CN108929406A - The preparation method of one metal ion species slow releasing function antifouling paint resin - Google Patents
The preparation method of one metal ion species slow releasing function antifouling paint resin Download PDFInfo
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- CN108929406A CN108929406A CN201810646939.3A CN201810646939A CN108929406A CN 108929406 A CN108929406 A CN 108929406A CN 201810646939 A CN201810646939 A CN 201810646939A CN 108929406 A CN108929406 A CN 108929406A
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- metal ion
- resin
- unsaturated acids
- preparation
- slow releasing
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- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 33
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 30
- 239000003973 paint Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 23
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 11
- -1 acids silicon ester Chemical class 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000007513 acids Chemical class 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 102000004895 Lipoproteins Human genes 0.000 claims description 7
- 108090001030 Lipoproteins Proteins 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 238000005498 polishing Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910001431 copper ion Inorganic materials 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000002519 antifouling agent Substances 0.000 description 10
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical class CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- GZWHKZMMMSLXNV-UHFFFAOYSA-N benzene;1,2-xylene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1C GZWHKZMMMSLXNV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 206010016165 failure to thrive Diseases 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- SMRKTBLEVAAJIF-UHFFFAOYSA-N propanamide;prop-2-enoic acid Chemical class CCC(N)=O.OC(=O)C=C SMRKTBLEVAAJIF-UHFFFAOYSA-N 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 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
- 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
- C08F230/08—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 containing silicon
-
- 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
-
- 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
- C09D5/1668—Vinyl-type polymers
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
The invention discloses the preparation methods of a metal ion species slow releasing function antifouling paint resin, including being copolymerized using the monomers such as unsaturated acids Arrcostab, unsaturated acids silicon ester, unsaturated acids aminoalkyl chemical combination object, the copolymer resin with metallic ion coordination effect is prepared, marine anti-pollution coating is used for.It is demonstrated experimentally that the complex compound that the amino and metal ion in resin copolymer are formed, can be effectively controlled the rate of release of metal ion, achievees the purpose that sustained release.Compared with tradition is from polishing metal acrylate compound coat, the antifouling period can be extended by about one time using nonpolluting coating prepared by resin of the invention.The process for preparing resins that the present invention uses is simple, yield close to 100%, resin need not separating-purifying, can be used directly, be suitable for industrialized production.
Description
Technical field
The invention belongs to macromolecule material preparation areas, are related to a kind of preparation method of marine antifouling coating resin.
Background technique
Marine biofouling refers to the marine organisms for being attached to the marine structures such as hull, buoy and fish pot surface.Attachment
The roughness of hull surface will be increased in the biodeterioration of hull surface, cause oil consumption to increase up to 40% or more, single voyage cost
Increase up to 70% or more.In the method for many prevention and treatment marine biofoulings, brushing antifouling paint is side the most cost-effective
Method.Since the organo-tin compound of severe toxicity is accumulated in the seawater in marine antifouling coating containing organotin, lead to fish and shellfish etc.
Marine organisms are distorted, and cause significant damage to marine environment, threaten human health, therefore organic from January 1st, 2008
Tin coating is disabled by the whole world.Many novel sea nonpolluting coatings have been developed at present to replace organotin-based paints, but in reality
Some problems are still had in.Ship anti-fouling effect of the pollution release type nonpolluting coating to route speed lower than 30 sections is paid no attention to
Think, the ship that is not suitable for berthing or run at a low speed for a long time [Chemical. Reviews., 2012, 112(8), 4347-
4390];For tin-free self-polishing nonpolluting coating containing cuprous oxide using relatively broad, resin contains polyacrylate and poly- third
The copolymer of olefin(e) acid estersil, under the action of seawater, estersil hydrolysis realize copper ion release, but copper ion release duration compared with
The rate of release of difference, initial stage is excessively high, causes later period amount of copper ions released insufficient, influences the anti-fouling effect and service life of coating
【Progress in Organic Coatings, 2004, 50(2), 75-104], the main reason is that the resinoid and gold
Between category anti-fouling agent mainly based on the physical action of machinery embedding, therefore the weaker [US of the active force of resin and metal anti-fouling agents
Patent, No.4593055,1986].And as the hydrolysis of resin polishes, most metal ion anti-fouling agent quickly flows
It loses in seawater, does not play the role of due antifouling.Anti-fouling effect and service life in order to ensure coating, it has to increase antifouling
The usage amount of agent, thus at present coating anti-fouling agent actual interpolation amount will much higher than theoretical value [coatings industry, 2012,42,
45-48].The copper ion of high additive amount equally has a negative impact to environment, and the copper ion of coastal area high concentration leads to mussel
And the aquatiles growth failure such as oyster, some countries have promulgated that relevant regulations are subject to the rate of release of copper ion in coating
Limitation.
