloride at 5 ° C for 12 hours.
- a betaine-type precursor having an R 2 group of triisopropylsilane; wherein a molar ratio of triisopropylsilane acrylate to acryloyl chloride is 1:1.5;
- the antifouling resin solid sea plate of the present embodiment can effectively prevent marine fouling bioadhesion for 14 months.
- a preparation method of a self-polishing zwitterionic antifouling resin having main chain degradability comprising the following steps:
- the molar ratio of copper benzoate acrylate to 2-(methylamino)ethanol was 1:1 at 0 ° C to obtain an addition product; the addition product was reacted with acryloyl chloride at 5 ° C for 10 hours to obtain R.
- 2 is a betaine type precursor of copper benzoate; wherein the molar ratio of copper benzoate to acryloyl chloride is 1:1.5;
- the antifouling resin solid sea plate of the present embodiment can effectively prevent marine fouling bioadhesion for 10 months.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明属于海洋防污材料的技术领域,公开了一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用。自抛光两性离子防污树脂,由以下三种单体共聚而成,以单体总质量计:烯类反应单体1~80%,环烯酮缩醛单体1~80%,甜菜碱型前驱体1~80%。所述的防污树脂具备主链降和侧链水解性,通过表面的水解作用,实现涂层由疏水到亲水的转变,产生超亲水两性离子表面,进一步增强该体系的防污能力。该材料不仅克服了两性离子材料力学性能差、在有机溶剂中溶解性差的缺点,还能有效控制防污剂长期稳定释放,达到防污剂与抗蛋白协同抗污的效果。本发明的方法简单,成本较低,适合工业化生产。该材料用于海洋防污涂层领域。
Description
本发明属于海洋防污材料的技术领域,具体涉及一种具有主链降解性的自抛光两性离子防污树脂及其制备方法与应用。
海洋中生活着多种生物,它们会在船舶、采油平台、冷却水管道等设施的表面聚集、生长、繁殖,形成海洋生物污损。它给航运、海洋工程、海洋养殖业带来一系列问题,诸如增加船行阻力、加大燃油量,缩短海洋设施的使用寿命,堵塞渔网等。目前主要的防污控制技术有释放型防污涂层和低表面防污涂层法,其中释放型防污涂层占据主导地位。其主要由高分子树脂、防污剂、溶剂、填料等组成。其中防污剂为生物毒素,主要防止和抑制污损生物的吸附和生长。高分子树脂作为涂层的基体以及防污剂的载体,直接影响涂层的性能并控制防污剂的释放,决定着其防污性、环保性、使用寿命等。
根据所用树脂的不同,防污涂料可以分为基料不溶性、可控消融以及自抛光型。其中目前占据主导地位的是自抛光防污涂料,包括丙烯酸铜聚合物,丙烯酸锌聚合物和丙烯酸硅烷酯聚合物基防污涂料,其基本原理是通过侧链的水解使聚合物变成亲水性聚合物,然后在海水的冲刷下,发生溶解,实现防污剂的释放。然后由于其结构本身只有侧链可以发生水解作用,很难调控聚合物的水解和溶解的协同性,使得其自抛光性依赖于船的运动和周围海水的冲刷,很难满足静态防污的要求。同时,现有自抛光聚合物体系本身不具有防污功能,只能依赖于防污剂的释放来抑制污损生物,然而现有防污剂对污损生物的毒杀有效,而对污损过程初期蛋白质、多糖等生物大分子的粘附无能为力。
在自抛光体系中引入两性离子,将有效提升对初期生物膜形成的抑制作用,但由于两性离子聚合物是一种聚电解质,存在亲水性强、和涂料树脂不相容,力学性能差、施工性能不好等缺陷。更为重要的是,现有自抛光树脂是乙烯基聚合物,无法在自然条件下降解,在海洋中形成“塑料垃圾污染”问题。因此, 在有效规避两性离子聚合物缺陷的同时,赋予传统自抛光树脂生物降解和多功能协同防污,有望制备出一种使长效,多功能协同、环境友好防污涂料用树脂。
