CN104530894A - Environment-friendly antifouling marine paint preparing method - Google Patents
Environment-friendly antifouling marine paint preparing method Download PDFInfo
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- CN104530894A CN104530894A CN201510006628.7A CN201510006628A CN104530894A CN 104530894 A CN104530894 A CN 104530894A CN 201510006628 A CN201510006628 A CN 201510006628A CN 104530894 A CN104530894 A CN 104530894A
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 55
- 239000003973 paint Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 8
- 229920002521 macromolecule Polymers 0.000 claims abstract description 21
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 13
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 63
- 239000003999 initiator Substances 0.000 claims description 52
- 238000002360 preparation method Methods 0.000 claims description 47
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 38
- 239000011248 coating agent Substances 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 26
- 239000004925 Acrylic resin Substances 0.000 claims description 24
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 23
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 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
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 claims description 2
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 claims description 2
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005553 drilling Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 4
- WYLIRYQDDKDHLT-UHFFFAOYSA-N CC1=CC=CC=C1C.CC1=CC=CC=C1C Chemical compound CC1=CC=CC=C1C.CC1=CC=CC=C1C WYLIRYQDDKDHLT-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 238000004500 asepsis Methods 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
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
-
- 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
Abstract
The invention relates to an environment-friendly antifouling marine paint preparing method and belongs to the field of antifouling paint synthesis. The method is characterized in that the base material of antifouling paint is synthetized by means of macromolecule prepolymer, zinc hydroxide and organic dicarboxylic acid according to the synthetic route of R[1]AH+2Zn (OH)[2]+HOOCR[2]COOH+R[3]AH->R[1]AZnOOCR[2]COOZnAR[3], and then mixed rust-resisting pigment and auxiliaries are added for fixation to obtain the environment-friendly antifouling marine paint. The preparing process is simple, production is easy, the prepared antifouling marine paint meets the ocean protection environment, antifouling property is good, durability is high, and the preparing antifouling marine paint can be widely applied to marine facilities such as a ship body, a drilling platform and a wharf.
Description
Technical field
The present invention relates to the synthesis field of antifouling paint, be specifically related to a kind of preparation method of environmentally friendly marine antifouling coating.
Background technology
Current hull, harbour, drilling unit etc. are stained or corrode the harm that causes in order to reduce marine organisms attachment, external coating antifouling paint be still solve this problem uniquely can widespread use and economy, efficient important method.The filmogen of marine antifouling coating is generally macromolecular organic compound, stain control agent generally adopts active organic salt, also have adopt Chinese medicinal materials solvent extractable matter and metal oxide composite, more having employing nanotechnology, is composite anti-fouling agent by nano-Ag particles, zinc oxide Zinc Pyrithione or other organic stain control agents.In these antifouling paints or the organometallic compound such as the Red copper oxide that there is high-content, very large pollution is caused to ocean environment, can be worked the mischief to the healthy of people by food chain, or complicated process of preparation, actual production difficulty is large, antifouling long-lasting difference.Along with the progress of science and technology and the continuous improvement of people's economic condition, the environmental requirement of people to Marine Paints also unprecedentedly improves.The main direction of studying preparing antifouling paint is at present environment-protecting asepsis, stability and high efficiency and long-acting.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of preparation method of environmentally friendly marine antifouling coating, preparation technology is simple, and easily produce, the marine antifouling coating of preparation meets sea environment-friendly requirement, and antifouling property is good and long-acting.
