CN108690447A - The preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint - Google Patents
The preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint Download PDFInfo
- Publication number
- CN108690447A CN108690447A CN201710610531.6A CN201710610531A CN108690447A CN 108690447 A CN108690447 A CN 108690447A CN 201710610531 A CN201710610531 A CN 201710610531A CN 108690447 A CN108690447 A CN 108690447A
- Authority
- CN
- China
- Prior art keywords
- zinc salt
- rosin
- modified polypropene
- rosin acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 title claims abstract description 57
- 239000002253 acid Substances 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 150000003751 zinc Chemical class 0.000 title claims abstract description 40
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 39
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 22
- 239000003973 paint Substances 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229940007718 zinc hydroxide Drugs 0.000 claims description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 4
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 230000003071 parasitic effect Effects 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical class CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000238586 Cirripedia Species 0.000 description 1
- 241000295146 Gallionellaceae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 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
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to coating preparation field, more particularly to a kind of preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint is counted, the rosin acid modified polypropene acid resin zinc salt antifouling paint is composed of the following components in parts by weight:900 ~ 1100 parts of rosin acid modified polypropene acid resin zinc salt mixes 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive.Introduce modified rosin acid structure in the present invention has the characteristics that strong adhesive force, flexibility are good, cohesive performance is excellent, quick-drying, and minimum to the pollution of marine environment compared with general coating, more environmentally friendly.Displacement property ionization reaction will occur in the seawater for coating containing zinc salt, dissociate and generate the sodium salt and zinc ion of rosin acid, have inhibition growth to ocean small parasitic biology, also have obvious cleaning protection to ship, dyke, bank base.
Description
Technical field
The present invention relates to coating preparation field, more particularly to a kind of rosin acid modified polypropene acid resin zinc salt antifouling paint
Preparation method.
Background technology
The part that hull, harbour, drilling platforms etc. are located under water line at present is aerobic by sulfur-oxidizing bacteria, iron bacteria etc.
The attachment of bacterium, the marine organisms such as anaerobic bacterias and barnacle such as sulfate reducing bacteria (SRB) is stained, a large amount of to adhere to waste not only
Increase the dead weight of ship, reduce the load-carrying of ship, while the resistance that hull will be greatly increased, the speed of a ship or plane of ship is caused to reduce and fire
The increase of oil consumption.And fall off after fouling organism death, it is also possible to be inhaled into the pipeline of equipment, cause the blocking of pipeline.
The breeding of fouling organism can also cause the damage of the corrosion protective layer of ship or off-shore structure, accelerate the corrosion of metal component,
Reduce the service life of ship and marine structure.Usually all it is to apply antifouling paint in these parts to prevent marine organisms attached
It, the marine antifouling coating of traditional tin system is larger due to being polluted to the marine eco-environment, has been forbidden to use.
Invention content
In order to make up the above deficiency, the present invention discloses a kind of system of rosin acid modified polypropene acid resin zinc salt antifouling paint
Preparation Method, rosin acid and certain fatty alcohol glycerine(Such as glycerine)Formed fat is good preservative and pest repellant, rosin acid
Metal salt(Such as sodium salt and sylvite)It is referred to as resin soap emulsifiable concentrate and strong insecticide.Based on rosin acid and its derivative
Want the rosin of ingredient little to the toxic effect of macro-organism, it, can be to various micro- lifes among it is used for marine antifouling coating
Object includes that ocean parasitic organism plays inhibiting effect, but will not cause damages to big shape animal, will not be to marine environment
Cause serious pollution.
The present invention is achieved through the following technical solutions:A kind of rosin acid modified polypropene acid resin zinc salt antifouling paint
Preparation method, count in parts by weight, the rosin acid modified polypropene acid resin zinc salt antifouling paint by following components group
At:900 ~ 1100 parts of rosin acid modified polypropene acid resin zinc salt mixes 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive.
Preferably, it is prepared by following technique preparation processes:
Step 1:Rosin acid refines
Ethanol water is added in rosin, adds the aqueous solution of sodium hydroxide, is heated to boiling, return stirring reaction 3 ~ 4
Hour, activated carbon decolorizing, filtering is added, filtrate is cooled to 0 ~ 4 DEG C, is slowly dropped into the aqueous solution of hydrochloric acid, filters again, omited
Band yellow solid, is washed with water to neutrality.
