CN118063715A - Organic silicon metal acrylate resin with excellent marine antifouling property, and preparation method and application thereof - Google Patents
Organic silicon metal acrylate resin with excellent marine antifouling property, and preparation method and application thereof Download PDFInfo
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- CN118063715A CN118063715A CN202410304588.3A CN202410304588A CN118063715A CN 118063715 A CN118063715 A CN 118063715A CN 202410304588 A CN202410304588 A CN 202410304588A CN 118063715 A CN118063715 A CN 118063715A
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- Prior art keywords
- acid
- acrylate
- monomer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 32
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 siloxane structure Chemical group 0.000 claims abstract description 32
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- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- BKLGNGGEJNHIQT-UHFFFAOYSA-N prop-2-enoic acid;silicon Chemical compound [Si].OC(=O)C=C BKLGNGGEJNHIQT-UHFFFAOYSA-N 0.000 claims abstract description 7
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
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- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 13
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 12
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
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- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 6
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000126 substance Substances 0.000 description 9
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005498 polishing Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002519 antifouling agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical compound [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- LGERWORIZMAZTA-UHFFFAOYSA-N silicon zinc Chemical compound [Si].[Zn] LGERWORIZMAZTA-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 241000238586 Cirripedia Species 0.000 description 1
- 229920013731 Dowsil Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 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
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of ocean functional polymer materials, and provides an organosilicon acrylic acid metal salt resin with excellent ocean antifouling property, and a preparation method and application thereof. The organic silicon acrylic acid metal salt resin provided by the invention introduces a siloxane structure and zinc/copper ions into a side chain, and adds functional monomers and adjusts zinc and copper content to endow a coating with certain interlayer adhesion, so that the coating still keeps smooth under the condition of actual seawater scouring, has an antifouling effect for more than 4 months under the condition of actual seawater scouring, and has better development potential in the marine antifouling field.
Description
Technical Field
The invention relates to the technical field of ocean functional polymer materials, in particular to an organosilicon acrylic acid metal salt resin with excellent ocean antifouling property, and a preparation method and application thereof.
Background
In marine environment, microorganisms, plants and animals can grow on the surface of underwater marine equipment in an attached mode to form marine biofouling, normal operation of the marine equipment is affected, and adverse effects are generated on marine shipping and resource development. At present, the most economical and efficient method is to coat an antifouling paint on the surface of marine facilities such as ships, wherein the tin-free self-polishing antifouling paint is a common antifouling paint, the tin-free self-polishing antifouling paint can be continuously updated on the surface based on the hydrolysis of acrylic acid self-polishing resin under the effect of seawater scouring to release an antifouling agent, and the antifouling paint has the advantages of controllable release rate of the antifouling agent, long antifouling period and high antifouling performance, and is the most effective and widely used antifouling paint at home and abroad at present. However, in order to achieve more excellent antifouling performance, a large amount of an antifouling agent such as cuprous oxide needs to be added to the tin-free self-polishing antifouling paint, which causes irreversible damage to the marine environment. Therefore, the method for improving the antifouling performance of the resin in the antifouling paint and reducing the use of an antifouling agent is one of the most effective methods for reducing the negative effect of the tin-free self-polishing antifouling paint on the environment.
The low surface energy antifouling paint is prepared by utilizing the hydrophobic property of the resin such as organic silicon, so that marine organisms are difficult to attach or easy to fall off after attaching, thereby realizing antifouling, and is completely friendly to the environment because the toxic and killing effects of the antifouling agent are not relied on, and the low surface energy antifouling paint becomes the main research direction of the antifouling paint without the antifouling agent at present. However, the paint is still difficult to be widely applied in a short period of time, and the reasons for the paint are mainly two aspects: firstly, the antifouling mechanism is relatively single and limited to specific fouling organisms and application environments (such as ships running at high speed); secondly, the antifouling paint has poor adhesion with the epoxy anticorrosive paint, and one or even two intermediate connecting layers are needed to enhance interlayer fusion, so that the system has complex construction and high manufacturing cost. Therefore, although the organosilicon modified acrylic self-polishing resin becomes a solution, the problems of easy gel production, unstable storage and the like are easy to occur, and the film forming property of the coating is extremely easy to be damaged due to poor adhesion between the coating, the intermediate paint and the anti-corrosion paint in the use process.
Therefore, how to provide a marine antifouling paint with strong adhesion, good antifouling performance and small environmental pollution is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides an organosilicon metal acrylate resin with excellent marine antifouling performance, and a preparation method and application thereof, and aims to solve the technical problem that the existing low-surface-energy antifouling paint has poor adhesion with an anticorrosive primer.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides an organic silicon metal acrylate resin with excellent marine antifouling performance, which has the following structural formula:
Wherein a=5 to 15, m=20 to 100, n=4 to 10, x=5 to 15, y=0 to 40, z=0 to 5;
R is-CH 2CH2-、-CH2CH2CH2 -or-CH 2CH2CH2CH2 -;
R 1 is-H or-CH 3;
R 2 is-H or-CH 3;
R 3 is -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH(CH3)2、-C(CH3)3、-CH2CH2OH、-CH2CH(CH3)OH、-(CH2)3CH3、-(CH2)4CH3、-(CH2)5CH3、-(CH2)6CH3、-(CH2)7CH3、-(CH2)8CH3、-(CH2)9CH3、-(CH2)10CH3、-(CH2)11CH3、-C8H17 or- (CH 2)17CH3);
R 4 is-H or-CH 3;
X is zinc ion, copper ion, iron ion, calcium ion or magnesium ion;
R 5 is the acid radical of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid or p-chlorobenzoic acid;
R 6 is-H or-CH 3;
R 7 is -C4H8N、-C5H9O、-C6H13O2、-C7H13、-C8H9O or-C 10H17;
the number average molecular weight of the organosilicon acrylic acid metal salt resin is 2000-60000, and the molecular weight distribution is 1-2.5.
