CN104530894B - A kind of preparation method of environmentally friendly marine antifouling coating - Google Patents
A kind of preparation method of environmentally friendly marine antifouling coating Download PDFInfo
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- CN104530894B CN104530894B CN201510006628.7A CN201510006628A CN104530894B CN 104530894 B CN104530894 B CN 104530894B CN 201510006628 A CN201510006628 A CN 201510006628A CN 104530894 B CN104530894 B CN 104530894B
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 229920002521 macromolecule Polymers 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims abstract description 14
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 5
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 59
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 55
- 239000003999 initiator Substances 0.000 claims description 50
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 44
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005553 drilling Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen Zinc oxide Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical class OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
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- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/12—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
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- 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
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of preparation method of environmentally friendly marine antifouling coating, belong to the synthesis field of antifouling paint.It is characterized in synthesizing using macromolecule prepolymer, zinc hydroxide and organic dicarboxylic acid the base-material of antifouling paint, the following R of its synthetic route1AH+2Zn(OH)2+HOOCR2COOH+R3AH→R1AZnOOCR2COOZnAR3, then add mixing rust resisting pigment and auxiliary agent filtering obtain final product the environmentally friendly marine antifouling coating.Preparation process is simple of the present invention, easily production, the marine antifouling coating of preparation meet sea environment-friendly requirement, and antifouling property is good and long-acting, and marine antifouling coating prepared by the present invention can be widely applied to the marine facilities such as hull, drilling platforms, harbour.
Description
Technical field
The present invention relates to the synthesis field of antifouling paint, and in particular to a kind of preparation of environmentally friendly marine antifouling coating
Method.
Background technology
Current hull, harbour, drilling platforms etc. are stained or corrode caused harm to reduce marine organisms attachment,
External coating antifouling paint be still solve the problem uniquely can extensively using and economic, efficient important method.Prevent ocean
The film forming matter of dirty coating is generally macromolecular organic compound, and anti-fouling agent typically using active organic salt, also uses Chinese medicine
Material solvent extractable matter and metal oxide are compounded, and more use nanometer technology, by nano-Ag particles, zinc oxide ZPT or
Other organic anti-fouling agents are composite anti-fouling agent.Or there is the organometallics such as the cuprous oxide of high content in these antifouling paints
Compound, very big pollution is caused to marine environment, the healthy of people can be caused harm by food chain, otherwise prepare work
Skill is complicated, and actual production difficulty is big, antifouling long-lasting difference.With the progress of science and technology and constantly changing for people's economic condition
Kind, environmental requirement of the people to Marine Paints is also unprecedentedly improved.The main direction of studying for preparing antifouling paint at present is environmentally friendly nothing
Poison, stability and high efficiency and long-acting.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of preparation of environmentally friendly marine antifouling coating
Method, preparation process is simple, easily production, the marine antifouling coating of preparation meets sea environment-friendly requirement, and antifouling property is good and long-acting.
Task of the invention is achieved through the following technical solutions, a kind of preparation side of environmentally friendly marine antifouling coating
Method, is characterized in synthesizing using macromolecule prepolymer, zinc hydroxide and organic dicarboxylic acid the base-material of antifouling paint, its synthetic route
It is as follows：
R1AH+2Zn(OH)2+HOOCR2COOH+R3AH→R1AZnOOCR2COOZnAR3
Wherein R1AH、R3AH is macromolecule prepolymer, is one of alkyd resin, polyacrylic resin, epoxy resin,
R1AH、R3AH can be one species resin, or variety classes resin；HOOCR2COOH is organic dicarboxylic acid, is grass
One of acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, terephthalic acid (TPA), M-phthalic acid；
Dope preparing process is as follows：
By R1AH solution, R3AH solution, zinc hydroxide, HOOCR2COOH and butanol mix, R1AH solution, R3AH solution, hydrogen
Zinc oxide, HOOCR2The rate of charge of COOH is mol ratio 1: 1: 2: 1, is added to during device has a reaction bulb of agitator and water knockout drum
Reflux state is stirred and heated to, maintains the reflux for the acid number of reactant being down to less than 80, obtained living polymer compound and be
The base-material of antifouling paint, is then cooled to less than 70 DEG C, and addition mixing rust resisting pigment and auxiliary agent filtering obtain final product described environment-friendly
Type marine antifouling coating.