Task of the present invention is achieved through the following technical solutions, a kind of preparation method of environmentally friendly marine antifouling coating, and be characterized in the base-material adopting macromolecule prepolymer, zinc hydroxide and organic dicarboxylic acid synthesis antifouling paint, its synthetic route is as follows:
R
1AH+2Zn(OH)
2+HOOCR
2COOH+R
3AH→R
1AZnOOCR
2COOZnAR
3
Wherein R
1aH, R
3aH is macromolecule prepolymer, for Synolac, polyacrylic resin, epoxy resin one of them, R
1aH, R
3aH can be one species resin, also can be different sorts resin; HOOCR
2cOOH is organic dicarboxylic acid, for oxalic acid, propanedioic acid, succinic acid, toxilic acid, fumaric acid, pentanedioic acid, hexanodioic acid, terephthalic acid, m-phthalic acid one of them;
Dope preparing process is as follows:
By R
1aH solution, R
3aH solution, zinc hydroxide, HOOCR
2cOOH and butanols mixing, R
1aH solution, R
3aH solution, zinc hydroxide, HOOCR
2the feed ratio of COOH is mol ratio 1: 1: 2: 1, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, obtain the base-material that living polymer compound is antifouling paint, then be cooled to less than 70 DEG C, interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating.
Described R
1aH solution, R
3the concentration of AH solution is 40 ~ 60%.
The preparation method of described macromolecule prepolymer---polyacrylic resin is as follows:
A, preparation monomer mixed solution (by weight): by the ethyl propenoate of 3 ~ 35%, 25 ~ 50% methyl methacrylate, 5% butyl methacrylate, 3 ~ 10% vinylbenzene, 30 ~ 35% vinylformic acid mix;
B, preparation initiator solution:
Preparation initiator solution I: the weight ratio of initiator and solvent II is 9: 50;
Preparation initiator solution II: the weight ratio of initiator and solvent II is 1: 10;
Preparation initiator solution III: the weight ratio of initiator and solvent II is 1: 20;
The mixed solution of c, preparation molecular weight regulator and butanols: the weight ratio of molecular weight regulator and butanols is 1: 220;
D, in the five mouthfuls of flasks being equipped with mechanical stirrer, condenser, thermometer, add solvent II I, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution I simultaneously, dropwise in 3hr, insulation 1hr, drip initiator solution II again, dropwise in 30mins, insulation 1hr, then drip appropriate initiator solution III, after being incubated 90mins again, add the mixed solution of molecular weight regulator and butanols.Cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
The weight ratio of solvent II I and monomer mixed solution is (17 ~ 20): (60 ~ 80).The weight ratio of initiator solution I and monomer mixed solution is (9.5 ~ 10): 100; The weight ratio of initiator solution II and monomer mixed solution is (3.5 ~ 4): 100; The weight ratio of initiator solution III and monomer mixed solution is (3 ~ 4): 100.The mixed solution of molecular weight regulator and butanols and the weight ratio of monomer mixed solution are (18 ~ 20): 100.
Described solvent II, solvent II I are dimethylbenzene.
Described initiator is peroxidized t-butyl perbenzoate.
Described molecular weight regulator is tert-dodecyl mercaptan.
The present invention has initiated two zinc salt copolymer structure, by organic polymer material and the ingenious combination of organic active composition, be multiplied the quantity of the suppression marine bioactivity composition in applied per area material, paint coatings surfactivity effective constituent concentration is high, some halobiontic attachment of effective suppression, forms a kind of anti-fouling effect efficiently; By controlling branch lengths controlled hydrolysis speed, making paint coatings can have good anti-fouling effect, turn improving the work-ing life of paint coatings simultaneously, even antifouling requirement in more than 5 years that the marine antifouling coating of preparation can meet 2 ~ 5 years; Not containing the oxious component on ocean environment impact in the coating of preparation, active ingredient can be degraded to harmless composition in the seawater, thus does not cause hazard residue to ocean environment, meets sea environment-friendly requirement.
Positively effect of the present invention is: preparation technology is simple, and easily produce, the marine antifouling coating of preparation meets sea environment-friendly requirement, and antifouling property is good and long-acting.Marine antifouling coating prepared by the present invention can be widely used in the maritime facilitieies such as hull, drilling unit, harbour.
Embodiment
By the following examples, carry out comparatively detailed explanation to technical scheme of the present invention, the present invention is not limited to the following examples.