发明内容
为克服现有海洋防污涂料用自抛光树脂防污机理单一、无法生物降解的缺陷,本发明的首要目的在于提供一种具有主链降解性的自抛光两性离子防污树脂。
本发明的另一目的在于提供上述具有主链降解性的自抛光两性离子防污树脂的制备方法。
本发明的再一目的在于提供上述具有主链降解性的自抛光两性离子防污树脂的应用。
本发明的目的通过以下技术方案实现:
一种具有主链降解性的自抛光两性离子防污树脂,由以下三种单体共聚而成,以单体总质量计:
烯类反应单体1~80%;
环烯酮缩醛单体1~80%;
甜菜碱型前驱体1~80%。
所述烯类反应单体为:丙烯酸酯类单体、甲基丙烯酸酯类单体、丙烯酸,甲基丙烯酸,丙烯酰胺,甲基丙烯酰胺,N-羟甲基丙烯酰胺,异丙基丙烯酰胺,苯乙烯,乙烯基吡咯烷酮,4-乙烯基吡啶中的一种以上;
所述甲基丙烯酸酯类单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸-2-甲氧基乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸辛酯、甲基丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酸酯、聚乙二醇甲基丙烯酸酯,甲基丙烯酸羟乙酯,甲基丙烯酸缩水甘油酯,甲基丙烯酸二甲氨基乙酯,甲基丙烯酸二乙氨基乙酯中一种以上;
所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸-2-甲氧基乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸辛酯、丙烯酸异辛酯、丙烯酸月桂酯、丙烯酸硬脂酸酯、丙烯酸羟乙酯中一种以上;
所述环烯酮缩醛单体为:(1)2-亚甲基-1,3-二氧环戊烷、(2)2,4-二亚甲基-1,3-二氧环戊烷、(3)2-亚甲基-4-烷基-1,3二氧环戊烷、(4)2-亚甲基-4-苯基-1,3-二氧环戊烷、(5)2-亚甲基-1,3-二氧-4,5-苯并环戊烷、(6)2-亚甲基-1,3-二氧环己烷、(7)2,5-二亚甲基-1,3-二氧环己烷、(8)2-亚甲基-4-烷基-1,3-二氧环己烷、(9)2-亚甲基-5-苯基-1,3-二氧环己烷、(10)2-乙叉-1,3-二氧环己烷、(11)2-亚甲基-1,3-二氧环庚烷、(12)2-亚甲基-5-烷基-1,3-二氧环庚烷、(13)2-亚甲基-1,3-二氧-5,6-苯并-环庚烷、(14)2-亚甲基-4,7-二甲基-1,3-二氧环庚烷、(15)2-亚甲基-5-苯基-1,3-二氧环庚、(16)2-亚甲基-1,3-二氧-5-环庚烯、(17)2-乙叉-1,3-二氧-5,6-苯并环庚烷、(18)2-乙叉-4-烷基-1,3-二氧环戊烷、(19)2-乙叉-1,3-二氧环庚烷、(20)2-烯丙叉-4-苯基-1,3-二氧环戊烷、(21)2-亚甲基-1,3,6三氧环辛烷、(22)1-乙烯基-4,7-二氧杂螺[2.4]庚烷、(23)1-乙烯基-4,9-二氧杂螺[2.6]壬烷、(24)1-乙烯基-6,7-苯并-4,9-二氧杂螺[2.6]壬烷、(25)1-乙烯基-5-苯基-4,7-二氧杂螺[2.4]庚烷中的一种或以上。
各环烯酮缩醛单体(1~25)对应的结构式如下:
其中m为1~12的整数。
所述甜菜碱型前驱体的结构通式如下:
R
1表示H或CH
3,R
2表示碳数为2~10的烷基(直链、带支链、环状)、有机防污基团、含铜基团、含锌基团、含硅基团;
有机防污基团为N-亚甲基异噻唑啉酮(26)、N-亚甲基苯并异噻唑啉酮(27)亚甲基丹皮酚(28)、N-(2,4,6-三氯苯基)马来酰胺(29)、和N-取代吲哚(30)、N-(4-羟基-3-亚甲基)苯甲基丙酰胺(31)的一种以上。
各有机防污基团(26~30)对应的结构式如下:“*”表示连接处,
所述含锌基团的结构为*-Zn-O-C(O)-R
3,R
3为苯环或碳数为1~10的饱和或不饱和烷基链,饱和或不饱和的环烷基,“*”表示连接处;-O-C(O)-表示的是酯基;
所述含铜基团的结构为为*-Cu-O-C(O)-R
4,R
4为苯环或碳数为1~10的饱和或不饱和烷基链,饱和或不饱和的环烷基,“*”表示连接处;-O-C(O)-表示的是酯基;
上述具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:含R
2的丙烯酸酯类与2-(甲氨基)乙醇在0~50℃下发生加成反应,得到加成产物;将加成产物与(甲基)丙烯酰氯在0~30℃发生酰化反应,得到甜菜碱型前驱体;所述(甲基)丙烯酰氯是指甲基丙烯 酰氯或丙烯酰氯;
