CN105542607B - A kind of acrylate self polishing copolymer antifouling paint of the ion modification containing betaine type amphoteric and preparation method thereof - Google Patents
A kind of acrylate self polishing copolymer antifouling paint of the ion modification containing betaine type amphoteric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of acrylate self polishing copolymer antifouling paint of ion modification containing betaine type amphoteric, mass percent of the component and each component which includes in coating is：The acrylic acid of betaine type amphoteric ion functionalization polishes resin 30%~50% certainly；Composite anti-fouling agent 15%~35%；Color stuffing 5%~15%；Auxiliary agent 1%~5%；Organic solvent 10%~20%；The acrylic acid of the betaine type amphoteric ion functionalization from polish resin structural formula be：Wherein, R1For H or CH3, R2Represent the alkyl that carbon number is 1~4, A represents the organic acidic group of monovalence, and m, p, x, y are 1 ~ 50 integer.Invention additionally discloses the preparation method of the coating.After coating of the present invention film forming, there is good binding ability with substrate, long period of soaking does not crack in seawater and other defect and can keep lasting brightness.
Description
Technical field
The invention belongs to marine antifouling coating field, it is related to a kind of foreign-going ship, speedboat, pipeline under the ocean and contains sweet tea
Acrylate self polishing copolymer antifouling paint that dish alkaline amphion is modified and preparation method thereof, coating obtained by the coating have with substrate
There is good binding ability to have concurrently from polishing antifouling and function amphion be antifouling and the characteristic of pollution release.
Background technology
In nature, the surface of any infiltration in the seawater, from static pipeline under the ocean to the ship of traveling, all can
It is subject to seawater and marine organisms the effect such as to be stained to the burn into that it is produced.Wherein marine organisms are stained its surface, to oil
The development of the ocean association areas such as excavation industry, ocean monitor instrument, sea transport industry, marine ecology safety causes greatly
Harm.On the one hand, biodeterioration causes the boundary resistance between ship and fluid to increase, and the speed of service reduces, the more combustions of consumption
Oil causes energy waste.According to statistics, the fuel consumption increase as caused by marime fouling is up to 40%, and flight number totle drilling cost increase can
Up to 77%.On the other hand, a large amount of different genera marine organisms are adhered to marine surface, while causing ship top layer biodeterioration
Freely migrated between different waters, have impact on the different waters ecological balance, the sound development to marine ecology causes potentially
Threaten.It can be seen from the above that marime fouling produces the negative effect such as many economy, the energy, environment, safety, or even biology dirt
Damage can also influence human health.
Therefore, reduce and avoid to have due to energy waste, the environmental threat caused by biodeterioration the problems such as extremely important
Scientific value and practice significance.Early stage doping tributyl tin（TBT）As long as five years effectively anti-can be realized from polishing antifouling coating
Dirty effect, but antifouling component therein stablizes in water and easily accumulation, some organisms can be caused lopsided, and possibly into food
Thing chain, becomes the hidden danger for influencing human health and ecological safety.Therefore marine convention method and sea environment-friendly mechanism prohibite
In January, 2008, marine surface do not use such nonpolluting coating.Thus a large number of researchers have been attracted to attempt the antifouling of substitutability
The preparation of coating.At present, prevent that the most effective means of biodeterioration are exactly brushing antifouling paint, thus various ships, pipeline are prevented
Dirty coating just comes into being.In numerous antifouling approach, wherein especially with Tin-free Spc Anti-fouling Paint and environmentally friendly antifouling
Coating is noticeable.Tin-free Spc Anti-fouling Paint (TF-SPC) coordinates low toxicity oxidation sub- using solvable or hydrolyzable base-material
Copper anti-fouling agent, under seawater eroding, new surface is constantly exposed in the slow ablation of base-material, dissolution anti-fouling agent, make film keep it is smooth and
Soil resistance.TF-SPC does not contain tin, and with the characteristic from polishing, it had both been overcome in original self polishing copolymer antifouling paint because stanniferous
And toxicity it is high the shortcomings that, and have the advantages that original self polishing copolymer antifouling paint service life is long, surface is smooth.Although TF-SPC
Can be excellent, but it is that static anti-fouling agent leaching rate is small to have a problem that, is not enough to kill the ocean life for attempting to be attached to hull
Thing.And betaine type function amphion resin can rely on itself distinctive quaternary ammonium salt, sulfonate functional, make to be attached to coating
The marine microorganism cell wall rupture on surface and it is dead, afterwards current shearing or other external force effect under be easy to come off, energy
Effectively avoid or slow down green alga, diatom spore adheres to form microorganism mucous membrane in substrate, play antifouling and pollution release effect.