Embodiment 1:
1) preparation of macromolecule prepolymer---polyacrylic resin
Monomer mixed solution is made in 30g ethyl propenoate, 300g methyl methacrylate, 30g butyl methacrylate, 60g vinylbenzene, the pre-mixing of 180g vinylformic acid, 9g peroxidized t-butyl perbenzoate and 50g dimethylbenzene are mixed with initiator solution I.Be equipped with mechanical stirrer, condenser, 200ml dimethylbenzene is added in 3000ml five mouthfuls of flasks of thermometer, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution I simultaneously, add in 3hr, then 1hr is incubated, drip the initiator solution II that 2g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, 30mins dropwises, insulation 1hr, drip the initiator solution III that 1g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, again after insulation reaction 1.5hr, add the mixed solution that 0.5g tert-dodecyl mercaptan and 110g butanols are prepared, finally cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
2) preparation of environmentally friendly marine antifouling coating
It is the mixing of the 142g polyacrylic resin solution of 60%, 35g zinc hydroxide, 21g terephthalic acid and 30g butanols by concentration, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, temperature drops to less than 70 DEG C, and interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating WP1.
Embodiment 2:
1) preparation of macromolecule prepolymer---polyacrylic resin
Monomer mixed solution is made in 125g ethyl propenoate, 200g methyl methacrylate, 30g butyl methacrylate, 60g vinylbenzene, the pre-mixing of 185g vinylformic acid, 9g peroxidized t-butyl perbenzoate and 50g dimethylbenzene are mixed with initiator solution I.Be equipped with mechanical stirrer, condenser, 200ml dimethylbenzene is added in 3000ml five mouthfuls of flasks of thermometer, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution I simultaneously, add in 3hr, then 1hr is incubated, drip the initiator solution II that 2g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, 30mins dropwises, insulation 1hr, drip the initiator solution III that 1g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, again after insulation reaction 1.5hr, add the mixed solution that 0.5g tert-dodecyl mercaptan and 110g butanols are prepared, finally cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
2) preparation of environmentally friendly marine antifouling coating
It is the mixing of the 142g polyacrylic resin solution of 60%, 35g zinc hydroxide, 21g terephthalic acid and 30g butanols by concentration, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, temperature drops to less than 70 DEG C, and interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating WP2.
Embodiment 3:
1) preparation of macromolecule prepolymer---polyacrylic resin
Monomer mixed solution is made in 155g ethyl propenoate (BA), 175g methyl methacrylate (MMA), 30g butyl methacrylate (BMA), 50g vinylbenzene (Styrene), 190g vinylformic acid (AA) pre-mixing, 9g peroxidized t-butyl perbenzoate (TBPB) and 50g dimethylbenzene (Xylene) are mixed with initiator solution I.Be equipped with mechanical stirrer, condenser, 200ml dimethylbenzene is added in 3000ml five mouthfuls of flasks of thermometer, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution simultaneously, add in 3hr, then 1hr is incubated, drip the initiator solution II that 2g peroxidized t-butyl perbenzoate (TBPB) is mixed with 20g dimethylbenzene (Xylene) again, 30mins dropwises, insulation 1hr, drip the initiator solution III that 1g peroxidized t-butyl perbenzoate (TBPB) is mixed with 20g dimethylbenzene (Xylene) again, again after insulation reaction 1.5hr, add the mixed solution that 0.5g tert-dodecyl mercaptan and 110g butanols are prepared, finally cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
2) preparation of environmentally friendly marine antifouling coating
It is the mixing of the 142g polyacrylic resin solution of 60%, 35g zinc hydroxide, 21g terephthalic acid and 30g butanols by concentration, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, temperature drops to less than 70 DEG C, and interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating WP3.