(2)防污树脂的制备:无氧条件下,以有机溶剂为介质,将烯类反应单体、环烯酮缩醛单体和甜菜碱型前驱体在引发剂作用下,于60~150℃反应24~48h,分离,得到自抛光两性离子防污树脂。所述的自抛光两性离子防污树脂用于海洋防污材料。
步骤(1)中所述加成反应的时间为6~12小时,酰化反应的时间为6~12小时。
步骤(1)中所述含R
2的丙烯酸酯类、2-(甲氨基)乙醇与(甲基)丙烯酰氯的摩尔比为1∶(1~1.5)∶(1~2)。
步骤(2)中所述有机溶剂为四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺、乙腈、正丁醇、甲苯、二甲苯中的一种或几种。
步骤(2)中所述引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰或叔丁基过氧化氢。
步骤(2)中所述引发剂的用量为烯类反应单体、环烯酮缩醛单体和甜菜碱型前驱体总质量的0.1~5%。
与现有技术相比,本发明具有如下优点及有益效果:
(1)本发明通过烯类反应单体、环烯酮缩醛单体以及可水解释放防污剂的疏水性甜菜碱型前驱体发生自由基开环聚合制备,该材料除了具备主链降解性(环烯酮缩醛单体赋予)和侧链水解性(可水解释放防污剂的疏水性甜菜碱型前驱体赋予)外,还可以通过防污剂的释放实现两性离子的转化,即通过表面的水解作用,实现涂层由疏水到亲水的转变,产生超亲水两性离子表面,进一步增强该体系的防污能力。
(2)该材料不仅克服了两性离子材料力学性能差、在有机溶剂中溶解性差的缺点,还结合了传统自抛光树脂的优点,能有效控制防污剂长期稳定释放,达到防污剂与抗蛋白协同抗污的效果。
(3)该树脂可在海洋环境中发生生物降解,是一种环境友好型材料。
(4)该方法工艺简单,成本较低,适合工业化生产,该材料在制备海洋防污涂层领域具有很好的应用前景。
下面结合具体实施例对本发明作进一步详细描述,但本发明的实施方式不限于此。
实施例1
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将丙烯酸乙酯与2-(甲氨基)乙醇按摩尔比为1∶1在30℃下反应6小时,得到加成产物;将加成产物与丙烯酰氯在0℃反应12小时,得到R
2基团为乙基的甜菜碱型前驱体;其中丙烯酸乙酯与丙烯酰氯按1∶1.2;
(2)将20ml四氢呋喃加入聚合管中,再加入5g甲基丙烯酸甲酯、5g的R
2基团为乙基的甜菜碱型前驱体、5g 2-亚甲基-1,3-二氧环庚烷和0.1g偶氮二异丁腈,通氮气30分钟脱除氧气后,放入60℃油浴锅中反应24h,取出后浓缩溶剂,再用正己烷沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂实海挂板6个月无海洋污损生物粘附。
实施例2
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将丙烯酸N-亚甲基苯并异噻唑啉酮酯与2-(甲氨基)乙醇按摩尔比为1∶1.5在0℃下反应12小时,得到加成产物;将加成产物与丙烯酰氯在10℃反应12小时,得到R
2基团为N-亚甲基苯并异噻唑啉酮的甜菜碱型前驱体;其中丙烯酸N-亚甲基苯并异噻唑啉酮酯与丙烯酰氯的摩尔比为1∶2;
(2)将20ml 1,4-二氧六环加入聚合管中,再加入5g丙烯酸乙酯、2.5g的R
2基团为N-亚甲基苯并异噻唑啉酮的甜菜碱型前驱体、2.5g的2-亚甲基-4-甲基-1,3二氧环戊烷,0.1g偶氮二异庚腈,通氮气30分钟脱除氧气后,放入80℃油浴锅中反应48h,取出后浓缩溶剂,再用正己烷沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂能有效延缓微生物生物膜形成,实海挂板8个月能有效防止海洋污损生物粘附。
实施例3
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将丙烯酸亚甲基丹皮酚酯与2-(甲氨基)乙醇按摩尔比为1∶1.2在30℃下发生反应6小时,得到加成产物;将加成产物与丙烯酰氯在10℃反应12小时,得到R
2基团为亚甲基丹皮酚的甜菜碱型前驱体;其中丙烯酸亚甲基丹皮酚酯与丙烯酰氯的摩尔比为1∶1.1;
(2)将20ml N,N-二甲基甲酰胺加入聚合管中,再加入1g丙烯酸,2g的R
2基团为亚甲基丹皮酚的甜菜碱型前驱体、1g的2-亚甲基-1,3-二氧-5,6-苯并- 环庚烷和0.2g偶氮二异丁腈,冻抽三次脱除氧气后,放入70℃油浴锅中反应36h,取出后浓缩溶剂,再用石油醚沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂在对蛋白吸附完全阻抗,极大减少海洋细菌的粘附,树脂实海挂板12个月能有效防止海洋污损生物附着。