Therefore, betaine type function amphion anti-fouling effect can effectively be made up into respective lack with being organically combined from polishing antifouling
Fall into, strengthen the antifouling property of antifouling paint.
The content of the invention
Self polishing copolymer antifouling paint poor adhesive force, static state the technical problem to be solved in the present invention is existing unitary system is anti-
The problem of dirty agent leaching rate is small, antifouling mechanism is single and the water degradable antifouling paint effectively antifouling cycle is short.Asked for above-mentioned
Topic, the object of the present invention is to provide a kind of environmental-friendly, multiple antifouling, persistent, of low cost contains betaine type amphoteric
Acrylate self polishing copolymer antifouling paint of ion modification and preparation method thereof.
A kind of acrylate self polishing copolymer antifouling paint of ion modification containing betaine type amphoteric, it is characterised in that the coating bag
Mass percent of the component and each component included in coating be：The acrylic acid of betaine type amphoteric ion functionalization polishes tree certainly
Fat 30%~50%；Composite anti-fouling agent 15%~35%；Color stuffing 5%~15%；Auxiliary agent 1%~5%；Organic solvent 10%~20%；
The acrylic acid of the betaine type amphoteric ion functionalization from polish resin structural formula be
Wherein, R1For H or CH3, R2Represent the alkyl that carbon number is 1~4, A represents the organic acidic group of monovalence, and m, p, x, y are 1 ~ 50
Integer.
The composite anti-fouling agent is made of cuprous oxide and copper pyrithione, both mass ratioes are 6:1~12:1.
The color stuffing is iron oxide red, zinc oxide, titanium dioxide, silica, at least two of blanc fixe.
The organic solvent is the mixed solution of dimethylbenzene and n,N dimethylformamide, mass ratio 1:1.
The auxiliary agent is wetting dispersing agent, levelling agent, defoamer, the mixture of anti-settling agent, mass ratio 2:1:1:4.
The wetting dispersing agent is 103,104,161, one or both of 163 of Germany BYK series.
The defoamer is BYK051,052, one or both of 066.
The levelling agent is BYK 300.
The anti-settling agent is one or both of BYK 410, BYK405, organobentonite, talcum powder.
The preparation method of above-mentioned self polishing copolymer antifouling paint, it is characterised in that comprise the following steps：
1）Preparation of the acrylic acid of betaine type amphoteric ion functionalization from polishing resin
By betaine type amphoteric ion monomer, the soft or hard monomer of acrylic compounds, acrylic acid, styrene in the presence of initiator into
Row is free-radical polymerized, the acrylic resin prepolymer of betaine type amphoteric ion functionalization is obtained, then by the prepolymer and hydrogen
The mixture of both zinc oxide and monovalence organic acid reacts acrylic acid up to betaine type amphoteric ion functionalization from polishing tree
Fat；
2）The preparation of coating
By the acrylic acid of betaine type amphoteric ion functionalization from polishing in resin, organic solvent addition dispersion cylinder, fully
It is 10 minutes scattered, sequentially add auxiliary agent, color stuffing high speed dispersion 10 minutes, be less than 50 within subsequent ball milling 6-10 hours to coating fineness
μm, obtain marine antifouling coating.
The betaine type amphoteric ion monomer is [2- (methylacryloyl epoxide) ethyl] dimethyl-(3- sulfonic acid third
Base) ammonium hydroxide, its preparation method is：By methacrylic acid N, N- dimethylaminoethyls add the 1,3- propane containing equimolar amounts
In the acetonitrile solution of sultone, when reaction 4-10 is small, white crystal precipitation is obtained, is filtered, washing, up to zwitterionic monomer.
The soft or hard monomer of acrylic acid is methyl methacrylate and the mixture of butyl acrylate.
The initiator is azodiisobutyronitrile, its dosage is zwitterionic monomer, the soft or hard monomer of acrylic compounds, acrylic acid
With the 1 ~ 3% of styrene gross mass.
The molar ratio of the zinc hydroxide, monovalence organic acid and acrylic acid is 1:1:1.
The monovalence organic acid is benzoic acid.