The invention provides a preparation method of the organic silicon acrylic acid metal salt resin, which comprises the following steps:
S1, mixing an acrylic acid hydroxy ester monomer, organic silicon, a catalyst and a solvent, and then reacting to obtain a macromolecular organic silicon monomer;
s2, mixing a macromolecular organic silicon monomer, an acrylic ester basic monomer, a methacrylic ester basic monomer, acrylic acid, methacrylic acid, acrylamide and a functional acrylic ester monomer to obtain a monomer mixture M 1; the molar ratio of the macromolecular organic silicon monomer to the acrylic ester base monomer to the methacrylic ester base monomer to the acrylic acid to the methacrylic acid to the acrylamide to the functional acrylic ester monomers is 5-15: 20-80: 0 to 20:0 to 20:0 to 20: 5-15: 0 to 5;
S3, mixing a first part of M 1 and a first part of initiator to obtain a monomer mixture M 2; mixing a second portion M 1 with a second portion of initiator to obtain a monomer mixture M 3;
s4, in the protective gas, mixing M 2、M3, a third part of initiator, a chain transfer agent and a solvent, and then reacting to obtain an acrylic prepolymer;
S5, mixing the acrylic acid prepolymer, the metal compound, the organic acid and the solvent in the protective gas, and then reacting to obtain the organosilicon acrylic acid metal salt resin.
Further, in the step S1, the molar ratio of the hydroxyl acrylate monomer to the silicone is 1:0.5 to 5; the mass ratio of the catalyst to the organic silicon to the solvent is 0.5-1.5: 100: 30-300 parts; the reaction temperature is 125-135 ℃ and the reaction time is 3.5-5 h.
In step S4, the first reaction product is obtained by mixing M 2, the chain transfer agent and the solvent, the second reaction product is obtained by mixing the first reaction product with M 3, and the third reaction is performed after mixing the second reaction product with a third portion of initiator.
Further, the mass ratio of the solvent, the chain transfer agent and the M 1 is 75-150: 0.3 to 2:100; the temperature of the first reaction is 75-110 ℃, and the time of the first reaction is 15-45 min; the temperature of the second reaction is 80-95 ℃, and the time of the second reaction is 30-60 min; the temperature of the third reaction is 80-95 ℃, and the time of the third reaction is 2.5-3.5 h.
Further, in the step S5, the molar ratio of the metal compound to the organic acid is 0.6 to 1:1, a step of; the total molar amount of the metal compound and the organic acid is 1 to 2 times of the total molar amount of the acrylic acid and the methacrylic acid; the mass ratio of the total mass of the metal compound and the organic acid to the solvent is 1:1 to 2; the reaction temperature is 75-110 ℃, and the reaction time is 3-10 h.
Further, the first part M 1 and the second part account for 10-20% of the total mass of M 1; the mass ratio of the total mass of the first part of initiator, the second part of initiator and the third part of initiator to M 1 is 0.8-3.2: 100; the first part of initiator accounts for 15-30% of the total mass of the initiator, and the second part of initiator accounts for 50-70% of the total mass of the initiator.
Further, the shielding gas in the step S4 and the step S5 independently includes any one of nitrogen, argon, helium and neon;
The solvent in the steps S1, S4 and S5 independently comprises one or more of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone and methyl isobutyl ketone;
The silicone comprises a silicone resin.
Further, the hydroxy acrylate monomer comprises one or more of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate and 4-hydroxy butyl acrylate;
the catalyst comprises titanate catalyst and/or organotin catalyst;
The acrylic ester basic monomer comprises one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate and stearyl acrylate;
The methacrylate base monomer comprises one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, lauryl methacrylate and stearyl methacrylate;
The functional acrylic ester monomer comprises one or more of isobornyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, ethoxyethoxyethyl acrylate, 2-phenoxyethyl acrylate and 4-acryloylmorpholine;
the initiator comprises one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate;
the chain transfer agent comprises one or more of n-dodecyl mercaptan, tertiary dodecyl mercaptan and aliphatic mercaptan;
The metal compound comprises one or more of zinc oxide, copper oxide, magnesium oxide, calcium oxide, zinc hydroxide, copper hydroxide, ferric hydroxide, magnesium hydroxide and calcium hydroxide;
The organic acid comprises one or more of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid and p-chlorobenzoic acid.
The invention also provides application of the organic silicon acrylic acid metal salt resin in preparing marine antifouling coatings.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the organosilicon resin and the hydroxy acrylate are grafted to prepare the macromolecular organosilicon monomer, and the macromolecular organosilicon monomer and different acrylic ester monomers are copolymerized to prepare the acrylic metal salt resin, so that the problem that an organosilicon system and an acrylic resin system are mutually incompatible is effectively solved, and the prepared product has the characteristics of homogeneous state and transparency. The coating formed by brushing the product on an ABS plate is placed in a dynamic paddle rotary drum experimental device, and the coating is found to have good substrate adhesion, difficult falling off and excellent mechanical strength. Through the real sea antifouling test, the coating has a static real sea antifouling effect of more than 4 months.
Drawings
FIG. 1 is a graph showing the results of testing C, si, N, cu, zn content of a zinc/copper silicone acrylate resin (ACMO-Zn 1Cu1) prepared in example 3 using HITACHI SU1000 FlexSEM II EDS;
FIG. 2 is a graph showing the results of testing C, si, N, cu content of the copper organosilicon acrylate resin prepared in example 5, using HITACHI SU1000FlexSEM II EDS;
FIG. 3 is a diagram of a dynamic drum apparatus for a simulation experiment of application example 1;
FIG. 4 is a graph showing the test results of the simulation test of application example 1;
FIG. 5 is a graph showing the results of the real sea test in the yellow sea area of Qingdao city in Shandong province in application example 2.
Detailed Description
The invention provides an organic silicon metal acrylate resin with excellent marine antifouling performance, which has the following structural formula:
Wherein a=5 to 15, preferably 7 to 13, more preferably 8 to 12; m=20 to 100, preferably 30 to 80, more preferably 40 to 60; n=4 to 10, preferably 5 to 9, more preferably 6 to 7; x=5 to 15, preferably 7 to 13, and more preferably 8 to 12; y=0 to 40, preferably 5 to 35, more preferably 10 to 30; z=0 to 5, preferably 1 to 4, and more preferably 2 to 3;
R is-CH 2CH2-、-CH2CH2CH2 -or-CH 2CH2CH2CH2 -;
R 1 is-H or-CH 3;
R 2 is-H or-CH 3;
R 3 is -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH(CH3)2、-C(CH3)3、-CH2CH2OH、-CH2CH(CH3)OH、-(CH2)3CH3、-(CH2)4CH3、-(CH2)5CH3、-(CH2)6CH3、-(CH2)7CH3、-(CH2)8CH3、-(CH2)9CH3、-(CH2)10CH3、-(CH2)11CH3、-C8H17 or- (CH 2)17CH3);
R 4 is-H or-CH 3;
x is zinc ion, copper ion, iron ion, calcium ion or magnesium ion, preferably zinc ion, copper ion, iron ion or calcium ion, further preferably zinc ion or copper ion;
R 5 is the acid radical of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid or p-chlorobenzoic acid;
R 6 is-H or-CH 3;
R 7 is -C4H8N、-C5H9O、-C6H13O2、-C7H13、-C8H9O or-C 10H17;
The number average molecular weight of the organosilicon acrylic acid metal salt resin is 2000-60000, preferably 4000-50000, more preferably 6000-30000; the molecular weight distribution is 1 to 2.5, preferably 1.2 to 2.2, and more preferably 1.6 to 2.0.