How under the premise of not influencing the anti-fouling effect and service life of coating, the addition of the anti-fouling agents such as copper ion is reduced
Amount is critical issue urgently to be resolved.As described above, reducing the excessive loss of metal ion, it is important to promote resinous polymer pair
Metal ion slow-release capability increases the interaction of resinous polymer and metal ion.It develops to have and be formed with metal ion
The new type resin of coordination ability, makes metal ion and resin structure unit forms strong active force, can not only slow down metal from
The excessive loss of son can also play its antifouling effect, therefore develop novel in the enrichment of coating interface formation metal ion
Antifouling paint resin is one of the most effective method for increasing the nonpolluting coating service life.
Summary of the invention
The present invention is too fast in order to overcome the problems, such as the anti-fouling agents plasma diffusing W,Mos such as the existing copper from polishing marine antifouling coating, mentions
For the preparation method of a metal ion species slow releasing function antifouling paint resin.This method is by unsaturated acids Arrcostab, unsaturated acids
Alkyl estersil, the copolymerization of unsaturated acids aminoalkyl chemical combination object, obtain the novel self polishing copolymer antifouling paint containing amino structure unit
Resin.Its innovation is, forms the effect of coordination using amino in copolymer side chain and metal ion (such as copper ion), subtracts
The loss of few metal ion anti-fouling agent, realizes the slow releasing function of metal ion, achievees the purpose that extend coating anti-fouling effect.Ocean
Panel experiment the result shows that, using having the new type resin with bit function that can effectively extend antifouling period nearly one of antifouling paint
Times.Resin manufacturing conditions of the present invention are mild, the conversion ratio of polymerized monomer close to 100%, prepared new type resin and coating other
It can directly be applied after component mixing, it is not necessary to isolate and purify, be suitable for industrialized production.
Preparation method of the present invention about a metal ion species slow releasing function antifouling paint resin, the specific steps are as follows:
Radical initiator, unsaturated acids Arrcostab, unsaturated acids alkyl estersil, unsaturated acids aminoalkyl chemical combination object are pressed one
Fixed molar ratio, is dissolved in organic solvent, under nitrogen atmosphere, 50oC~120oC carries out polymerisation in solution, reacts 3 ~ 15 hours, generates
Homogeneous copolymer resin lipoprotein solution.The copolymer resin lipoprotein solution of this method preparation uses the side of traditional free radical solution polymerization
Method, it is advantageous that monomer is close to quantitative reaction, polymerization reaction is easily controllable, and product can be applied directly, be fitted without isolating and purifying
In industrialized production.
With metal ion coordination can occur for the amino structure unit in copolymer resin prepared by the present invention, can
Conventional metals ion anti-fouling agent is effectively reduced and is lost too fast problem, to reduce the usage amount of metal ion anti-fouling agent.Through sea
Foreign hanging plate comparative experiments test, under conditions of same metering, the painting of the cupric anti-fouling agent of resin preparation prepared by the present invention
Material is 2 times of the antifouling period of traditional antifouling paint, thus can illustrate that having to metal ion for resin prepared by the present invention is aobvious
The slow releasing function of work.
In order to realize foregoing invention task, the present invention adopts the following technical scheme:
By radical initiator, unsaturated acids Arrcostab, unsaturated acids alkyl estersil, unsaturated acids diformazan aminoalkyl base ester with
The mixing of 1.0:50 ~ 80:5 ~ 40:5 ~ 40 molar ratio, is dissolved in organic solvent, the mass concentration for controlling mix monomer exists
20% ~ 70%, under nitrogen atmosphere, 50oC~120oIt under the conditions of C, reacts 3 ~ 15 hours, acquisition mass concentration is 20% ~ 70% copolymer resin
Lipoprotein solution.
Radical initiator used in above-mentioned process for preparing resins is one in azodiisobutyronitrile or benzoyl peroxide
The mixture of kind or two kinds of initiators；Organic solvent used includes the mixture of dimethylbenzene, ethyl acetate or both.
Unsaturated acids Arrcostab used in polymerization reaction, unsaturated acids alkyl estersil, unsaturated acids aminoalkyl chemical combination object
Structure as shown in formula 1-3,
Wherein: the R in formula 11For methyl or hydrogen atom, n is the integer between 0 ~ 8；R in formula 22For methyl or hydrogen atom, R3For
Methyl, ethyl, propyl, isopropyl or butyl；R in formula 34Methyl or hydrogen atom, X are oxygen atom or NH, the integer that m is 2 ~ 16.
Metal ion described in process for preparing resins of the present invention includes Cu2+, Cu1+, Zn2+Or in which the two or three
Mixture, above-mentioned metal ion mostly come from Cu in antifouling paint2O, CuO, ZnO additive dissociating product in the seawater.