The betaine type amphoteric ion monomer, acrylic acid, methyl methacrylate, butyl acrylate and styrene rub
You are than being 1 ~ 4：25~45：25~45：5：15~30.
The present invention is effective from characteristic is polished with zinc acrylate resin with the good bonding performance of substrate by phenyl functional group in coating
With reference to the organotin without world disabling（TBT）Poison, is a kind of environmental-friendly, antifouling persistent, ocean of low cost
Antifouling paint.Betaine type function amphion resin is introduced in the system at the same time and effectively avoids or slow down green alga, diatom spore
Son adheres to form microorganism mucous membrane in substrate, plays antifouling and pollution release synergy.Used film forming resin of the present invention is
The polishing resin, and introducing wherein certainly of betaine type amphoteric ion monomer, zinc acrylate resin/acrylic acid copper, acrylic ester copolymer
Styrene units, improve nonpolluting coating and the binding ability of substrate, and coating surface is smooth, easy for construction, and the four seasons can be used.
A kind of acrylate self polishing copolymer antifouling paint of ion modification containing betaine type amphoteric of the present invention, is sprayed at
The traditional performance of tinplate is as follows：
1）Adhesive force：GB1720-79 （Scratch）, 1 grade；
2）Impact resistance：GB1732-79, 50 Kg；
3）Hardness：GB6379-86, HB grades；
4）Pliability：GB1731-79, 1mm；
5）Coating surface energy：Less than 40 mJm-2；
6）Paint film drying time：GB1728-79,16~25 DEG C of room temperature, when surface drying 1 is small, when the actual drying time 12 is small.
A kind of acrylate self polishing copolymer antifouling paint of functionalization of ion containing betaine type amphoteric of the present invention, can lead to
Crossing spraying or brushing mode and be coated on has on the low carbon steel plate of anti-corrosion primer（150×250×1.5 mm）, anti-corrosion primer dried film thickness
Spend for 200 μm or so, nonpolluting coating thickness control is at 100 μm~200 μm, you can obtains promising result.
By this antifouling paint by the way that model is made on low carbon steel plate of the spraying means coated on epoxy anticorrosion primer, room temperature is filled
After dividing drying, shallow sea panel experiment is carried out.Simultaneous selection international top-brand anti-fouling paint, as Zuo Dun companies produce Seaforce90 from
Polish Wuxi anti-fouling paint（Hereinafter referred to as assistant is honest）, brushed respectively on same size steel plate, brushing thickness is identical with this coating.Together
When select same specification steel plate to do blank, a brushing epoxy anticorrosion primer.To be painted with the experiment models of various antifouling paints with
Blank plate is placed in 6 meters of depths of undersea and carries out real extra large hanging plate dynamic test.Test period 2015,4~2015,8（Marine growth is prosperous
Phase）, test site：Shenzhen Daya Bay.Specially took out and observed and recorded as a result, then rapid when 40 days, 100 days
Put back in seawater and continue to test.For this coating model shallow sea hanging plate after 100 days, paint film is intact, without blistering, come off, specimen surface without
Large ocean fouling organism adheres to, and shows that it has good antifouling and pollution release effect.The experimental results are shown inthe following table.
Embodiment
Heretofore described betaine type amphoteric ion monomer and a kind of functionalization propylene of ion containing betaine type amphoteric
Acid esters is standby as follows from resin-made is polished：
By 12.2 grams of 1,3-propane sultone, 50 grams of anhydrous acetonitriles are added in reactor, are added dropwise under nitrogen protection
Acetonitrile solution containing 15.7 grams of methacrylic acid N, N- dimethylaminoethyls, reaction 8 it is small when after have white crystal precipitation, by white
Crystal filters, and is washed with acetonitrile, is drying to obtain betaine type amphoteric ion monomer.