Embodiment 4:
1) preparation of macromolecule prepolymer---polyacrylic resin
Monomer mixed solution is made in 20g ethyl propenoate, 300g methyl methacrylate, 30g butyl methacrylate, 60g vinylbenzene, the pre-mixing of 190g vinylformic acid, 9g peroxidized t-butyl perbenzoate and 50g dimethylbenzene are mixed with initiator solution I.Be equipped with mechanical stirrer, condenser, 200ml dimethylbenzene is added in 3000ml five mouthfuls of flasks of thermometer, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution simultaneously, add in 3hr, then 1hr is incubated, drip the initiator solution II that 2g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, 30mins dropwises, insulation 1hr, drip the initiator solution III that 1g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, again after insulation reaction 1.5hr, add the mixed solution that 0.5g tert-dodecyl mercaptan and 110g butanols are prepared, finally cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
2) preparation of environmentally friendly marine antifouling coating
It is the mixing of the 142g polyacrylic resin solution of 60%, 35g zinc hydroxide, 21g terephthalic acid and 30g butanols by concentration, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, temperature drops to less than 70 DEG C, and interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating WP4.
Embodiment 5:
1) preparation of macromolecule prepolymer---polyacrylic resin
Monomer mixed solution is made in 200g ethyl propenoate, 150g methyl methacrylate, 30g butyl methacrylate, 30g vinylbenzene, the pre-mixing of 190g vinylformic acid, 9g peroxidized t-butyl perbenzoate and 50g dimethylbenzene are mixed with initiator solution I.Be equipped with mechanical stirrer, condenser, 200ml dimethylbenzene is added in 3000ml five mouthfuls of flasks of thermometer, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution simultaneously, add in 3hr, then 1hr is incubated, drip the initiator solution II that 2g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, 30mins dropwises, insulation 1hr, drip the initiator solution III that 1g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, again after insulation reaction 1.5hr, add the mixed solution that 0.5g tert-dodecyl mercaptan and 110g butanols are prepared, finally cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
2) preparation of environmentally friendly marine antifouling coating
It is the mixing of the 142g polyacrylic resin solution of 60%, 35g zinc hydroxide, 21g terephthalic acid and 30g butanols by concentration, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, temperature drops to less than 70 DEG C, and interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating WP5.
Embodiment 6:
1) preparation of macromolecule prepolymer---polyacrylic resin
Monomer mixed solution is made in 180g ethyl propenoate, 180g methyl methacrylate, 30g butyl methacrylate, 20g vinylbenzene, the pre-mixing of 190g vinylformic acid, 9g peroxidized t-butyl perbenzoate and 50g dimethylbenzene are mixed with initiator solution I.Be equipped with mechanical stirrer, condenser, 200ml dimethylbenzene is added in 3000ml five mouthfuls of flasks of thermometer, after being heated to 115 ~ 125 DEG C, drip monomer mixed solution and initiator solution simultaneously, add in 3hr, then 1hr is incubated, drip the initiator solution II that 2g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, 30mins dropwises, insulation 1hr, drip the initiator solution III that 1g peroxidized t-butyl perbenzoate and 20g dimethylbenzene are mixed with again, again after insulation reaction 1.5hr, add the mixed solution that 0.5g tert-dodecyl mercaptan and 110g butanols are prepared, finally cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
2) preparation of environmentally friendly marine antifouling coating
It is the mixing of the 142g polyacrylic resin solution of 60%, 35g zinc hydroxide, 21g terephthalic acid and 30g butanols by concentration, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, temperature drops to less than 70 DEG C, and interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating WP6.