The invention provides a preparation method of the organic silicon acrylic acid metal salt resin, which comprises the following steps:
S1, mixing an acrylic acid hydroxy ester monomer, organic silicon, a catalyst and a solvent, and then reacting to obtain a macromolecular organic silicon monomer;
S2, mixing a macromolecular organic silicon monomer, an acrylic ester basic monomer, a methacrylic ester basic monomer, acrylic acid, methacrylic acid, acrylamide and a functional acrylic ester monomer to obtain a monomer mixture M 1; the molar ratio of the macromolecular organic silicon monomer to the acrylic ester base monomer to the methacrylic ester base monomer to the acrylic acid to the methacrylic acid to the acrylamide to the functional acrylic ester monomers is 5-15: 20-80: 0 to 20:0 to 20:0 to 20: 5-15: 0 to 5, preferably 7 to 13: 30-70: 1 to 16:1 to 16:1 to 16: 7-13: 1 to 4, more preferably 8 to 12: 40-60: 5 to 12:5 to 12:5 to 12: 8-12: 2 to 3;
S3, mixing a first part of M 1 and a first part of initiator to obtain a monomer mixture M 2; mixing a second portion M 1 with a second portion of initiator to obtain a monomer mixture M 3;
s4, in the protective gas, mixing M 2、M3, a third part of initiator, a chain transfer agent and a solvent, and then reacting to obtain an acrylic prepolymer;
S5, mixing the acrylic acid prepolymer, the metal compound, the organic acid and the solvent in the protective gas, and then reacting to obtain the organosilicon acrylic acid metal salt resin.
In the present invention, in the step S1, the molar ratio of the hydroxy acrylate monomer to the silicone is 1:0.5 to 5, preferably 1:1 to 4, more preferably 1:2 to 3; if the amount of the organosilicon is less than 0.5, the residual hydroxyl acrylate is excessive, and self-polymerization occurs in the grafting process due to higher temperature, so that the polymerization of the next step is affected; the mass ratio of the catalyst to the organic silicon to the solvent is 0.5-1.5: 100:30 to 300, preferably 0.7 to 1.3:100:50 to 260, more preferably 0.8 to 1.2:100: 100-200 parts; the temperature of the reaction is 125-135 ℃, preferably 127-133 ℃, and more preferably 130 ℃; the reaction time is 3.5 to 5 hours, preferably 3.8 to 4.6 hours, and more preferably 4.0 to 4.2 hours.
In the invention, in the step S1, the hydroxyl acrylate monomer is added dropwise at a rate of 2-5 drops/S, preferably 3-4 drops/S; the dropping temperature is 60-100 ℃, preferably 70-90 ℃, and more preferably 80-85 ℃; the purpose of the dropwise addition is to prevent the concentration of the hydroxy acrylate monomer from becoming too high and self-polymerization from occurring.
In the present invention, in the step S4, the first reaction product is obtained by mixing M 2, the chain transfer agent and the solvent, then the second reaction product is obtained by mixing the first reaction product with M 3, and finally the third reaction is performed after mixing the second reaction product with the third initiator, thus obtaining the acrylic acid prepolymer.
In the invention, the mass ratio of the solvent, the chain transfer agent and the M 1 is 75-150: 0.3 to 2:100, preferably 80 to 130:0.5 to 1.6:100, more preferably 90 to 120:1.0 to 1.5:100; the temperature of the first reaction is 75-110 ℃, preferably 80-105 ℃, and more preferably 85-100 ℃; the time of the first reaction is 15 to 45 minutes, preferably 20 to 40 minutes, and more preferably 25 to 35 minutes; if the temperature of the first reaction is lower than 75 ℃, monomer mixing is not easy to initiate, and if the temperature of the first reaction is higher than 110 ℃, active species failure can be caused; the temperature of the second reaction is 80-95 ℃, preferably 83-92 ℃, and more preferably 85-90 ℃; the second reaction time is 30-60 min, preferably 35-55 min, and more preferably 40-50 min; the temperature of the third reaction is 80-95 ℃, preferably 83-92 ℃, and more preferably 85-90 ℃; the time for the third reaction is 2.5 to 3.5 hours, preferably 2.7 to 3.3 hours, and more preferably 2.8 to 3.0 hours.
In the present invention, in the step S4, the M 3 is equally divided into 9 to 19 parts, preferably 10 to 18 parts, and more preferably 12 to 16 parts; adding one part at intervals of 10-20 min, preferably 12-18 min, and more preferably 14-16 min; the M 3 is added in batches to avoid agglomeration caused by overlarge single addition amount or explosion caused by overhigh local temperature, and the purpose of synthesizing the acrylic prepolymer is to generate a high polymer with a large number of carboxyl groups in a side chain through free radical polymerization reaction, so that a precursor is provided for preparing metal salt resin in the next step.
In the present invention, in the step S5, the molar ratio of the metal compound to the organic acid is 0.6 to 1:1, preferably 0.7 to 0.9:1, further preferably 0.8:1, the aim is to ensure the sufficient reaction of the two as much as possible, and excessive content can cause a large amount of metal compounds to remain in the polymer solution; the total molar amount of the metal compound and the organic acid is 1 to 2 times, preferably 1.2 to 1.8 times, more preferably 1.4 to 1.6 times the total molar amount of the acrylic acid and the methacrylic acid, in order to ensure sufficient progress of the dehydration condensation reaction; the mass ratio of the total mass of the metal compound and the organic acid to the solvent is 1:1 to 2, preferably 1:1.2 to 1.8, more preferably 1:1.4 to 1.6; the reaction temperature is 75-110 ℃, preferably 80-105 ℃, and more preferably 85-100 ℃; the reaction time is 3 to 10 hours, preferably 4 to 9 hours, and more preferably 5 to 8 hours.