实施例4
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将3-((4-羟基-3-甲氧基苄基)氨基)-3-氧代丙基丙烯酸酯与2-(甲氨基)乙醇按摩尔比为1∶1.3在50℃下反应10小时,得到加成产物;将加成产物与丙烯酰氯在15℃反应12小时,得到R
2基团为N-(4-羟基-3-亚甲基)苯甲基丙酰胺的甜菜碱型前驱体;其中3-((4-羟基-3-甲氧基苄基)氨基)-3-氧代丙基丙烯酸酯与丙烯酰氯的摩尔比为1∶1.8;
(2)将10ml二甲苯加入聚合管中,再加入1g苯乙烯、1g的R
2基团为N-(4-羟基-3-亚甲基)苯甲基丙酰胺的甜菜碱型前驱体、1g的2-亚甲基-1,3-二氧环己烷和0.02g的叔丁基过氧化氢,冻抽三次脱除氧气后,放入150℃油浴锅中反应24h,取出后浓缩溶剂,再用乙醚沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂实海挂板12个月能有效防止海洋污损生物粘附。
实施例5
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将丙烯酸醋酸锌酯与2-(甲氨基)乙醇按摩尔比为1∶1.2在40℃下反应10小时,得到加成产物;将加成产物与丙烯酰氯在5℃反应10小时,得到R
2基团为醋酸锌的甜菜碱型前驱体;其中丙烯酸醋酸锌酯与丙烯酰氯的摩尔比为1∶1.5;
(2)将20ml正丁醇加入聚合管中,再加入1g的丙烯酸羟乙酯,1g的R
2基团为醋酸锌的甜菜碱型前驱体、1g的2-亚甲基-1,3-二氧-5-环庚烯和0.02g的过氧化二苯甲酰,通氮气30分钟脱除氧气后,放入80℃油浴锅中反应48h,取出后浓缩溶剂,再用正己烷沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂实海挂板14个月能有效防止海洋污损生物粘附。
实施例6
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将丙烯酸三异丙基硅烷酯与2-(甲氨基)乙醇按摩尔比为1∶1在50℃下反应10小时,得到加成产物;将加成产物与丙烯酰氯在5℃反应12小时,得到R
2基团为三异丙基硅烷的甜菜碱型前驱体;其中丙烯酸三异丙基硅烷酯与丙烯酰氯的摩尔比为1∶1.5;
(2)将5ml乙腈加入聚合管中,再加入1.6g的丙烯酸甲酯、0.4g的R
2基团为三异丙基硅烷的甜菜碱型前驱体和1g的2-亚甲基-5-苯基-1,3-二氧环庚和0.02g的偶氮二异丁腈,通氮气30分钟脱除氧气后,放入70℃油浴锅中反应24h,取出后浓缩溶剂,再用正己烷沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂实海挂板14个月能有效防止海洋污损生物粘附。
实施例7
一种具有主链降解性的自抛光两性离子防污树脂的制备方法,包括如下步骤:
(1)甜菜碱型前驱体的制备:
将丙烯酸苯甲酸铜酯与2-(甲氨基)乙醇按摩尔比为1∶1在0℃下反应10小时,得到加成产物;将加成产物与丙烯酰氯在5℃反应10小时,得到R
2基团 为苯甲酸铜的甜菜碱型前驱体;其中丙烯酸苯甲酸铜酯与丙烯酰氯的摩尔比为1∶1.5;
(2)将20ml二甲苯加入聚合管中,再加入1g的4-乙烯基吡啶,0.5g的R
2基团为苯甲酸铜的甜菜碱型前驱体、2g的2-亚甲基-1,3,6三氧环辛烷和0.02g过氧化二苯甲酰,通氮气30分钟脱除氧气后,放入80℃油浴锅中反应24h,取出后浓缩溶剂,再用正己烷沉淀,真空中50℃干燥24小时,得到产物自抛光两性离子防污树脂。所得自抛光两性离子防污树脂结构如下:
本实施例的防污树脂实海挂板10个月能有效防止海洋污损生物粘附。
Claims (10)
- 根据权利要求1所述具有主链降解性的自抛光两性离子防污树脂,其特征在于:所述甲基丙烯酸酯类单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸-2-甲氧基乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸辛酯、甲基丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酸酯、聚乙二醇甲基丙烯酸酯,甲基丙烯酸羟乙酯,甲基丙烯酸缩水甘油酯,甲基丙烯酸二甲氨基乙酯,甲基丙烯酸二乙氨基乙酯中一种以上;所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸-2-甲氧基乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸辛酯、丙烯酸异辛酯、丙烯酸月桂酯、丙烯酸硬脂酸酯、丙烯酸羟乙酯中一种以上。