The R1AH solution, R3The concentration of AH solution is 40~60%.
The preparation method of the macromolecule prepolymer --- polyacrylic resin is as follows：
A, preparation monomer mixed solution：By weight, by 3~35% ethyl acrylate, 25~50% methacrylic acid
Methyl esters, 5% butyl methacrylate, 3~10% styrene, the mixing of 30~35% acrylic acid；
B, preparation initiator solution：
Prepare initiator solution I：Initiator is 9: 50 with the weight ratio of solvent II；
Prepare initiator solution II：Initiator is 1: 10 with the weight ratio of solvent II；
Prepare initiator solution III：Initiator is 1: 20 with the weight ratio of solvent II；
C, the mixed liquor for preparing molecular weight regulator and butanol：Molecular weight regulator is 1: 220 with the weight ratio of butanol；
D, solvent II I is added in five mouthfuls of flasks of mechanical agitator, condenser, thermometer are equipped with, it is heated to 115~
After 125 DEG C, while monomer mixed solution and initiator solution I is added dropwise, completion of dropping in 3hr is incubated 1hr, then that initiator is added dropwise is molten
Liquid II, the completion of dropping in 30mins is incubated 1hr, then appropriate initiator solution III is added dropwise, then after being incubated 90mins, adds point
The mixed liquor of son amount conditioning agent and butanol.Macromolecule prepolymer polyacrylic resin is obtained after cooling filtering.
Solvent II I is (17~20): (60~80) with the weight ratio of monomer mixed solution.Initiator solution I mixes with monomer
The weight ratio of liquid is (9.5~10): 100；Initiator solution II is (3.5~4) with the weight ratio of monomer mixed solution: 100；Trigger
Agent solution III is (3~4) with the weight ratio of monomer mixed solution: 100.Molecular weight regulator is mixed with the mixed liquor of butanol with monomer
The weight ratio for closing liquid is (18~20): 100.
The solvent II, solvent II I are dimethylbenzene.
The initiator is peroxidized t-butyl perbenzoate.
The molecular weight regulator is tert-dodecyl mercaptan.
The present invention has initiated double zinc salt copolymer structures, by high-molecular organic material and the ingenious combination of organic active composition,
The quantity of the suppression marine bioactivity composition being multiplied in applied per area material, paint coatings surface-active is effective
Constituent concentration is high, effectively suppresses the attachment of some marine organisms, forms a kind of efficient anti-fouling effect；By controlling branch lengths
Control hydrolysis rate, makes paint coatings to have good anti-fouling effect, while improve the service life of paint coatings again, prepares
Marine antifouling coating can meet 2~5 years even antifouling requirement in more than 5 years；Do not contained in the coating of preparation to marine environment shadow
Loud oxious component, active ingredient can be degraded to harmless composition in the seawater, from without causing hazard residue to marine environment,
Meet sea environment-friendly requirement.
The positive effect of the present invention is：Preparation process is simple, easily production, the marine antifouling coating of preparation meet sea environment-friendly
It is required that, antifouling property is good and long-acting.Marine antifouling coating prepared by the present invention can be widely applied to hull, drilling platforms, harbour
Deng marine facility.
Specific embodiment
By the following examples, more explanation in detail is carried out to technical scheme, the present invention does not limit to
In the following examples.
Embodiment 1：
1) preparation of macromolecule prepolymer --- polyacrylic resin
By 30g ethyl acrylates, 300g methyl methacrylates, 30g butyl methacrylates, 60g styrene, 180g third
Olefin(e) acid premixing is made monomer mixed solution, and 9g peroxidized t-butyl perbenzoates and 50g dimethylbenzene are configured into initiator solution I.