In the present invention, in the step S5, a reaction represented by the following formula occurs:
-COOH+X-OH+-COOH＝-COO-X-OOC-+H2O；
The acrylic prepolymer is cooled to 70 ℃ or lower, preferably 65 ℃ or lower, more preferably 60 ℃ or lower before the reaction, in order to prevent the reaction from being violent when other substances are added thereto due to the excessive temperature.
In the invention, the first part M 1 and the second part account for 10 to 20 percent, preferably 12 to 18 percent, and more preferably 14 to 16 percent of the total mass of M 1; the mass ratio of the total mass of the first part of initiator, the second part of initiator and the third part of initiator to M 1 is 0.8-3.2: 100, preferably 1.0 to 3.0:100, more preferably 1.5 to 2.5:100; the first part of initiator accounts for 15-30% of the total mass of the initiator, preferably 18-26%, and more preferably 20-25%; the second part of the initiator accounts for 50 to 70% of the total mass of the initiator, preferably 55 to 65%, more preferably 60%.
In the present invention, the shielding gas in the step S4 and the step S5 independently includes any one of nitrogen, argon, helium and neon, preferably nitrogen or argon, and more preferably nitrogen;
The solvent in the steps S1, S4 and S5 independently comprises one or more of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone and methyl isobutyl ketone, preferably one or more of toluene, xylene, n-butanol, cyclohexanone and methyl isobutyl ketone, and more preferably one or more of toluene, xylene, cyclohexanone and methyl isobutyl ketone; excessive solvent consumption not only causes air pollution, but also causes solvent waste; the solvent consumption is too small, so that the system solubility is poor, the prepolymer viscosity is high, the heat transfer in the system is not facilitated, and the reaction process is influenced; the solvent is purchased from the national chemical reagent limited company or the Tianjin chemical reagent limited company;
The silicone comprises a silicone resin, preferably DOWSILTM RSN-6018Resin Intermediate、DOWSILTM RSN-0255Flake Resin、DOWSILTM RSN-0249Flake Resin、DOWSILTMRSN-0233Flake Resin、DOWSILTM RSN-0220Flake Resin、DOWSILTM RSN-0217Flake Resin、DOWSILTM RSN-0409HS Resin、DOWSILTM RSN-0431HS Resin、DOWSILTM RSN-0804Resin、DOWSILTM RSN-0805Resin、DOWSILTM RSN-0806Resin、DOWSILTM RSN-0808Resin、DOWSILTMRSN-0840Resin, further preferably a silicone intermediate resin sold under the trade name DOWSIL TM RSN-6018Resin Intermediate by the dow chemical company; the organosilicon has the function of enhancing the hydrophobicity of the acrylic acid metal salt resin, realizing the low surface energy characteristic of the resin, and being incapable of participating in polymerization, so that the organosilicon is grafted with the hydroxyl acrylate to prepare the organosilicon macromer containing double bonds, thus preparing for the next copolymerization process.
In the present invention, the hydroxy acrylate monomer includes one or more of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate and 4-hydroxy butyl acrylate, preferably one or more of hydroxy ethyl acrylate, hydroxy ethyl methacrylate and 4-hydroxy butyl acrylate, further preferably hydroxy ethyl acrylate and/or hydroxy ethyl methacrylate;
the catalyst comprises titanate catalysts and/or organotin catalysts, the titanate catalysts have the functions of preventing self-polycondensation of the organic silicon resin, and the organotin catalysts have the functions of promoting grafting of hydroxy acrylate and the organic silicon resin and increasing grafting efficiency; the titanate catalyst is preferably tetrabutyl titanate and/or tetraisopropyl titanate, and is further preferably tetrabutyl titanate; the organotin catalyst is preferably stannous octoate and/or dibutyltin dilaurate, and more preferably stannous octoate; the catalyst was purchased from national pharmaceutical chemicals company, inc;
The acrylic ester basic monomer comprises one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate and stearyl acrylate, preferably one or more of methyl acrylate, n-butyl acrylate, lauryl acrylate and stearyl acrylate, and more preferably one or more of methyl acrylate, lauryl acrylate and stearyl acrylate; the main function of the acrylic ester basic monomer is to change the length of a side chain in the preparation of the acrylic acid prepolymer, adjust the viscosity of the prepolymer, and facilitate the preparation of metal salt resin with excellent viscosity state in the later period; the acrylate base monomer was purchased from large Tang Shiji or national pharmaceutical chemicals company, inc;
The methacrylate base monomer comprises one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, lauryl methacrylate and stearyl methacrylate, preferably one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and stearyl methacrylate, and further preferably one or more of methyl methacrylate, n-butyl methacrylate and stearyl methacrylate; one function of the methacrylate base monomer is to adjust the hardness of the metal salt resin material; the other function is to change the length of the side chain of the prepolymer, adjust the viscosity of the prepolymer, and facilitate the preparation of metal salt resin with excellent viscosity state in the later period; the methacrylate base monomer is purchased from national pharmaceutical chemicals company or from the Tianjin market metallocene chemical reagent factory.
In the present invention, the main role of acrylic acid and methacrylic acid in the preparation of acrylic acid prepolymer is to polymerize into prepolymer having a large number of carboxyl groups in the side chain and participate in the dehydration reaction with metal compound in step S5; acrylic acid and methacrylic acid were both purchased from large Tang chemical Co.
In the invention, the acrylamide has the function of enhancing the hydrophilicity of the resin in the preparation of the organosilicon modified acrylic acid metal salt resin, and in addition, the acrylamide can be hydrolyzed into acrylic acid, so that the self-polishing performance of the coating can be realized, and the antifouling property of the resin is enhanced; acrylamide was purchased from national pharmaceutical chemicals company.