- 根据权利要求1~4任一项所述具有主链降解性的自抛光两性离子防污树脂的制备方法,其特征在于:包括如下步骤:(1)甜菜碱型前驱体的制备:含R 2的丙烯酸酯类与2-(甲氨基)乙醇在0~50℃下发生加成反应,得到加成产物;将加成产物与(甲基)丙烯酰氯在0~30℃发生酰化反应,得到甜菜碱型前驱体;(2)防污树脂的制备:无氧条件下,以有机溶剂为介质,将烯类反应单体、环烯酮缩醛单体和甜菜碱型前驱体在引发剂作用下,于60~150℃反应24~48h,分离,得到自抛光两性离子防污树脂。
- 根据权利要求5所述具有主链降解性的自抛光两性离子防污树脂的制备方法,其特征在于:步骤(1)中所述含R 2的丙烯酸酯类、2-(甲氨基)乙醇与(甲基)丙烯酰氯的摩尔比为1∶(1~1.5)∶(1~2)。
- 根据权利要求5所述具有主链降解性的自抛光两性离子防污树脂的制备方法,其特征在于:步骤(1)中所述加成反应的时间为6~12小时,酰化反应的时间为6~12小时。
- 根据权利要求5所述具有主链降解性的自抛光两性离子防污树脂的制备 方法,其特征在于:步骤(2)中所述有机溶剂为四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺、乙腈、正丁醇、甲苯、二甲苯中的一种或几种;步骤(2)中所述引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、叔丁基过氧化氢。
- 根据权利要求5所述具有主链降解性的自抛光两性离子防污树脂的制备方法,其特征在于:步骤(2)中所述引发剂的用量为烯类反应单体、环烯酮缩醛单体和甜菜碱型前驱体总质量的0.1~5%。
- 根据权利要求1~4任一项所述具有主链降解性的自抛光两性离子防污树脂的应用,其特征在于:所述自抛光两性离子防污树脂用于海洋防污材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/605,112 US11512158B2 (en) | 2017-04-14 | 2018-03-29 | Self-polishing zwitterionic anti-fouling resin having main chain degradability and preparation therefor and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710245180.3 | 2017-04-14 | ||
CN201710245180.3A CN107033278B (zh) | 2017-04-14 | 2017-04-14 | 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018188488A1 true WO2018188488A1 (zh) | 2018-10-18 |
Family
ID=59536395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2018/080997 WO2018188488A1 (zh) | 2017-04-14 | 2018-03-29 | 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 |
Country Status (3)
Country | Link |
---|---|
US (1) | US11512158B2 (zh) |
CN (1) | CN107033278B (zh) |
WO (1) | WO2018188488A1 (zh) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB202107159D0 (en) | 2021-03-23 | 2021-06-30 | Jotun As | Monitoring a vessel |
WO2021180588A2 (en) | 2020-03-09 | 2021-09-16 | Jotun A/S | Hull cleaning robot |
WO2021191388A1 (en) | 2020-03-27 | 2021-09-30 | Jotun A/S | Antifouling coating composition |
CN113861375A (zh) * | 2021-10-22 | 2021-12-31 | 东莞市米儿塑胶原料有限公司 | 耐黄变tpu及tpu保护膜的制备方法 |
WO2022200430A1 (en) | 2021-03-23 | 2022-09-29 | Jotun A/S | Monitoring the cleanliness of an underwater surface of a stationary object |