There is the coordination with metal ion in order to illustrate the amino structure unit in polymer, the present invention has done as follows
Model experiment is verified:
By 0.157 g(1 mmol) N, N- urethane dimethacrylate ethyl ester (DMA) and 1.6 mg(10 μm of ol) two isobutyl of azo
75 after cyanogen (AIBN) mixing deoxygenationoIt is reacted under C and obtains within 8 hours polymer N, N- urethane dimethacrylate ethyl ester PDMA.
Compound concentration is the CuSO of 5,10,15,20 and 25 mmol/L4·5H2O methanol solution, to above-mentioned solution in 400-1000 nm
Absorbance in range is tested to obtain its maximum absorption wavelength, draws CuSO4The standard of concentration of methanol solution and absorbance
Curve (Fig. 1);The amount for weighing 8.9 mg PDMA(PDMA amino unit substances is 0.057 mmol) and 25 mg(0.1 mmol)
CuSO4·5H2O is dissolved separately in 5 mL methanol, and two kinds of solution are mixed, and obtains complex compound sediment after 10 min of ultrasound,
It is 0.160 that absorbance of its supernatant at 810 nm of maximum absorption wavelength is measured after centrifugation;As a result being averaged for five experiments is taken
Value, according to standard curve, determines CuSO in supernatant4·5H2The quality of O be 15.75 mg, be computed, 37% copper ion with
PDMA occurs to be coordinated and generate complex compound sedimentation, and ligand complex occurs for average each copper ion and 1.52 tertiary amine groups.
In order to further illustrate the amino structure unit in polymer to the slow releasing function of metal ion, the present invention done as
Drag experiment:
The verification result that complex compound is formed according to metal copper ion and polymer amino, by 0.2 mmol copper ion and containing 0.4
High-molecular complex, the 0.2 mmol CuSO of the PDMA generation of mmol amino4And 0.4 mmol PDMA be respectively put into three fine jades
Rouge gel cylindrical center (shown in Fig. 2) can be migrated using ion in gel, and being discharged into water by gel will
Enhance the principle of water conductive capability, measures the conductivity variations of gel column outer layer water to determine ion release rate.In gel column
Periphery plus 50 mL deionized waters more renew water, testing time 8 after 24 h carry out conductance measurement to gel periphery water
It.Fig. 3 is that the conductivity of gel column periphery water changes with time.It can be seen from figure 3, bright sulfur acid copper sample conductivity drop
Low is most rapid, illustrates that its migration is most fast；And the conductivity of the pure PDMA sample of blank control test always with the conductivity of pure water
Unanimously, illustrate that PDMA is not moved to outside gel column；And it is most slow with the copper ion release of tertiary amine complexing, hence it is demonstrated that polymer
Amino and the slow releasing function that copper ion complexing may be implemented copper ion.
Fig. 1 is CuSO4The standard curve of concentration of methanol solution and absorbance.
Fig. 2 is that schematic diagram is tested in gel column-conductance measurement.
Fig. 3 is that copper ion, amine polymer, copper and the conductivity of amine complex release change over time.
Resin prepared by the present invention is illustrated below with reference to embodiment, but the present invention is not limited only to embodiment model
It encloses.
Embodiment 1
Weigh the dibenzoyl peroxide of 2.42 grams (0.01 mol), 80 grams of (0.80 mol) methyl methacrylates (MMA, point
Son amount 100), 91.2 grams (0.40 mol) of acrylic acid triisopropyl estersil (TIPSA, molecular weight 228), 62.80 gram (0.40
Mol) dimethylaminoethyl methacrylate (DMA, molecular weight 157) and 101 grams of dimethylbenzene, are dissolved in 1 liter of glass container, lead to
Nitrogen deoxygenation 30 minutes, under nitrogen protection 100oC reacts 5 hours, obtains and contains 70% copolymer resin lipoprotein solution.
Embodiment 2
By 1.67 grams of (0.01 mol) azodiisobutyronitriles (AIBN, molecular weight 167), 50 grams of (0.50 mol) methyl methacrylates
Ester, 12.1 grams of (0.05 mol) methacrylic acid triisopropyl silicon, 7.85 grams of (0.05 mol) dimethylaminoethyl second
Ester and 286.40 grams of dimethylbenzene, are dissolved in 1 liter of glass container, lead to nitrogen deoxygenation 30 minutes, and under nitrogen protection 50oC reaction 7
Hour, it obtains and contains 20% copolymer resin lipoprotein solution.
Embodiment 3
Weigh dibenzoyl peroxide, 102.4 grams of (0.80 mol) butyl methacrylates, 85.2 of 2.42 grams (0.01 mol)
The methacrylic acid tributyl estersil of gram (0.30 mol), 106 grams of (0.30 mol) dimethylaminoethyl hexadecyl esters,
296 grams of ethyl acetate, are dissolved in 1 liter of glass container, lead to nitrogen deoxygenation 30 minutes, and under nitrogen protection 110oC reaction 5 is small
When, it obtains and contains 50% copolymer resin lipoprotein solution.