In the invention, the functional acrylate monomer comprises one or more of isobornyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, ethoxyethoxyethyl acrylate, 2-phenoxyethyl acrylate and 4-acryloylmorpholine, preferably one or more of isobornyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate and 4-acryloylmorpholine, and more preferably one or more of isobornyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate and 4-acryloylmorpholine; the functional acrylic ester monomer has the main function of providing a certain function for the final product, such as 4-acryloylmorpholine monomer, can enhance the mechanical property of the coating, and ensures that the coating is not easy to deform under the action of seawater scouring; when the dosage of the functional acrylic ester monomer is in the range, if the hardness and interlayer adhesion of the product are better, the dosage can be 0, if the hardness and interlayer adhesion of the resin are worse, the dosage is determined according to the reaction state during polymerization, and when the dosage is higher than 5, the pole climbing phenomenon can be generated, and the high polymer cannot be obtained; functional acrylate monomers were purchased from Shanghai Ala Biochemical technology Co., ltd;
The initiator comprises one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate, preferably one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide, ammonium persulfate and potassium persulfate, and further preferably one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, ammonium persulfate and potassium persulfate; the main function of the initiator in the preparation of the acrylic prepolymer is to decompose into active species to initiate the polymerization of monomers; the use amount of the initiator is too small, so that the polymerization of the acrylic resin is incomplete, the conversion rate is low, and the use amount of the initiator is too large, so that the viscosity of the acrylic resin is relatively high, the molecular chain is relatively short, and the adhesion and film formation of the resin are not facilitated; the initiator is purchased from Tianjin metallocene chemical reagent plant or Tianjin Hedong red rock reagent plant;
the chain transfer agent comprises one or more of n-dodecyl mercaptan, tertiary dodecyl mercaptan and aliphatic mercaptan, preferably n-dodecyl mercaptan and/or tertiary dodecyl mercaptan, and further preferably tertiary dodecyl mercaptan; the chain transfer agent has the main function of enabling free radicals of chain extension to generate free radical transfer in the process of preparing the acrylic prepolymer, thereby controlling the molecular weight of the acrylic prepolymer; if the amount of the chain transfer agent is below the range defined in the present invention, it may cause the radical polymerization to be difficult to terminate; if the amount of the chain transfer agent is higher than the range defined in the present invention, it may result in a decrease in the viscosity of the polymer and an excessively short molecular chain; chain transfer agents are purchased from national pharmaceutical chemicals, inc;
the metal compound comprises one or more of zinc oxide, copper oxide, magnesium oxide, calcium oxide, zinc hydroxide, copper hydroxide, ferric hydroxide, magnesium hydroxide and calcium hydroxide, preferably one or more of zinc oxide, copper oxide, magnesium oxide, zinc hydroxide, copper hydroxide, magnesium hydroxide and calcium hydroxide, and more preferably one or more of zinc oxide, copper oxide, magnesium oxide, copper hydroxide and calcium hydroxide;
the organic acid comprises one or more of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid and p-chlorobenzoic acid, preferably one or more of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, leucine, phenylalanine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid and p-chlorobenzoic acid, and further preferably one or more of benzoic acid, naphthenic acid, lauric acid, acetic acid, propionic acid, butyric acid, phenylalanine, disproportionated abietic acid, salicylic acid, furoic acid and p-chlorobenzoic acid; organic acids are purchased from national pharmaceutical chemicals, inc. or Shanghai Engelt chemical, inc.
The invention also provides application of the organic silicon acrylic acid metal salt resin in preparing marine antifouling coatings.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The molar ratio of the hydroxypropyl acrylate to the 6018 organosilicon intermediate resin is 1:1, the catalyst (stannous octoate) is used in an amount of 1 percent by weight of the 6018 organosilicon intermediate, and the mass ratio of the solvent (toluene) to the 6018 is 0.3:0.7, respectively placing 6018 organosilicon intermediate, catalyst and solvent in a three-mouth bottle, placing hydroxypropyl acrylate monomer in a dropping funnel, ensuring that the dropping speed of the hydroxypropyl acrylate monomer is 2 drops/second at 80 ℃, heating to 130 ℃ after the dropping is finished, reacting for 5 hours, and obtaining the macromolecular organosilicon monomer containing double bonds after the dehydration is finished;
S2, mixing the obtained macromolecular organic silicon monomer with acrylic acid basic monomer, acrylic acid, acrylamide and 4-Acryloylmolin (ACMO) according to a molar ratio of 10:69:15:7.5:1 to obtain a monomer mixture (M 1); wherein, the acrylic acid basic monomer is selected from n-butyl acrylate, ethyl acrylate and lauryl acrylate, and the mol ratio of the n-butyl acrylate to the ethyl acrylate to the lauryl acrylate is 30:30:9, a step of performing the process; 1.0% initiator (azobisisobutyronitrile) by weight of M 1 was weighed;
S3, uniformly mixing 10wt% of the monomer mixture (M 1) and 15wt% of an initiator to obtain an initial monomer mixture (M 2) containing the initiator; adding 65% of initiator to the remaining monomer mixture (M 1) to give a batch monomer mixture (M 3) containing initiator;
S4, respectively adding 100% of solvent (xylene: n-butanol=4:1) based on the weight of the monomer mixture (M 1), 0.8% of chain transfer agent (n-dodecyl mercaptan) based on the weight of the monomer mixture (M 1) and the initial monomer mixture (M 2) into a three-port bottle, stirring and introducing nitrogen for 20min, and simultaneously controlling the first reaction temperature to be 100 ℃ under the protection of nitrogen for 20 min; after the first reaction, the batch monomer mixture (M 3) was divided equally into 10 parts, and one part of material was fed at 15 minutes intervals, the reaction temperature was controlled at 100℃and the reaction was carried out for 40 minutes; then, adding the rest initiator uniformly for two times, and reacting for 3 hours at 100 ℃ to obtain a pale yellow, transparent and sticky organosilicon modified acrylic prepolymer;
S5, cooling the acrylic prepolymer to a temperature below 70 ℃ under the protection of nitrogen, and then adding organic acid (the dosage of abietic acid, naphthenic acid, benzoic acid and lactic acid is the same) and zinc oxide; the molar ratio of zinc oxide to organic acid is 1:1, a step of; the total molar amount of zinc oxide and organic acid is 1 time the total molar amount of acrylic acid and methacrylic acid; then adding a mixed solvent (dimethylbenzene: n-butyl alcohol: butyl acetate=4.4:1:10.6) which is equal to the total weight of the zinc oxide and the organic acid, uniformly mixing, reacting for 4 hours at the temperature of 110 ℃, and then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the organosilicon zinc acrylate resin.
Example 2
The same as in example 1, except that zinc oxide in step S5 of example 1 was replaced with zinc oxide and copper hydroxide, wherein the molar ratio of zinc oxide to copper hydroxide was 2:1, obtaining the organic silicon zinc/copper acrylate resin.