EP4001345A4 (en) * | 2019-07-18 | 2023-07-12 | South China University of Technology | DEGRADABLE HYPERBRANCHED RESIN, METHOD OF MANUFACTURE THEREOF AND USE THEREOF |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107033278B (zh) | 2017-04-14 | 2019-05-14 | 华南理工大学 | 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 |
CN110218519B (zh) * | 2019-05-09 | 2020-04-28 | 华南理工大学 | 一种静态抗污自分层有机硅涂料及其制备方法与应用 |
CN110511328B (zh) * | 2019-07-18 | 2020-11-24 | 华南理工大学 | 一种支化点断裂型超支化树脂及其制备方法与应用 |
CN113105826B (zh) * | 2020-01-13 | 2022-02-18 | 四川大学 | 一种用于镁合金表面改性的可生物降解抗菌聚(酯)-聚(弱两亲性丙烯酸)共聚物涂层 |
CN111303326B (zh) * | 2020-04-09 | 2021-07-06 | 中国科学技术大学 | 一种降解单元可控,单体利用率高的聚烯烃材料及其制备方法 |
CN112279985A (zh) * | 2020-11-01 | 2021-01-29 | 福建师范大学 | 一种可降解扩链剂及其制备方法和应用 |
CN113881069B (zh) * | 2021-11-05 | 2022-11-15 | 中国海洋大学 | 一种丙烯酸基水凝胶防污材料制备方法及该材料的用途 |
CN114230738A (zh) * | 2021-12-14 | 2022-03-25 | 南方海洋科学与工程广东省实验室(湛江) | 一种自降解的阳离子聚合物及其制备方法与应用 |
CN115197360B (zh) * | 2022-07-08 | 2023-08-01 | 哈尔滨工程大学 | 一种丁香酚酯基甲基丙烯酸氟自抛光防污树脂及制备方法 |
CN115340626B (zh) * | 2022-10-07 | 2024-05-24 | 广东省漆色彩新型材料有限公司 | 一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03190974A (ja) * | 1989-12-20 | 1991-08-20 | Showa Highpolymer Co Ltd | 防汚塗料組成物 |
JPH11255869A (ja) * | 1998-03-11 | 1999-09-21 | Toyobo Co Ltd | 加水分解型ポリエステルおよびそれを含有する防汚塗料用組成物 |
CN102702422A (zh) * | 2012-06-18 | 2012-10-03 | 中国船舶重工集团公司第七二五研究所 | 一种双性离子型防污添加剂的制备方法 |
CN103396513A (zh) * | 2013-07-24 | 2013-11-20 | 华南理工大学 | 一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用 |
CN105542607A (zh) * | 2015-11-25 | 2016-05-04 | 中国科学院兰州化学物理研究所 | 一种含甜菜碱型两性离子改性的丙烯酸酯自抛光防污涂料及其制备方法 |
CN107033278A (zh) * | 2017-04-14 | 2017-08-11 | 华南理工大学 | 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9533006B2 (en) * | 2007-11-19 | 2017-01-03 | University Of Washington | Marine coatings |
KR20150118096A (ko) * | 2013-02-12 | 2015-10-21 | 디아이씨 가부시끼가이샤 | 절연 재료용 수지 조성물, 절연 잉크, 절연막 및 그것을 사용한 유기 전계 효과 트랜지스터 |
CN103467728B (zh) * | 2013-09-13 | 2015-10-28 | 浙江大学 | 一种具有生物缔合性的可降解两性离子聚合物及其制备方法 |