Embodiment 4
Weigh dibenzoyl peroxide, 80 grams of (0.80 mol) methyl methacrylates, 45.6 grams of 2.42 grams (0.01 mol)
The acrylic acid trimethylsilyl group of (0.20 mol), 68 grams of (0.40 mol) acrylate propionamides and 290 grams of dimethylbenzene
It is dissolved in 1 liter of glass container, leads to nitrogen deoxygenation 20 minutes, under nitrogen protection 120oC reacts 3 hours, obtains total containing 40%
Copolymer resin solution.
Embodiment 5
Ratio as shown in Table 1 is separately added into initiator azodiisobutyronitrile (AIBN), first in six groups 1 liter of three-necked flask
Base methyl acrylate (MMA), acrylic acid trimethylsilyl group (TIPSA), dimethylaminoethyl methacrylate (DMA) and diformazan
Benzene (Xylene) leads to nitrogen deoxygenation 30 minutes, and under nitrogen protection 100oC reacts 6 hours, obtains and contains 50% copolymer resin
Solution.It is respectively R0, R1, R2, R3, R4 and R5 with reaction condition resulting polymers resin described in table 1.Wherein, polymer R0
It is not amino-containing tradition from polishing resin, R1-R5 is the novel polymeric resin of different amino contents.
The cuprous oxide of 5 wt% is added in above-mentioned synthetic resin R0 ~ R5, is stirred evenly, C0-C5 is obtained respectively and applies
Material, sprays on epoxy resin board (30x20cm2), carry out marine anti-pollution test.12 weeks ocean panel experiment results such as 2 institute of table
Show,
2 ocean place panel experiment result of table explanation, the polymer anti-fouling effect of the amido-containing group with coordination structure are obvious
It is better than conventional resins coating, with the increase of amino amount in resin, the anti-fouling effect of coating also enhances.Compare conventional resins R0
One times of left side of antifouling renewal of the nonpolluting coating of the nonpolluting coating C5 preparation of the nonpolluting coating C0 of preparation, new type resin R5 preparation
It is right.
The preparation method of metal ion species slow releasing function antifouling paint resin provided by the invention has been carried out in detail above
Thin to introduce, used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention, it is noted that for the common skill of the art
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for art personnel, these change
Into the range for also belonging to rights protection of the present invention with modification.
Claims (4)
1. the preparation method of a metal ion species slow releasing function antifouling paint resin, it is characterised in that: by radical initiator, no
Saturation acid alkyl ester, unsaturated acids alkyl estersil, unsaturated acids aminoalkyl chemical combination object are rubbed with 1.0:50 ~ 80:5 ~ 40:5 ~ 40
You mix ratio, are dissolved in organic solvent, control the mass concentration of mix monomer in 20% ~ 70%, under nitrogen atmosphere, 50oC~
120oIt under the conditions of C, reacts 3 ~ 15 hours, acquisition mass concentration is 20% ~ 70% copolymer resin lipoprotein solution.
2. the preparation method of a metal ion species slow releasing function antifouling paint resin according to claim 1, it is characterised in that: institute
The radical initiator stated is the mixture of one or both of azodiisobutyronitrile or benzoyl peroxide compound；It is described
Organic solvent be or mixtures thereof dimethylbenzene or ethyl acetate.
3. the preparation method of a metal ion species slow releasing function antifouling paint according to claim 1, it is characterised in that: described
Unsaturated acids Arrcostab, unsaturated acids alkyl estersil, unsaturated acids aminoalkyl chemical combination object structure respectively as shown in following formula 1 ~ 3,
Wherein: the R in formula 11For methyl or hydrogen atom, n is the integer between 0 ~ 8；R in formula 22For methyl or hydrogen atom, R3
For methyl, ethyl, propyl, isopropyl or butyl；R in formula 34For methyl or hydrogen atom, X is oxygen atom or NH, m be 2 ~ 16 it is whole
Number.
4. the preparation method of a metal ion species slow releasing function antifouling paint resin according to claim 1, it is characterised in that: institute
The metal ion stated includes Cu2+, Cu1+, Zn2+Or in which two or three of mixture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150628A (en) * | 2021-03-16 | 2021-07-23 | 赵青山 | Self-polishing graphene antifouling paint and preparation method thereof |
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| JPH08269389A (en) * | 1995-03-30 | 1996-10-15 | Nippon Oil & Fats Co Ltd | Coating composition |
| CN103396513A (en) * | 2013-07-24 | 2013-11-20 | 华南理工大学 | Preparation method and application of main chain fracture type polyacrylic acid silane ester resin |
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