Example 3
The same as in example 1, except that zinc oxide in step S5 of example 1 was replaced with zinc oxide and copper hydroxide, wherein the molar ratio of zinc oxide to copper hydroxide was 1:1, obtaining the organic silicon zinc/copper acrylate resin.
Example 4
The same as in example 1, except that zinc oxide in step S5 of example 1 was replaced with zinc oxide and copper hydroxide, wherein the molar ratio of zinc oxide to copper hydroxide was 1:2, obtaining the organosilicon zinc acrylate/copper resin.
Example 5
As in example 1, except that zinc oxide in step S5 of example 1 was substituted for copper hydroxide, a silicone copper acrylate resin was obtained.
Example 6
The molar ratio of the hydroxyethyl methacrylate to the 6018 organosilicon intermediate resin is 1:1, the catalyst (tetrabutyl titanate) is used in an amount of 1 percent based on the weight of the 6018 organosilicon intermediate, and the mass ratio of the solvent (toluene) to the 6018 is 0.3:0.7, respectively placing 6018 organic silicon intermediate, catalyst and solvent in a three-mouth bottle, placing hydroxyethyl methacrylate monomer in a dropping funnel, ensuring that the dropping speed of the hydroxyethyl methacrylate monomer is 2 drops/second at 80 ℃, heating to 130 ℃ after the dropping is finished, reacting for 5 hours, and obtaining a macromolecular organic silicon monomer containing double bonds after the dehydration is finished;
S2, mixing the obtained macromolecular organic silicon monomer with acrylic acid basic monomer, acrylic acid, acrylamide and cyclohexyl methacrylate (CHMA) according to a molar ratio of 10:69:15:7.5:1 to obtain a monomer mixture (M 1); wherein, the acrylic acid basic monomer is selected from n-butyl acrylate, ethyl acrylate and lauryl acrylate, and the molar ratio of the n-butyl acrylate to the ethyl acrylate to the lauryl acrylate is 40:20:9, a step of performing the process; 1.0% initiator (azobisisobutyronitrile) by weight of M 1 was weighed;
S3, uniformly mixing 10wt% of the monomer mixture (M 1) and 15wt% of an initiator to obtain an initial monomer mixture (M 2) containing the initiator; adding 65% of initiator to the remaining monomer mixture (M 1) to give a batch monomer mixture (M 3) containing initiator;
S4, respectively adding 100% of solvent (xylene: n-butanol=4:1) based on the weight of the monomer mixture (M 1), 0.8% of chain transfer agent (tertiary dodecyl mercaptan) based on the weight of the monomer mixture (M 1) and the initial monomer mixture (M 2) into a three-port bottle, stirring and introducing nitrogen for 20min, and simultaneously controlling the first reaction temperature to be 100 ℃ under the protection of nitrogen for 20 min; after the first reaction, the batch monomer mixture (M 3) was divided equally into 10 parts, and one part of material was fed at 15 minutes intervals, the reaction temperature was controlled at 100℃and the reaction was carried out for 40 minutes; then, adding the rest initiator uniformly for two times, and reacting for 3 hours at 100 ℃ to obtain a pale yellow, transparent and sticky organosilicon modified acrylic prepolymer;
S5, cooling the acrylic prepolymer to a temperature below 70 ℃ under the protection of nitrogen, and then adding organic acid (the dosage of abietic acid, naphthenic acid and benzoic acid is the same) and zinc oxide; the molar ratio of zinc oxide to organic acid is 0.6:1, a step of; the total molar amount of zinc oxide and organic acid is 1 time the total molar amount of acrylic acid and methacrylic acid; then adding a mixed solvent (dimethylbenzene: n-butyl alcohol=4.4:1:10.6) which is equal to the total weight of the zinc oxide and the organic acid, uniformly mixing, reacting for 4 hours at the temperature of 110 ℃, and then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the organosilicon zinc acrylate resin.
Example 7
The molar ratio of the hydroxyethyl acrylate to the 6018 organosilicon intermediate resin is 1:1, the catalyst (tetraisopropyl titanate) is used in an amount of 1% by weight of 6018 organosilicon intermediate, and the mass ratio of the solvent (toluene) to 6018 is 0.3:0.7, respectively placing 6018 organic silicon intermediate, catalyst and solvent in a three-mouth bottle, placing hydroxyethyl acrylate monomer in a dropping funnel, ensuring that the dropping speed of the hydroxyethyl acrylate monomer is 2 drops/second at 80 ℃, heating to 130 ℃ after the dropping is finished, reacting for 5 hours, and obtaining a macromolecular organic silicon monomer containing double bonds after the dehydration is finished;
S2, mixing the obtained macromolecular organic silicon monomer with acrylic acid basic monomer, acrylic acid, acrylamide and cyclohexyl methacrylate (CHMA) according to a molar ratio of 10:69:15:7.5:1 to obtain a monomer mixture (M 1); wherein, the acrylic acid basic monomer is selected from n-butyl acrylate, ethyl acrylate and lauryl acrylate, and the molar ratio of the n-butyl acrylate to the ethyl acrylate to the lauryl acrylate is 40:20:9, a step of performing the process; 1.0% initiator (azobisisobutyronitrile) by weight of M 1 was weighed;
S3, uniformly mixing 10wt% of the monomer mixture (M 1) and 15wt% of an initiator to obtain an initial monomer mixture (M 2) containing the initiator; adding 65% of initiator to the remaining monomer mixture (M 1) to give a batch monomer mixture (M 3) containing initiator;
S4, respectively adding 100% of solvent (xylene: n-butanol=4:1) based on the weight of the monomer mixture (M 1), 0.8% of chain transfer agent (tertiary dodecyl mercaptan) based on the weight of the monomer mixture (M 1) and the initial monomer mixture (M 2) into a three-port bottle, stirring and introducing nitrogen for 20min, and simultaneously controlling the first reaction temperature to be 100 ℃ under the protection of nitrogen for 20 min; after the first reaction, the batch monomer mixture (M 3) was divided equally into 10 parts, and one part of material was fed at 15 minutes intervals, the reaction temperature was controlled at 100℃and the reaction was carried out for 40 minutes; then, adding the rest initiator uniformly for two times, and reacting for 3 hours at 100 ℃ to obtain a pale yellow, transparent and sticky organosilicon modified acrylic prepolymer;
S5, cooling the acrylic prepolymer to a temperature below 70 ℃ under the protection of nitrogen, and then adding organic acid (the dosage of abietic acid, naphthenic acid and benzoic acid is the same) and zinc oxide; the molar ratio of zinc oxide to organic acid is 0.6:1, a step of; the total molar amount of zinc oxide and organic acid is 1 time the total molar amount of acrylic acid and methacrylic acid; then adding a mixed solvent (dimethylbenzene: n-butyl alcohol=4.4:1:10.6) which is equal to the total weight of the zinc oxide and the organic acid, uniformly mixing, reacting for 4 hours at the temperature of 110 ℃, and then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the organosilicon zinc acrylate resin.
Example 8
The molar ratio of the hydroxypropyl acrylate to the 6018 organosilicon intermediate resin is 1:2.5 catalyst (dibutyltin dilaurate) 0.5% by weight of the 6018 silicone intermediate, solvent (MIBK: toluene=1:1) to 6018 mass ratio of 0.6:0.4, respectively placing 6018 organosilicon intermediate, catalyst and solvent in a three-mouth bottle, placing hydroxypropyl acrylate monomer in a dropping funnel, ensuring that the dropping speed of the hydroxypropyl acrylate monomer is 2 drops/second at 80 ℃, heating to 125 ℃ after the dropping is finished, reacting for 6 hours, and obtaining the macromolecular organosilicon monomer containing double bonds after the dehydration is finished;
S2, mixing the obtained macromolecular organic silicon monomer with acrylic acid basic monomer, acrylic acid, acrylamide and 4-Acryloylmolin (ACMO) according to a molar ratio of 10:69:15:7.5:1 to obtain a monomer mixture (M 1); wherein, the acrylic acid basic monomer is selected from n-butyl acrylate, ethyl acrylate and lauryl acrylate, and the molar ratio of the n-butyl acrylate to the ethyl acrylate to the lauryl acrylate is 40:20:9, a step of performing the process; 1.0% initiator (azobisisobutyronitrile) by weight of M 1 was weighed;
S3, uniformly mixing 10wt% of the monomer mixture (M 1) and 15wt% of an initiator to obtain an initial monomer mixture (M 2) containing the initiator; adding 65% of initiator to the remaining monomer mixture (M 1) to give a batch monomer mixture (M 3) containing initiator;
S4, respectively adding 100% of solvent (xylene: n-butanol=4:1) based on the weight of the monomer mixture (M 1), 0.8% of chain transfer agent (tertiary dodecyl mercaptan) based on the weight of the monomer mixture (M 1) and the initial monomer mixture (M 2) into a three-port bottle, stirring and introducing nitrogen for 20min, and simultaneously controlling the first reaction temperature to be 100 ℃ under the protection of nitrogen for 20 min; after the first reaction, the batch monomer mixture (M 3) was divided equally into 10 parts, and one part of material was fed at 15 minutes intervals, the reaction temperature was controlled at 100℃and the reaction was carried out for 40 minutes; then, adding the rest initiator uniformly for two times, and reacting for 3 hours at 100 ℃ to obtain a pale yellow, transparent and sticky organosilicon modified acrylic prepolymer;
s5, cooling the acrylic prepolymer to a temperature below 70 ℃ under the protection of nitrogen, and then adding organic acid (the dosage of abietic acid, naphthenic acid and benzoic acid is the same) and zinc oxide; the molar ratio of zinc oxide to organic acid is 1:1, a step of; the total molar amount of zinc oxide and organic acid is 1 time the total molar amount of acrylic acid and methacrylic acid; then adding a mixed solvent (dimethylbenzene: n-butyl alcohol=4.4:1:10.6) which is equal to the total weight of the zinc oxide and the organic acid, uniformly mixing, reacting for 4 hours at the temperature of 110 ℃, and then heating to the azeotropic temperature for dehydration until no distilled water is discharged, thus obtaining the organosilicon zinc acrylate resin.
Application example 1
The organosilicon acrylic acid metal salt resins prepared in examples 1 to 8 were respectively coated on an ABS plate of 10cm×25cm, dried in the air in the dark for 24 hours to form a coating, and placed in a dynamic simulation experiment device (see FIG. 3), wherein the used seawater was taken from the yellow sea area of Qingdao, the temperature was 25 ℃, the rotational speed was 80r/min, and 7 days was a test period, and the test was carried out for 5 periods, and the results are shown in FIG. 4. The resin coating of example 1 started to wrinkle at 7 days, but the wrinkle area did not rise greatly at the subsequent time, while the surface of the resin coating added with copper hydroxide remained flat after 5 test cycles, indicating that copper ions can improve the seawater scouring resistance of the metal salt acrylate resin; the coating of the zinc acrylate resin prepared by the organosilicon macromer prepared by the hydroxyethyl methacrylate still keeps smooth after 5 periods of test, which shows that the coating can effectively enhance the seawater scouring resistance of the resin coating; the zinc acrylate resin coating prepared by increasing the content of 6018 organic silicon intermediate resin still keeps smooth after 5 periods, so that the organic silicon can effectively improve the interlayer adhesion between the zinc acrylate resin coating and the substrate.
Application example 2
The organic silicon acrylic acid metal salt resin prepared in examples 1-8 is coated on a PVC plate, and is dried in the air for 24 hours in a dark place to form a coating, the coating is placed at the position 2 meters under the water of a real sea floating-cut antifouling test platform, the sea area is Qingdao yellow sea area, the growth inhibition effect of the coating on marine fouling organisms is tested in the growth vigorous period of the fouling organisms, and the result is shown in figure 5. In the experimental process of 4 months, the zinc/copper acrylate resin coating prepared by adding copper hydroxide (examples 2-5) has good surface antifouling effect, no large-scale fouling organisms grow, and a blank template is attached with large-scale fouling organisms (barnacles); the resin coating of example 7 was subject to large-area peeling after 1 month; the resin coating of example 8 remained non-shedding and had good anti-fouling effect in the actual sea area for 4 months, demonstrating that increasing the silicone content can effectively improve the mechanical strength and anti-fouling effect of zinc acrylate resin in the actual sea test.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An organosilicon metal acrylate resin with excellent marine antifouling performance, which is characterized by having the following structural formula:
Wherein a=5 to 15, m=20 to 100, n=4 to 10, x=5 to 15, y=0 to 40, z=0 to 5;
R is-CH 2CH2-、-CH2CH2CH2 -or-CH 2CH2CH2CH2 -;
R 1 is-H or-CH 3;
R 2 is-H or-CH 3;
R 3 is -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH(CH3)2、-C(CH3)3、-CH2CH2OH、-CH2CH(CH3)OH、-(CH2)3CH3、-(CH2)4CH3、-(CH2)5CH3、-(CH2)6CH3、-(CH2)7CH3、-(CH2)8CH3、-(CH2)9CH3、-(CH2)10CH3、-(CH2)11CH3、-C8H17 or- (CH 2)17CH3);
R 4 is-H or-CH 3;
X is zinc ion, copper ion, iron ion, calcium ion or magnesium ion;
R 5 is the acid radical of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid or p-chlorobenzoic acid;
R 6 is-H or-CH 3;
R 7 is -C4H8N、-C5H9O、-C6H13O2、-C7H13、-C8H9O or-C 10H17;
the number average molecular weight of the organosilicon acrylic acid metal salt resin is 2000-60000, and the molecular weight distribution is 1-2.5.