CN104031236B (zh) * | 2014-06-05 | 2016-06-01 | 浙江大学 | 带有两性离子前体刷状侧链的聚氨酯及其制备方法和用途 |
WO2017030950A1 (en) * | 2015-08-14 | 2017-02-23 | Arrow International, Inc. | Photoactivatable fouling-resistant copolymers |
CN105273594B (zh) * | 2015-10-30 | 2017-10-20 | 华南理工大学 | 一种键合防污因子的有机硅聚氨酯/脲防污材料及制备与应用 |
-
2017
- 2017-04-14 CN CN201710245180.3A patent/CN107033278B/zh active Active
-
2018
- 2018-03-29 US US16/605,112 patent/US11512158B2/en active Active
- 2018-03-29 WO PCT/CN2018/080997 patent/WO2018188488A1/zh active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03190974A (ja) * | 1989-12-20 | 1991-08-20 | Showa Highpolymer Co Ltd | 防汚塗料組成物 |
JPH11255869A (ja) * | 1998-03-11 | 1999-09-21 | Toyobo Co Ltd | 加水分解型ポリエステルおよびそれを含有する防汚塗料用組成物 |
CN102702422A (zh) * | 2012-06-18 | 2012-10-03 | 中国船舶重工集团公司第七二五研究所 | 一种双性离子型防污添加剂的制备方法 |
CN103396513A (zh) * | 2013-07-24 | 2013-11-20 | 华南理工大学 | 一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用 |
CN105542607A (zh) * | 2015-11-25 | 2016-05-04 | 中国科学院兰州化学物理研究所 | 一种含甜菜碱型两性离子改性的丙烯酸酯自抛光防污涂料及其制备方法 |
CN107033278A (zh) * | 2017-04-14 | 2017-08-11 | 华南理工大学 | 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4001345A4 (en) * | 2019-07-18 | 2023-07-12 | South China University of Technology | DEGRADABLE HYPERBRANCHED RESIN, METHOD OF MANUFACTURE THEREOF AND USE THEREOF |
WO2021180588A2 (en) | 2020-03-09 | 2021-09-16 | Jotun A/S | Hull cleaning robot |
WO2021191388A1 (en) | 2020-03-27 | 2021-09-30 | Jotun A/S | Antifouling coating composition |
GB202107159D0 (en) | 2021-03-23 | 2021-06-30 | Jotun As | Monitoring a vessel |
WO2022200427A1 (en) | 2021-03-23 | 2022-09-29 | Jotun A/S | Monitoring a vessel |
WO2022200430A1 (en) | 2021-03-23 | 2022-09-29 | Jotun A/S | Monitoring the cleanliness of an underwater surface of a stationary object |
CN113861375A (zh) * | 2021-10-22 | 2021-12-31 | 东莞市米儿塑胶原料有限公司 | 耐黄变tpu及tpu保护膜的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20200157338A1 (en) | 2020-05-21 |
US11512158B2 (en) | 2022-11-29 |
CN107033278B (zh) | 2019-05-14 |