200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml of mechanical agitator, condenser, thermometer are equipped with, it is heated to 115~
After 125 DEG C, while monomer mixed solution and initiator solution I is added dropwise, added in 3hr, be then incubated 1hr, then 2g peroxides are added dropwise
Change initiator solution II, the 30mins completion of dropping that t-butyl perbenzoate is configured to 20g dimethylbenzene, be incubated 1hr, then 1g is added dropwise
The initiator solution III that peroxidized t-butyl perbenzoate is configured to 20g dimethylbenzene, then after insulation reaction 1.5hr, add 0.5g
The mixed liquor that tert-dodecyl mercaptan is prepared with 110g butanol, macromolecule prepolymer polyacrylic acid tree is obtained after finally cooling filtering
Fat.
2) preparation of environmentally friendly marine antifouling coating
By 142g polyacrylic resins solution, 35g zinc hydroxides, 21g terephthalic acid (TPA)s and 30g butanol that concentration is 60%
Mixing, is added to during device has the reaction bulb of agitator and water knockout drum and is stirred and heated to reflux state, maintains the reflux for reactant
Acid number be down to less than 80, to less than 70 DEG C, addition mixing rust resisting pigment and auxiliary agent filtering obtain final product environment friend for temperature drop
Good type marine antifouling coating WP1.
Embodiment 2：
1) preparation of macromolecule prepolymer --- polyacrylic resin
By 125g ethyl acrylates, 200g methyl methacrylates, 30g butyl methacrylates, 60g styrene, 185g
Acrylic acid premixing is made monomer mixed solution, and 9g peroxidized t-butyl perbenzoates and 50g dimethylbenzene are configured into initiator solution
I.200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml of mechanical agitator, condenser, thermometer are equipped with, 115 are heated to
After~125 DEG C, while monomer mixed solution and initiator solution I is added dropwise, added in 3hr, be then incubated 1hr, then 2g mistakes are added dropwise
Initiator solution II, the 30mins completion of dropping that oxidation t-butyl perbenzoate is configured to 20g dimethylbenzene, is incubated 1hr, then be added dropwise
The initiator solution III that 1g peroxidized t-butyl perbenzoates are configured to 20g dimethylbenzene, then after insulation reaction 1.5hr, add
The mixed liquor that 0.5g tert-dodecyl mercaptans are prepared with 110g butanol, macromolecule prepolymer polyacrylic acid is obtained after finally cooling filtering
Resin.
2) preparation of environmentally friendly marine antifouling coating
By 142g polyacrylic resins solution, 35g zinc hydroxides, 21g terephthalic acid (TPA)s and 30g butanol that concentration is 60%
Mixing, is added to during device has the reaction bulb of agitator and water knockout drum and is stirred and heated to reflux state, maintains the reflux for reactant
Acid number be down to less than 80, to less than 70 DEG C, addition mixing rust resisting pigment and auxiliary agent filtering obtain final product environment friend for temperature drop
Good type marine antifouling coating WP2.
Embodiment 3：
1) preparation of macromolecule prepolymer --- polyacrylic resin
By 155g ethyl acrylates (BA), 175g methyl methacrylates (MMA), 30g butyl methacrylates (BMA),
50g styrene (Styrene), 190g acrylic acid (AA) premixing are made monomer mixed solution, by 9g peroxidized t-butyl perbenzoates
(TBPB) it is configured to initiator solution I with 50g dimethylbenzene (Xylene).It is being equipped with mechanical agitator, condenser, thermometer
200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml, after being heated to 115~125 DEG C, while monomer mixed solution and initiation is added dropwise
Agent solution, adds in 3hr, is then incubated 1hr, then 2g peroxidized t-butyl perbenzoates (TBPB) and 20g dimethylbenzene is added dropwise
(Xylene) initiator solution II, the 30mins completion of dropping being configured to, is incubated 1hr, then the tertiary fourth of 1g perbenzoic acids is added dropwise
The initiator solution III that ester (TBPB) is configured to 20g dimethylbenzene (Xylene), then after insulation reaction 1.5hr, add uncle 0.5g
The mixed liquor that DDM dodecyl mercaptan is prepared with 110g butanol, macromolecule prepolymer polyacrylic resin is obtained after finally cooling filtering.