By 100 gram masses than 1:1 dimethylbenzene is added in reaction bulb with n,N dimethylformamide mixed organic solvents,
80 °C of nitrogen purgings are lower to be added dropwise containing 5.6 grams of zwitterionic monomers, 36.5 grams of acrylic acid, 50 grams of methyl methacrylates, 31.2
Gram styrene, 12.8 grams of butyl acrylates, 2 grams of azodiisobutyronitriles, control it is interior when 1.5 is small drip off, and keep the temperature 2 it is small when.Again
The interior 30 grams of mixed solvents added dissolved with 0.7 gram of azodiisobutyronitrile when 0.5 is small, continue insulation 1 it is small when, obtain containing glycine betaine
Type amphion functionalized acrylic ester resin prepolymer.50 grams of zinc hydroxides and 61 are added into above-mentioned prepolymer system successively
Gram benzoic acid, is warming up to 110 °C, the reaction was continued 2 it is small when, that is, obtain the functionalized acrylic of ion containing betaine type amphoteric ester from
Resin I is polished, its molecular structural formula is：
。
By 100 gram masses than 1:1 dimethylbenzene is added in reaction bulb with n,N dimethylformamide mixed organic solvents,
80 °C of nitrogen purgings are lower to be added dropwise containing 14 grams of zwitterionic monomers, 36.5 grams of acrylic acid, 50 grams of methyl methacrylates, 31.2
Gram styrene, 12.8 grams of butyl acrylates, 2 grams of azodiisobutyronitriles, control it is interior when 1.5 is small drip off, and keep the temperature 2 it is small when.Again
The interior 30 grams of mixed solvents added dissolved with 0.7 gram of azodiisobutyronitrile when 0.5 is small, continue insulation 1 it is small when, obtain containing glycine betaine
Type amphion functionalized acrylic ester resin prepolymer.50 grams of zinc hydroxides and 61 are added into above-mentioned prepolymer system successively
Gram benzoic acid, is warming up to 110 °C, the reaction was continued 2 it is small when, that is, obtain the functionalized acrylic of ion containing betaine type amphoteric ester from
Resin II is polished, its molecular structural formula is：
。
By 200 gram masses than 1:1 dimethylbenzene is added in reaction bulb with n,N dimethylformamide mixed organic solvents,
80 °C of nitrogen purging is lower be added dropwise containing 22.3 grams of zwitterionic monomers, 65.7 grams of acrylic acid, 90 grams of methyl methacrylates,
62.4 grams of styrene, 12.8 grams of butyl acrylates, 4 grams of azodiisobutyronitriles, control it is interior when 1.5 is small drip off, and keep the temperature 2 small
When.The interior 50 grams of mixed solvents added dissolved with 1 gram of azodiisobutyronitrile when 0.5 is small again, continue insulation 1 it is small when, obtain containing sweet tea
Dish alkaline amphion functionalized acrylic ester resin prepolymer.90 grams of zinc hydroxides are added into above-mentioned prepolymer system successively
With 110 grams of benzoic acid, be warming up to 110 °C, the reaction was continued 2 it is small when, that is, obtain the functionalized acrylic of ion containing betaine type amphoteric
From resin III is polished, its molecular structural formula is ester：
。
Embodiment 1
The acrylate of above-mentioned betaine type amphoteric ion functionalization is added into dispersion cylinder from polishing resin I, organic solvent
In, it is fully dispersed, sequentially add composite anti-fouling agent, color stuffing, auxiliary agent and be stirred, high speed dispersion 10 minutes, subsequent ball milling 6 is small
When, obtain antifouling paint after checking viscosity, fineness.
This example betaine type amphoteric ion functionalized acrylic ester self polishing copolymer antifouling paint component proportion is as follows：
Acrylic acid polishes resin I certainly：40 grams；
Composite anti-fouling agent：25 grams of cuprous oxide, 3 grams of copper pyrithione；
Color stuffing：8 grams of iron oxide red, 3 grams of zinc oxide, 1.8 grams of blanc fixe；
Coating additive：0.4 gram of 0.8 gram of BYK163, BYK052,0.4 gram of BYK300,1.6 grams of organobentonite；
Organic solvent：8 grams of dimethylbenzene, 8 grams of n,N dimethylformamide.
Embodiment 2
This example antifouling paint preparation process is same as Example 1.
This example betaine type amphoteric ion functionalized acrylic ester self polishing copolymer antifouling paint component proportion is as follows：
Acrylic acid polishes resin II certainly：40 grams；
Composite anti-fouling agent：25 grams of cuprous oxide, 3 grams of copper pyrithione；
Color stuffing：8 grams of iron oxide red, 3 grams of zinc oxide, 1.8 grams of blanc fixe；
Coating additive：0.4 gram of 0.8 gram of BYK163, BYK052,0.4 gram of BYK300,1.6 grams of organobentonite；
Organic solvent：8 grams of dimethylbenzene, 8 grams of n,N dimethylformamide.
Embodiment 3
This example antifouling paint preparation process is same as Example 1.