Hanging test situation
| Sequence number | Production code member | Surface covered/m2 | Test period/year | Marine organisms attachment fraction of coverage/% | Test marine site |
| 1 | WP1 | 2 | 3 | Have no marine organisms attachment | Sunshine marine site |
| 2 | WP2 | 2 | 3 | Have no marine organisms attachment | Sunshine marine site |
| 3 | WP3 | 2 | 3 | Have no marine organisms attachment | Sunshine marine site |
| 4 | WP4 | 2 | 3 | Have no marine organisms attachment | Sunshine marine site |
| 5 | WP5 | 2 | 3 | Have no marine organisms attachment | Sunshine marine site |
| 6 | WP6 | 2 | 3 | Have no marine organisms attachment | Sunshine marine site |
Claims (10)
1. a preparation method for environmentally friendly marine antifouling coating, it is characterized in that the base-material adopting macromolecule prepolymer, zinc hydroxide and organic dicarboxylic acid synthesis antifouling paint, its synthetic route is as follows:
R
1AH+2Zn(OH)
2+HOOCR
2COOH+R
3AH→R
1AZnOOCR
2COOZnAR
3
Wherein R
1aH, R
3aH is macromolecule prepolymer, for Synolac, polyacrylic resin, epoxy resin one of them, R
1aH, R
3aH can be one species resin, also can be different sorts resin; HOOCR
2cOOH is organic dicarboxylic acid, for oxalic acid, propanedioic acid, succinic acid, toxilic acid, fumaric acid, pentanedioic acid, hexanodioic acid, terephthalic acid, m-phthalic acid one of them;
Dope preparing process is as follows:
By R
1aH solution, R
3aH solution, zinc hydroxide, HOOCR
2cOOH and butanols mixing, join device to have in the reaction flask of agitator and water trap and be stirred and heated to reflux state, the acid number being back to reactant is kept to be down to less than 80, obtain the base-material that living polymer compound is antifouling paint, then be cooled to less than 70 DEG C, interpolation mixing rust-stabilising pigment and auxiliary agent filter and obtain described environmentally friendly marine antifouling coating.
2. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 1, is characterized in that R
1aH solution, R
3aH solution, zinc hydroxide, HOOCR
2the feed ratio 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, is characterized in that described R
1aH solution, R
3the concentration of AH solution is 40 ~ 60%.
4. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 1, is characterized in that described macromolecule prepolymer---the preparation method of polyacrylic resin is as follows:
A, preparation monomer mixed solution (by weight): by the ethyl propenoate of 3 ~ 35%, 25 ~ 50% methyl methacrylate, 5% butyl methacrylate, 3 ~ 10% vinylbenzene, 30 ~ 35% vinylformic acid mix;
B, preparation initiator solution:
Preparation initiator solution I: the weight ratio of initiator and solvent II is 9: 50;
Preparation initiator solution II: the weight ratio of initiator and solvent II is 1: 10;
Preparation initiator solution III: the weight ratio of initiator and solvent II is 1: 20;
The mixed solution of c, preparation molecular weight regulator and butanols: the weight ratio of molecular weight regulator and butanols is 1: 220;
D, in the five mouthfuls of flasks being equipped with mechanical stirrer, condenser, thermometer, add solvent II I, after being heated to 115 ~ 125 DEG C, dripping monomer mixed solution and initiator solution I simultaneously, dropwise in 3hr, insulation 1hr, drip initiator solution II again, dropwise in 30mins, insulation 1hr, drip initiator solution III again, after being incubated 90mins again, add the mixed solution of molecular weight regulator and butanols, cooling obtains macromolecule prepolymer polyacrylic resin after filtering.
5. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 4, is characterized in that the weight ratio of solvent II I and monomer mixed solution is for (17 ~ 20): (60 ~ 80).
6. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 4, is characterized in that the weight ratio of initiator solution I and monomer mixed solution is for (9.5 ~ 10): 100; The weight ratio of initiator solution II and monomer mixed solution is (3.5 ~ 4): 100; The weight ratio of initiator solution III and monomer mixed solution is (3 ~ 4): 100.
7. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 4, is characterized in that the mixed solution of molecular weight regulator and butanols and the weight ratio of monomer mixed solution are (18 ~ 20): 100.
8. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 4, is characterized in that described solvent II, solvent II I are dimethylbenzene.
9. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 4, is characterized in that described initiator is peroxidized t-butyl perbenzoate.
10. the preparation method of a kind of environmentally friendly marine antifouling coating according to claim 4, is characterized in that described molecular weight regulator is tert-dodecyl mercaptan.
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| US5080892A (en) * | 1985-05-17 | 1992-01-14 | Nippon Paint Co., Ltd. | Hydrolyzable resin composition and an antifouling coating composition containing the same |
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| 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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2015
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| 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 |
| 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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