2) preparation of environmentally friendly marine antifouling coating
By 142g polyacrylic resins solution, 35g zinc hydroxides, 21g terephthalic acid (TPA)s and 30g butanol that concentration is 60%
Mixing, is added to during device has the reaction bulb of agitator and water knockout drum and is stirred and heated to reflux state, maintains the reflux for reactant
Acid number be down to less than 80, to less than 70 DEG C, addition mixing rust resisting pigment and auxiliary agent filtering obtain final product environment friend for temperature drop
Good type marine antifouling coating WP3.
Embodiment 4：
1) preparation of macromolecule prepolymer --- polyacrylic resin
By 20g ethyl acrylates, 300g methyl methacrylates, 30g butyl methacrylates, 60g styrene, 190g third
Olefin(e) acid premixing is made monomer mixed solution, and 9g peroxidized t-butyl perbenzoates and 50g dimethylbenzene are configured into initiator solution I.
200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml of mechanical agitator, condenser, thermometer are equipped with, it is heated to 115~
After 125 DEG C, while monomer mixed solution and initiator solution is added dropwise, added in 3hr, be then incubated 1hr, then 2g peroxidating is added dropwise
Initiator solution II, the 30mins completion of dropping that t-butyl perbenzoate is configured to 20g dimethylbenzene, is incubated 1hr, then 1g mistakes are added dropwise
The initiator solution III that oxidation t-butyl perbenzoate is configured to 20g dimethylbenzene, then after insulation reaction 1.5hr, add uncle 0.5g
The mixed liquor that DDM dodecyl mercaptan is prepared with 110g butanol, macromolecule prepolymer polyacrylic resin is obtained after finally cooling filtering.
2) preparation of environmentally friendly marine antifouling coating
By 142g polyacrylic resins solution, 35g zinc hydroxides, 21g terephthalic acid (TPA)s and 30g butanol that concentration is 60%
Mixing, is added to during device has the reaction bulb of agitator and water knockout drum and is stirred and heated to reflux state, maintains the reflux for reactant
Acid number be down to less than 80, to less than 70 DEG C, addition mixing rust resisting pigment and auxiliary agent filtering obtain final product environment friend for temperature drop
Good type marine antifouling coating WP4.
Embodiment 5：
1) preparation of macromolecule prepolymer --- polyacrylic resin
By 200g ethyl acrylates, 150g methyl methacrylates, 30g butyl methacrylates, 30g styrene, 190g
Acrylic acid premixing is made monomer mixed solution, and 9g peroxidized t-butyl perbenzoates and 50g dimethylbenzene are configured into initiator solution
I.200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml of mechanical agitator, condenser, thermometer are equipped with, 115 are heated to
After~125 DEG C, while monomer mixed solution and initiator solution is added dropwise, added in 3hr, be then incubated 1hr, then 2g peroxides are added dropwise
Change initiator solution II, the 30mins completion of dropping that t-butyl perbenzoate is configured to 20g dimethylbenzene, be incubated 1hr, then 1g is added dropwise
The initiator solution III that peroxidized t-butyl perbenzoate is configured to 20g dimethylbenzene, then after insulation reaction 1.5hr, add 0.5g
The mixed liquor that tert-dodecyl mercaptan is prepared with 110g butanol, macromolecule prepolymer polyacrylic acid tree is obtained after finally cooling filtering
Fat.