This example betaine type amphoteric ion functionalized acrylic ester self polishing copolymer antifouling paint component proportion is as follows：
Acrylic acid polishes resin III certainly：40 grams；
Composite anti-fouling agent：25 grams of cuprous oxide, 3 grams of copper pyrithione；
Color stuffing：8 grams of iron oxide red, 3 grams of zinc oxide, 1.8 grams of blanc fixe；
Coating additive：0.4 gram of 0.8 gram of BYK163, BYK052,0.4 gram of BYK300,1.6 grams of organobentonite；
Organic solvent：8 grams of dimethylbenzene, 8 grams of n,N dimethylformamide.
Embodiment 4
This example antifouling paint preparation process is same as Example 1.
This example betaine type amphoteric ion functionalized acrylic ester self polishing copolymer antifouling paint component proportion is as follows：
Acrylic acid polishes resin II certainly：50 grams；
Composite anti-fouling agent：20 grams of cuprous oxide, 2 grams of copper pyrithione；
Color stuffing：4 grams of iron oxide red, 3 grams of zinc oxide, 1.8 grams of blanc fixe；
Coating additive：0.4 gram of 0.8 gram of BYK163, BYK052,0.4 gram of BYK300,1.6 grams of organobentonite；
Organic solvent：8 grams of dimethylbenzene, 8 grams of n,N dimethylformamide.
Embodiment 5
This example antifouling paint preparation process is same as Example 1.
This example betaine type amphoteric ion functionalized acrylic ester is as follows from polishing antifouling component proportion：
Acrylic acid polishes resin II certainly：30 grams；
Composite anti-fouling agent：30 grams of cuprous oxide, 5 grams of copper pyrithione；
Color stuffing：6 grams of iron oxide red, 3 grams of zinc oxide, 2.8 grams of blanc fixe；
Coating additive：0.4 gram of 0.8 gram of BYK163, BYK052,0.4 gram of BYK300,1.6 grams of organobentonite；
Organic solvent：10 grams of dimethylbenzene, 10 grams of n,N dimethylformamide.
Claims (11)
1. the acrylate self polishing copolymer antifouling paint of a kind of ion modification containing betaine type amphoteric, it is characterised in that the coating includes
Mass percent in coating of component and each component be：The acrylic acid of betaine type amphoteric ion functionalization polishes resin certainly
30%~50%；Composite anti-fouling agent 15%~35%；Color stuffing 5%~15%；Auxiliary agent 1%~5%；Organic solvent 10%~20%；Institute
State the acrylic acid of betaine type amphoteric ion functionalization is from the structural formula for polishing resin
Wherein, R1For H or CH3, R2Represent the alkyl that carbon number is 1~4, A represents the organic acidic group of monovalence, m, p, x, y be 1 ~ 50 it is whole
Number；The composite anti-fouling agent is made of cuprous oxide and copper pyrithione；The color stuffing is iron oxide red, zinc oxide, dioxy
Change at least two in titanium, silica, blanc fixe；The organic solvent is dimethylbenzene and N,N-dimethylformamide
Mixed solution；The auxiliary agent is wetting dispersing agent, levelling agent, defoamer, the mixture of anti-settling agent.
2. coating as claimed in claim 1, it is characterised in that the mass ratio of the cuprous oxide and copper pyrithione is 6:1~
12:1。
3. coating as claimed in claim 1, it is characterised in that the dimethylbenzene and the mass ratio of n,N-Dimethylformamide are
1:1。
4. coating as claimed in claim 1, it is characterised in that the wetting dispersing agent for Germany BYK it is serial 103,104,
161st, one or both of 163；The defoamer is BYK051, one or both of 052；The levelling agent is BYK
300；The anti-settling agent is one or both of BYK 410, BYK405, organobentonite, talcum powder.
5. the preparation method of coating as described in any one of Claims 1-4, it is characterised in that comprise the following steps：
1）Preparation of the acrylic acid of betaine type amphoteric ion functionalization from polishing resin
Betaine type amphoteric ion monomer, the soft or hard monomer of acrylic compounds, acrylic acid, styrene are carried out certainly in the presence of initiator
It is copolymerized by base, obtains the acrylic resin prepolymer of betaine type amphoteric ion functionalization, then by the prepolymer and hydroxide
The mixture of both zinc and monovalence organic acid reacts acrylic acid up to betaine type amphoteric ion functionalization from polishing resin；
2）The preparation of coating
The acrylic acid of betaine type amphoteric ion functionalization is polished certainly in resin, organic solvent addition dispersion cylinder, it is fully dispersed
10 minutes, sequentially add auxiliary agent, color stuffing high speed dispersion 10 minutes, be less than 50 μm within subsequent ball milling 6-10 hours to coating fineness,
Obtain marine antifouling coating.