CN107033278A (zh) | 2017-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018188488A1 (zh) | 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用 | |
JP6797442B2 (ja) | モノマー法により調製された主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法 | |
US9701794B2 (en) | Method for preparing main chain scission-type polysilyl (meth)acrylate resin and application thereof | |
CN102300944B (zh) | 一种海洋生物防污漆及其制备方法和应用 | |
CN110540652B (zh) | 一种可降解超支化树脂及其制备方法与应用 | |
CA1327863C (en) | Compositions for surface treatment, polymers therefor, and method of surface treatment | |
RU2372365C2 (ru) | Композиции для предотвращения обрастания морскими организмами, включающие полимер с солевыми группами | |
CN103788287B (zh) | 一种抗菌改性低表面能型海洋防污涂料树脂及其制备方法 | |
CN105542607B (zh) | 一种含甜菜碱型两性离子改性的丙烯酸酯自抛光防污涂料及其制备方法 | |
US20080038241A1 (en) | Self-Polishing Anti-Fouling coating Compositions Comprising An Enzyme | |
WO2018196542A1 (zh) | 一种主链降解型聚丙烯酸铜树脂及其制备方法与应用 | |
AU2004202176A1 (en) | Triarylsilyl(meth)acryloyl-containing polymers for marine coating compositions | |
RU2009147082A (ru) | Дисперсия, включающая неорганические частицы, воду и, по меньшей мере, одну полимерную добавку | |
RU2005106212A (ru) | Кватернизованный полимер с кислотными блокирующими группами и композиции, содержащие такой полимер | |
CN103044632A (zh) | 一种杂化水解树脂及其制备方法与应用 | |
CN106977659A (zh) | 一种后接枝法制备的主链降解型聚丙烯酸锌树脂及其方法与应用 | |
RU2000122439A (ru) | Препятствующее обрастанию покрытие | |
ES2214741T3 (es) | Un procedimiento para la reduccion del ensuciamiento del reactor. | |
CN1418922A (zh) | 涂料组合物 | |
CN106977642A (zh) | 一种丙烯酸锌与硅共聚防污树脂及其制备方法 | |
CN111040087A (zh) | 一种自抛光防污树脂的制备方法 | |
JP2007530723A5 (zh) | ||
JPH04120183A (ja) | 塗料組成物 | |
CN109836583A (zh) | 一种可降解型有机硅自抛光型海洋防污材料的制备方法及其应用 | |
CN106521945B (zh) | 多元协同防污共聚物修饰氨纶纤维及制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18783752 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 22/01/2020) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18783752 Country of ref document: EP Kind code of ref document: A1 |