2) preparation of environmentally friendly marine antifouling coating
By 142g polyacrylic resins solution, 35g zinc hydroxides, 21g terephthalic acid (TPA)s and 30g butanol that concentration is 60%
Mixing, is added to during device has the reaction bulb of agitator and water knockout drum and is stirred and heated to reflux state, maintains the reflux for reactant
Acid number be down to less than 80, to less than 70 DEG C, addition mixing rust resisting pigment and auxiliary agent filtering obtain final product environment friend for temperature drop
Good type marine antifouling coating WP5.
Embodiment 6：
1) preparation of macromolecule prepolymer --- polyacrylic resin
By 180g ethyl acrylates, 180g methyl methacrylates, 30g butyl methacrylates, 20g styrene, 190g
Acrylic acid premixing is made monomer mixed solution, and 9g peroxidized t-butyl perbenzoates and 50g dimethylbenzene are configured into initiator solution
I.200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml of mechanical agitator, condenser, thermometer are equipped with, 115 are heated to
After~125 DEG C, while monomer mixed solution and initiator solution is added dropwise, added in 3hr, be then incubated 1hr, then 2g peroxides are added dropwise
Change initiator solution II, the 30mins completion of dropping that t-butyl perbenzoate is configured to 20g dimethylbenzene, be incubated 1hr, then 1g is added dropwise
The initiator solution III that peroxidized t-butyl perbenzoate is configured to 20g dimethylbenzene, then after insulation reaction 1.5hr, add 0.5g
The mixed liquor that tert-dodecyl mercaptan is prepared with 110g butanol, macromolecule prepolymer polyacrylic acid tree is obtained after finally cooling filtering
Fat.
2) preparation of environmentally friendly marine antifouling coating
By 142g polyacrylic resins solution, 35g zinc hydroxides, 21g terephthalic acid (TPA)s and 30g butanol that concentration is 60%
Mixing, is added to during device has the reaction bulb of agitator and water knockout drum and is stirred and heated to reflux state, maintains the reflux for reactant
Acid number be down to less than 80, to less than 70 DEG C, addition mixing rust resisting pigment and auxiliary agent filtering obtain final product environment friend for temperature drop
Good type marine antifouling coating WP6.
Hanging test situation
| Sequence number | Production code member | Spreading area/m2 | Test period/year | Marine organisms adhere to coverage rate/% | Experiment marine site |
| 1 | WP1 | 2 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| 2 | WP2 | 2 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| 3 | WP3 | 2 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| 4 | WP4 | 2 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| 5 | WP5 | 2 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| 6 | WP6 | 2 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
Claims (8)
1. a kind of preparation method of environmentally friendly marine antifouling coating, it is characterised in that using macromolecule prepolymer, hydroxide
Zinc and organic dicarboxylic acid synthesize the base-material of antifouling paint, and its synthetic route is as follows：
R1AH+2Zn(OH)2+HOOCR2COOH+R3AH→R1AZnOOCR2COOZnAR3
Wherein R1AH、R3AH is macromolecule prepolymer, is one of alkyd resin, polyacrylic resin, epoxy resin, R1AH、
R3AH can be one species resin, or variety classes resin；HOOCR2COOH is organic dicarboxylic acid, is oxalic acid, the third two
One of acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, terephthalic acid (TPA), M-phthalic acid；
Dope preparing process is as follows：
By R1AH solution, R3AH solution, zinc hydroxide, HOOCR2COOH and butanol mix, and being added to device has agitator and Fen Shui
Reflux state is stirred and heated in the reaction bulb of device, maintains the reflux for the acid number of reactant being down to less than 80, obtain active high score
Sub- compound is the base-material of antifouling paint, is then cooled to less than 70 DEG C, and addition mixing rust resisting pigment and auxiliary agent filtering are obtained final product
The environmentally friendly marine antifouling coating.
2. a kind of preparation method of environmentally friendly marine antifouling coating according to claim 1, it is characterised in that R1AH is molten
Liquid, R3AH solution, zinc hydroxide, HOOCR2The rate of charge of COOH is mol ratio 1: 1: 2: 1.
3. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 1, it is characterised in that described
The preparation method of macromolecule prepolymer --- polyacrylic resin is as follows：
A, preparation monomer mixed solution：By weight, by 3~35% ethyl acrylate, 25~50% methyl methacrylate,
5% butyl methacrylate, 3~10% styrene, the mixing of 30~35% acrylic acid；
B, preparation initiator solution：
Prepare initiator solution I：Initiator is 9: 50 with the weight ratio of solvent II；
Prepare initiator solution II：Initiator is 1: 10 with the weight ratio of solvent II；
Prepare initiator solution III：Initiator is 1: 20 with the weight ratio of solvent II；
C, the mixed liquor for preparing molecular weight regulator and butanol：Molecular weight regulator is 1: 220 with the weight ratio of butanol；
D, the addition solvent II I in five mouthfuls of flasks of mechanical agitator, condenser, thermometer are equipped with, are heated to 115~125
After DEG C, while monomer mixed solution and initiator solution I is added dropwise, completion of dropping in 3hr is incubated 1hr, then initiator solution is added dropwise
II, the completion of dropping in 30mins is incubated 1hr, then initiator solution III is added dropwise, then after being incubated 90mins, adds molecular weight to adjust
Section agent and the mixed liquor of butanol, macromolecule prepolymer polyacrylic resin is obtained after cooling filtering；
Initiator solution I is (9.5~10) with the weight ratio of monomer mixed solution: 100；Initiator solution II and monomer mixed solution
Weight ratio is (3.5~4): 100；Initiator solution III is (3~4) with the weight ratio of monomer mixed solution: 100.
4. a kind of preparation method of environmentally friendly marine antifouling coating according to claim 3, it is characterised in that solvent
III is (17~20): (60~80) with the weight ratio of monomer mixed solution.
5. a kind of preparation method of environmentally friendly marine antifouling coating according to claim 3, it is characterised in that molecule
Amount conditioning agent is (18~20) with the weight ratio of monomer mixed solution with the mixed liquor of butanol: 100.
6. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 3, it is characterised in that described
Solvent II, solvent II I are dimethylbenzene.
7. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 3, it is characterised in that described
Initiator is peroxidized t-butyl perbenzoate.
8. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 3, it is characterised in that described
Molecular weight regulator is tert-dodecyl mercaptan.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5080892A (en) * | 1985-05-17 | 1992-01-14 | Nippon Paint Co., Ltd. | Hydrolyzable resin composition and an antifouling coating composition containing the same |
| CN101033271A (en) * | 2007-04-23 | 2007-09-12 | 大连交通大学 | Grafted resin with hydrolysis and low surface energy characteristic and anti-fouling paint prepared by the same |
| CN103897092A (en) * | 2014-03-24 | 2014-07-02 | 海洋化工研究院有限公司 | Preparation and application of zinc acrylate-type self-polishing matrix resin for antifouling coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011026357A (en) * | 2007-11-21 | 2011-02-10 | Nitto Kasei Co Ltd | Contamination-proof coating composition, manufacturing method for the composition, contamination-proof coating film formed using the composition, coated article having the coating film on surface, and contamination-proofing treatment method for forming the coating film |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5080892A (en) * | 1985-05-17 | 1992-01-14 | Nippon Paint Co., Ltd. | Hydrolyzable resin composition and an antifouling coating composition containing the same |
| CN101033271A (en) * | 2007-04-23 | 2007-09-12 | 大连交通大学 | Grafted resin with hydrolysis and low surface energy characteristic and anti-fouling paint prepared by the same |
| CN103897092A (en) * | 2014-03-24 | 2014-07-02 | 海洋化工研究院有限公司 | Preparation and application of zinc acrylate-type self-polishing matrix resin for antifouling coating |
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| Title |
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| 丙烯酸锌树脂的制备和表征;于良民等;《涂料工业》;20050531;第35卷(第5期);24-27 * |
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