6. method as claimed in claim 5, it is characterised in that the betaine type amphoteric ion monomer is [2- (metering systems
Acyloxy) ethyl] dimethyl-(3- propyl sulfonic acids) ammonium hydroxide, its preparation method is：By methacrylic acid N, N- diformazan ammonia
Base ethyl ester is added in the acetonitrile solution of the 1,3-propane sultone containing equimolar amounts, when reaction 4-10 is small, obtains white crystal precipitation,
Filtering, washing, up to zwitterionic monomer.
7. method as claimed in claim 5, it is characterised in that the soft or hard monomer of acrylic acid is methyl methacrylate and third
The mixture of olefin(e) acid butyl ester.
8. method as claimed in claim 5, it is characterised in that the initiator is azodiisobutyronitrile, its dosage for both sexes from
The 1 ~ 3% of the soft or hard monomer of sub- monomer, acrylic compounds, acrylic acid and styrene gross mass.
9. method as claimed in claim 5, it is characterised in that the molar ratio of the zinc hydroxide, monovalence organic acid and acrylic acid
For 1:1:1.
10. the method as described in claim 5 or 9, it is characterised in that the monovalence organic acid is benzoic acid.
11. the method for claim 7, it is characterised in that the betaine type amphoteric ion monomer, acrylic acid, methyl-prop
The molar ratio of e pioic acid methyl ester, butyl acrylate and styrene is 1 ~ 4：25~45：25~45：5：15~30.
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| CN107033278B (en) * | 2017-04-14 | 2019-05-14 | 华南理工大学 | A kind of polishing amphoteric ion antifouling resin and its preparation and application certainly with main chain degradability |
| CN107141942A (en) * | 2017-05-15 | 2017-09-08 | 岭东核电有限公司 | Coastal Power Plant water tunnel drag reduction antifouling paint and preparation method thereof |
| CN107163748B (en) * | 2017-05-15 | 2019-09-10 | 岭东核电有限公司 | Marine biofouling prevention coating material and preparation method thereof |
| US20220220241A1 (en) * | 2019-05-10 | 2022-07-14 | Trustees Of Tufts College | Zwitterionic charged copolymer membranes |
| CN110265232B (en) * | 2019-06-11 | 2021-10-15 | 南京邮电大学 | Self-healing hydrogel electrolyte film and preparation method and application thereof |
| CN110655838B (en) * | 2019-10-29 | 2020-07-10 | 中国科学院兰州化学物理研究所 | Betaine type ionic liquid modified coating and preparation method and application thereof |
| US11319434B2 (en) | 2019-12-31 | 2022-05-03 | Industrial Technology Research Institute | Block copolymer, preparation method thereof, and thin film structure comprising the same |
| CN113121762B (en) * | 2019-12-31 | 2024-02-13 | 财团法人工业技术研究院 | Block copolymer, preparation method thereof and film structure comprising same |
| TWI742500B (en) * | 2019-12-31 | 2021-10-11 | 財團法人工業技術研究院 | Block copolymer, preparation method thereof, and thin film structure comprising the same |
| WO2021232236A1 (en) * | 2020-05-19 | 2021-11-25 | 厦门双瑞船舶涂料有限公司 | Ionic silicone gel antifouling coating and preparation method therefor |
| BR112023024712A2 (en) | 2021-05-27 | 2024-02-15 | Metro Int Biotech Llc | CRYSTALLINE SOLIDS OF NICOTINE ACID MONONUCLEOTIDE AND ESTERS THEREOF AND METHODS OF MANUFACTURING AND USE |
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| CN103122187B (en) * | 2011-11-18 | 2015-10-07 | 中国科学院兰州化学物理研究所 | ionic liquid modified marine antifouling paint |
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Effective date of registration: 20220414 Address after: 264006 5, R & D building, Yeda Science Park, No. 300, Changjiang Road, Yantai Economic and Technological Development Zone, Shandong Province Patentee after: Yantai Zhongke advanced materials and green chemical industry technology Research Institute Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |