CN107033273B - One kind is from polishing antifouling resin and preparation method thereof - Google Patents
One kind is from polishing antifouling resin and preparation method thereof Download PDFInfo
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- CN107033273B CN107033273B CN201710178467.9A CN201710178467A CN107033273B CN 107033273 B CN107033273 B CN 107033273B CN 201710178467 A CN201710178467 A CN 201710178467A CN 107033273 B CN107033273 B CN 107033273B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention is to provide one kind from polishing antifouling resin and preparation method thereof.It is by parts by weight are as follows: 10~44 parts of difunctional zinc acrylate resin monomer solution, 55~70 parts of remaining esters of acrylic acid polymerizable unsaturated monomer, 0.8~5 part of initiator and 40~55 parts of mixed solvent are made.The present invention includes the unsaturated monomer that bifunctionality zinc acrylate resin class monomer and other free redicals cause polymerization, is copolymerized the manufactured matrix resin component being used as in environmental protection antifouling paint peculiar to vessel.The present invention is good to substrate adhesive force as the antifouling paint of main film forming substance using the cross-linking type acrylic acid zinc resin synthesized and with centainly from polishing speed, has good anti-fouling effect under marine environment, has good practical application and development prospect.
Description
Technical field
The present invention relates to a kind of marine antifouling coatings, and the present invention also relates to a kind of preparation sides of marine antifouling coating
Method.
Background technique
Marine fouling organism typically refers to be grown in all of part and ocean platform facility surface under ship housing waterline
Epizoite is stained plant, microorganism.Marine fouling organism is many kinds of, has very huge adverse effect to marine ship；
Marine fouling organism will increase frictional resistance when ship's navigation after bottom of ship absorption, increase ship's navigation oil consumption, waste
Increasingly precious fossil fuel；The absorption of fouling organism can also destroy the nonpolluting coating and corrosion-inhibiting coating of marine surface, antifouling painting
The destruction of layer can aggravate the absorption of fouling organism, form vicious circle, and the destruction of corrosion-inhibiting coating then will lead to the steel of ship
Material corrosion, causes the security risk of ship, endangers bigger；Fouling organism can also make ship return depressed place maintenance the destruction of coating for watercraft
Number increase, cause unnecessary economic loss；Fouling organism will lead to clogging in the online absorption of sea farming case,
Fouling organism can also consume a large amount of oxygen, keep aquaculture organism dead, cause the extensive underproduction of aquaculture, economic loss is huge
Greatly.
And up to the present so preventing the absorption of marine fouling organism is to have to solve the problems, such as, it is dirty to solve ocean
Damaging biological the best way is exactly to reach and fouling organism is prevented to adhere in ship or other marine settings external coating antifouling paints
Purpose.Traditional organotin self polishing copolymer antifouling paint is used for the ship in the whole world about 70% or more with brilliant antifouling properties,
Organotin structural material is then discharged constantly in marine environment due to it, and causes the deformity of marine organisms, International Maritime
Tissue, which has required to completely forbid in 2008, uses Organotin antifouling paints.
Tin-free Spc Anti-fouling Paint can satisfy a kind of antifouling paint of good anti-pollution and environmental requirement, such as
Disclose a kind of preparation of single functionality zinc acrylate resin/copper monomer in the patent document of Publication No. CN102167775A, and with
It is prepared from polishing antifouling resin.Also a kind of acrylic acid cu zn is disclosed in the patent document of Publication No. CN104725551A
From the synthetic method of polishing antifouling resin, this method is first by small point of organic cu zn of organic acid and hydroxide iron/zinc synthetic alkali formula
Sub- monomer, then by acrylic monomers mixture initiator effect under acrylic acid synthesizing resin prepolymer, finally alkali formula is had
Machine cu zn small molecule monomer and performed polymer acrylic acid synthesizing cu zn are from polishing antifouling resin.Acrylic acid synthesized by the above method
Zinc resin is single functionality, and synthesis technology is complicated, and serious from resin side reaction is polished.
Summary of the invention
It is good from polishing antifouling resin from polishing performance that the purpose of the present invention is to provide a kind of.The purpose of the present invention also exists
In providing, a kind of process is simple, is avoided that the preparation method from polishing antifouling resin of gel and side reaction.
It is of the invention from polishing antifouling resin by parts by weight are as follows: 10~44 parts of difunctional zinc acrylate resin monomer solution,
55~70 parts of remaining esters of acrylic acid polymerizable unsaturated monomer, 0.8~5 part of initiator and 40~55 parts of mixed solvent are made.
Of the invention can also include: from polishing antifouling resin
1, it is R that the difunctional zinc acrylate resin monomer, which is structural formula,1R2C=CR3-COO-Zn-OOCR4C=CR5Double officials
Zinc acrylate resin monomer can be rolled into a ball, wherein R1、R2、R5Indicate 1~7 alkyl, naphthenic base or aryl, R3、R4Indicate hydrogen atom or methyl.
2, remaining described esters of acrylic acid polymerizable unsaturated monomer is methyl methacrylate, methyl acrylate, methyl
Butyl acrylate, methoxyethyl acrylate, ethyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, propylene
At least one of nitrile, methacrylonitrile.
It is of the invention from polishing antifouling resin the preparation method comprises the following steps:
Step 1: by zinc oxide and solvent with mix after be fitted into container, be placed in reflux condensation mode in 75 DEG C of oil bath；By first
Base acrylic acid, acrylic acid are uniformly mixed with deionized water, are instilled in the container with constant speed through 3 hours, keep the temperature 2 hours
Afterwards, the bifunctionality zinc acrylate resin monomer solution of clear is obtained；
Step 2: the other monomers such as bifunctionality zinc acrylate resin monomer and remaining acrylate monomer that step 1 is generated and
Main initiator mixing, under 90 DEG C~105 DEG C of reflux temperature, is at the uniform velocity added dropwise to the reaction kettle containing mixed solvent in 6h
In, secondary initiator is added dropwise after being added dropwise to complete again and carries out second of initiation reaction, time for adding 0.5h, is further continued for reacting
1.5h, obtain it is colourless, clarification, it is transparent from polishing antifouling zinc acrylate resin solution.The parts by weight of each component are as follows: difunctionality
10~44 parts of zinc acrylate resin monomer solution of group, 55~70 parts of remaining esters of acrylic acid polymerizable unsaturated monomer, initiator 0.8~
5 parts and 40~55 parts of mixed solvent.
Preparation method from polishing antifouling resin of the invention can also include:
1, main initiator accounts for the 3/4 of initiator total amount, and secondary initiator accounts for the 1/4 of initiator total amount, the main initiator
For azodiisobutyronitrile and/or azobisisovaleronitrile, the secondary initiator is benzoyl peroxide.
2, it is propylene glycol monomethyl ether and dimethylbenzene that the mixed solvent, which is mass ratio 1:4~7,.
3, most preferably 95~102 DEG C of the reaction temperature.
Existing complicated from polishing synthetic technology of resins in order to overcome, the serious problem of side reaction, the present invention provides one kind
Marine antifouling coating is also resided in from polishing antifouling resin and is provided the synthetic method of this antifouling resin.The present invention passes through two steps
Method prepares the zinc acrylate resin self polishing copolymer antifouling paint film-forming resin of cross-linking type, and simple process, resin structure is regular, and side reaction is few,
It is not easy gel, there is good practical application and development prospect.
Innovative point and advantage of the invention is: reaction process is simple, and the zinc acrylate resin of bifunctionality is synthesized by the first step
Monomer effectively controls the quantity of crosslinking points in second step, avoids the generation of gel and side reaction；From polishing obtained by the present invention
The zinc acrylate resin that antifouling resin compares non-crosslinked type has more reliable from polishing performance, the real extra large anti-pollution of guarantee.
Specific embodiment
It illustrates below and the present invention is described in more detail.
Embodiment 1:
The synthesis of bifunctionality zinc acrylate resin monomer: by the propylene glycol monomethyl ether of zinc oxide (ZnO) and 256.2g of 122.1g
(PGM) it is added in the four-hole boiling flask of 1L, is uniformly mixed with strength mechanical agitator and is heated to 75 DEG C；By 129.3g methyl-prop
Olefin(e) acid (MAA), 108.3g acrylic acid (AA) and 15g water (H2O) after mixing, it is added in the constant pressure funnel of 500mL, at the uniform velocity
It instills in the four-hole boiling flask equipped with zinc oxide and propylene glycol monomethyl ether, this at the uniform velocity titration process control control is in 3h or so.Work as perseverance
After the completion of pressing the liquid in funnel to be added, the reaction was continued continues 2h, and temperature control is constant at 75 DEG C, is eventually adding the third the two of 108g
Alcohol methyl ether.In entire reaction process, the liquid in flask starts that milky is presented, and finally presents colorless and transparent, obtains
Bifunctionality zinc acrylate resin monomer.
Embodiment 2:
The synthesis of zinc acrylate resin: to four mouthfuls of burnings with thermometer, mechanical stirring, condensing reflux pipe and dropping funel
15g PGM, 57g dimethylbenzene are added in bottle, 5g EA opens mechanical stirring and is passed through nitrogen after mixing, and oil bath heating is to 100
℃；By a certain amount of uniformly mixed 10g MMA, 55g EA, 15g 2-MEA, 20g zinc acrylate resin monomer and 10g dimethylbenzene,
1.0g chain-transferring agent MSD, 2.5g chain initiator AIBN and 7g AMBN solution is instilled in flask with constant speed 6h；It is added dropwise to complete
After add a certain amount of auxiliary 0.5g initiator B PO solution and carry out second of initiation reaction, be added dropwise after 0.5h that the reaction was continued
1.5h；Add a certain amount of dimethylbenzene after reaction to get colourless, clarification, transparent zinc acrylate resin solution is arrived.
Embodiment 3:
The synthesis of zinc acrylate resin: to four mouthfuls of burnings with thermometer, mechanical stirring, condensing reflux pipe and dropping funel
15g PGM, 57g dimethylbenzene are added in bottle, 5g EA opens mechanical stirring and is passed through nitrogen after mixing, and oil bath heating is to 100
℃；By a certain amount of uniformly mixed 10g MMA, 45g EA, 10g EA, 20g 2-MEA, 15g zinc acrylate resin monomer and 10g bis-
Toluene, 1.0g chain-transferring agent MSD, 2.5g chain initiator AIBN and 7g AMBN solution are instilled in flask with constant speed 6h；It is added dropwise
A certain amount of co initiator 0.5g BPO solution is added after the completion and carries out second of initiation reaction, is continued instead after 0.5h is added dropwise
Answer 1.5h；Add a certain amount of dimethylbenzene after reaction to get colourless, clarification, transparent zinc acrylate resin solution is arrived.
Embodiment 4:
The synthesis of zinc acrylate resin: to four mouthfuls of burnings with thermometer, mechanical stirring, condensing reflux pipe and dropping funel
15g PGM, 57g dimethylbenzene are added in bottle, 5g EA opens mechanical stirring and is passed through nitrogen after mixing, and oil bath heating is to 100
℃；By a certain amount of uniformly mixed 10g MMA, 60g EA, 10g EA, 10g 2-MEA, 10g zinc acrylate resin monomer and 10g bis-
Toluene, 1.0g chain-transferring agent MSD, 2.5g chain initiator AIBN and 7g AMBN solution are instilled in flask with constant speed 6h；It is added dropwise
A certain amount of co initiator 0.5g BPO solution is added after the completion and carries out second of initiation reaction, is continued instead after 0.5h is added dropwise
Answer 1.5h；Add a certain amount of dimethylbenzene after reaction to get colourless, clarification, transparent zinc acrylate resin solution is arrived.
Claims (3)
1. a kind of preparation method from polishing antifouling resin, it is characterized in that:
Step 1: being fitted into container after zinc oxide is mixed with solvent, be placed in reflux condensation mode in 75 DEG C of oil bath；By metering system
Acid, acrylic acid are uniformly mixed with deionized water, are instilled in the container with constant speed through 3 hours, after heat preservation 2 hours, are obtained
To the bifunctionality zinc acrylate resin monomer solution of clear；
Step 2: bifunctionality zinc acrylate resin monomer and esters of acrylic acid polymerizable unsaturated monomer and master that step 1 generates are drawn
Agent mixing is sent out, is at the uniform velocity added dropwise in the reaction kettle containing mixed solvent under 90 DEG C~105 DEG C of reflux temperature, in 6h, is dripped
Secondary initiator is added dropwise after the completion of adding again and carries out second of initiation reaction, time for adding 0.5h, is further continued for reaction 1.5h, obtains
It is colourless, clarification, it is transparent from polishing antifouling zinc acrylate resin solution；The parts by weight of each component are as follows: difunctional acrylic acid
10~44 parts of zinc monomer solution, 55~70 parts of remaining esters of acrylic acid polymerizable unsaturated monomer, 0.8~5 part of initiator and mixed
40~55 parts of bonding solvent；Remaining described esters of acrylic acid polymerizable unsaturated monomer be methyl methacrylate, methyl acrylate,
Butyl methacrylate, methoxyethyl acrylate, ethyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, third
At least one of alkene nitrile, methacrylonitrile；Main initiator accounts for the 3/4 of initiator total amount, and secondary initiator accounts for initiator total amount
1/4, the main initiator be azodiisobutyronitrile and/or azobisisovaleronitrile, the secondary initiator be benzoyl peroxide first
Acyl.
2. the preparation method according to claim 1 from polishing antifouling resin, it is characterized in that: the mixed solvent is quality
Than the propylene glycol monomethyl ether and dimethylbenzene of 1:4~7.
3. the preparation method according to claim 1 or 2 from polishing antifouling resin, it is characterized in that: the reaction temperature is
95~102 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710178467.9A CN107033273B (en) | 2017-03-23 | 2017-03-23 | One kind is from polishing antifouling resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710178467.9A CN107033273B (en) | 2017-03-23 | 2017-03-23 | One kind is from polishing antifouling resin and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107033273A CN107033273A (en) | 2017-08-11 |
| CN107033273B true CN107033273B (en) | 2019-10-11 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452596B (en) * | 2019-07-24 | 2020-07-24 | 武汉理工大学 | Organic silicon modified zinc acrylate/zinc pyrithione composite antifouling paint and preparation method and application thereof |
| CN113881069B (en) * | 2021-11-05 | 2022-11-15 | 中国海洋大学 | Preparation method and application of acrylic-based hydrogel antifouling material |
| CN114716684B (en) * | 2022-03-31 | 2023-07-18 | 吴晓金 | Self-polishing antifouling resin with degradation and hydrolysis performances and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
| CN102167774A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Method for preparing fluorine modified zinc acrylate antifouling resin |
-
2017
- 2017-03-23 CN CN201710178467.9A patent/CN107033273B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
| CN102167774A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Method for preparing fluorine modified zinc acrylate antifouling resin |
Non-Patent Citations (3)
| Title |
|---|
| Synthesis of hybrid zinc/silyl acrylate copolymers and their surface properties in the microfouling stage;Rongrong Chen等;《RSC Advances》;20161231;第6卷;13858-13866 * |
| 无铜交联型丙烯酸锌防污树脂的研究;舒礼伟等;《化学工程师》;20131231(第12期);4-5、15 * |
| 环境友好型无铜自抛光防污涂料的制备与性能研究;曹京宜等;《涂料工业》;20150331;第45卷(第3期);33-36 * |
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