2. The method for preparing the organic silicon acrylic acid metal salt resin as claimed in claim 1, which is characterized by comprising the following steps:
S1, mixing an acrylic acid hydroxy ester monomer, organic silicon, a catalyst and a solvent, and then reacting to obtain a macromolecular organic silicon monomer;
s2, mixing a macromolecular organic silicon monomer, an acrylic ester basic monomer, a methacrylic ester basic monomer, acrylic acid, methacrylic acid, acrylamide and a functional acrylic ester monomer to obtain a monomer mixture M 1; the molar ratio of the macromolecular organic silicon monomer to the acrylic ester base monomer to the methacrylic ester base monomer to the acrylic acid to the methacrylic acid to the acrylamide to the functional acrylic ester monomers is 5-15: 20-80: 0 to 20:0 to 20:0 to 20: 5-15: 0 to 5;
S3, mixing a first part of M 1 and a first part of initiator to obtain a monomer mixture M 2;
Mixing a second portion M 1 with a second portion of initiator to obtain a monomer mixture M 3;
s4, in the protective gas, mixing M 2、M3, a third part of initiator, a chain transfer agent and a solvent, and then reacting to obtain an acrylic prepolymer;
S5, mixing the acrylic acid prepolymer, the metal compound, the organic acid and the solvent in the protective gas, and then reacting to obtain the organosilicon acrylic acid metal salt resin.
3. The method according to claim 2, wherein in the step S1, the molar ratio of the hydroxy acrylate monomer to the silicone is 1:0.5 to 5; the mass ratio of the catalyst to the organic silicon to the solvent is 0.5-1.5: 100: 30-300 parts; the reaction temperature is 125-135 ℃ and the reaction time is 3.5-5 h.
4. The method according to claim 2 or 3, wherein in the step S4, the first reaction is performed after mixing M 2, the chain transfer agent and the solvent to obtain a first reaction product, the second reaction is performed after mixing the first reaction product with M 3 to obtain a second reaction product, and finally the third reaction is performed after mixing the second reaction product with a third portion of the initiator to obtain the acrylic prepolymer.
5. The preparation method according to claim 4, wherein the mass ratio of the solvent, the chain transfer agent and the M 1 is 75-150: 0.3 to 2:100; the temperature of the first reaction is 75-110 ℃, and the time of the first reaction is 15-45 min; the temperature of the second reaction is 80-95 ℃, and the time of the second reaction is 30-60 min; the temperature of the third reaction is 80-95 ℃, and the time of the third reaction is 2.5-3.5 h.
6. The method according to claim 2,3 or 5, wherein in the step S5, the molar ratio of the metal compound to the organic acid is 0.6 to 1:1, a step of; the total molar amount of the metal compound and the organic acid is 1 to 2 times of the total molar amount of the acrylic acid and the methacrylic acid; the mass ratio of the total mass of the metal compound and the organic acid to the solvent is 1:1 to 2; the reaction temperature is 75-110 ℃, and the reaction time is 3-10 h.
7. The method of claim 6, wherein the first portion M 1 and the second portion account for 10-20% of the total mass of M 1; the mass ratio of the total mass of the first part of initiator, the second part of initiator and the third part of initiator to M 1 is 0.8-3.2: 100; the first part of initiator accounts for 15-30% of the total mass of the initiator, and the second part of initiator accounts for 50-70% of the total mass of the initiator.
8. The production method according to claim 2, 3, 5 or 7, wherein the shielding gas in step S4 and step S5 independently includes any one of nitrogen, argon, helium and neon;
The solvent in the steps S1, S4 and S5 independently comprises one or more of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone and methyl isobutyl ketone;
The silicone comprises a silicone resin.
9. The preparation method according to claim 8, wherein the hydroxy acrylate monomer comprises one or more of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate and hydroxy butyl 4-acrylate;
the catalyst comprises titanate catalyst and/or organotin catalyst;
The acrylic ester basic monomer comprises one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate and stearyl acrylate;
The methacrylate base monomer comprises one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, lauryl methacrylate and stearyl methacrylate;
The functional acrylic ester monomer comprises one or more of isobornyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, ethoxyethoxyethyl acrylate, 2-phenoxyethyl acrylate and 4-acryloylmorpholine;
the initiator comprises one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate and potassium persulfate;
the chain transfer agent comprises one or more of n-dodecyl mercaptan, tertiary dodecyl mercaptan and aliphatic mercaptan;
The metal compound comprises one or more of zinc oxide, copper oxide, magnesium oxide, calcium oxide, zinc hydroxide, copper hydroxide, ferric hydroxide, magnesium hydroxide and calcium hydroxide;
The organic acid comprises one or more of benzoic acid, naphthenic acid, stearic acid, lauric acid, acetic acid, propionic acid, butyric acid, abietic acid, proline, leucine, phenylalanine, arginine, dimerized abietic acid, disproportionated abietic acid, salicylic acid, furoic acid and p-chlorobenzoic acid.
10. Use of the metal salt of silicone acrylic resin of claim 1 for the preparation of marine antifouling coatings.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410304588.3A CN118063715A (en) | 2024-03-18 | 2024-03-18 | Organic silicon metal acrylate resin with excellent marine antifouling property, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410304588.3A CN118063715A (en) | 2024-03-18 | 2024-03-18 | Organic silicon metal acrylate resin with excellent marine antifouling property, and preparation method and application thereof |
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