Step 2:The preparation of rosin acid modified polypropene acid resin zinc salt
Solvent is added in reaction bulb, polyacrylic resin is then added, is heated to 80 ~ 85 DEG C, stirs to dissolve uniformly, so
After cosolvent is added, continue to stir, add zinc hydroxide, be warming up to boiling, divide water using oil water separator, until distilling out
Liquid become clarifying, be cooled to 70 ~ 75 DEG C, add refined rosin acid, be warming up to boiling, use oil water separator point
Water, until the liquid distilled out becomes clarifying, it is 80 hereinafter, being then cooled to 60 DEG C hereinafter, be washed with distilled water to measure acid value,
Filtering, is finally evaporated off solvent to get rosin acid modified polypropene acid resin zinc salt.
Step 3:The preparation of rosin acid modified polypropene acid resin zinc salt antifouling paint
By 900 ~ 1100 parts of the rosin acid modified alkyd resin zinc salt, 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive are mixed,
Dispersion is sanded to granularity as 40 μm hereinafter, to obtain the final product.
Preferably, in step 1:The volume fraction of the ethanol water is 75% ~ 90%, the hydroxide
The concentration of sodium water solution and aqueous hydrochloric acid solution is 1 ~ 3mol/L, and the molar ratio of the rosin, sodium hydroxide and hydrochloric acid is 10:1:
1.2, the mass ratio of rosin, ethyl alcohol and activated carbon is 100:150~170:1~3.
Preferably, in step 2:The solvent is in toluene, dimethylbenzene, 200# solvent naphthas or butyl acetate
One kind, the cosolvent be polyethylene glycol 400, Macrogol 600, polyethylene glycol-800 or cetomacrogol 1000 in one kind
Or a variety of mixing, polyacrylic resin, cosolvent, zinc hydroxide and refined rosin acid weight ratio be 25:45~55:5~7:8
~12。
The beneficial effects of the invention are as follows:Modified rosin acid structure is introduced in the present invention, compared with general coating, is had attached
Put forth effort the features such as strong, flexibility is good, cohesive performance is excellent, quick-drying, and minimum to the pollution of marine environment, it is more environmentally friendly.Containing zinc
Displacement property ionization reaction will occur in the seawater for salt coating, dissociate and generate the sodium salt and zinc ion of rosin acid, small to ocean
Parasite has inhibition growth, also has obvious cleaning protection to ship, dyke, bank base.
Description of the drawings
Fig. 1 is the hanging test of the embodiment of the present invention 1.
Specific implementation mode
Below by embodiment, the present invention will be further described, but the scope of the invention is not limited.
Embodiment 1:
Rosin acid refines:The ethyl alcohol 800ml that volume fraction is 75% is added in 300g rosin, adds the 2mol/L of 50ml
Sodium hydrate aqueous solution is heated to boiling, and return stirring reacts 3.5 hours, and 6g activated carbon decolorizings, filtering, filtrate cooling is added
To 0 ~ 4 DEG C, 60ml 2mol/L aqueous hydrochloric acid solutions are slowly dropped into, are filtered again, yellowish solid is obtained, are washed with water to neutrality.
The preparation method of rosin acid modified polypropene acid resin zinc salt is as follows:
A, the preparation of polyacrylic resin:By 60g ethyl acrylates, 600g methyl methacrylates, 60g methacrylic acid fourths
Monomer mixed solution is made in ester, 120g styrene, the premixing of 360g acrylic acid, by 18g peroxidized t-butyl perbenzoates and 100g bis-
Toluene is configured to initiator solution I, is added in the five mouthfuls of flasks of 3000ml for being equipped with mechanical agitator, condenser, thermometer
400ml dimethylbenzene after being heated to 115~125 DEG C, while being added dropwise monomer mixed solution and initiator solution I, added in 3h, so
After keep the temperature 1h, then the initiator solution II that 4g peroxidized t-butyl perbenzoates and 40g dimethylbenzene are configured to is added dropwise, 30min is added dropwise
It finishes, keeps the temperature 1h, then the initiator solution III that 2g peroxidized t-butyl perbenzoates are configured to 40g dimethylbenzene is added dropwise, then keep the temperature
After reacting 1.5h, the mixed liquor that 1.0g tert-dodecyl mercaptans are prepared with 220g butanol is added, is finally obtained by filtration after 60 DEG C of cooling
Polyacrylic resin.
B, the preparation of rosin acid modified polypropene acid resin zinc salt:It is being equipped with mechanical agitator, condenser, thermometer
200ml toluene is added in five mouthfuls of flasks of 3000ml, 150g polyacrylic resins are then added, is heated with stirring to 80 DEG C, keeps its molten
Solution is uniform, and the polyethylene glycol 400 of 300g is then added, continues to stir, adds 36g zinc hydroxides, be warming up to boiling, use oil
Separator divides water, until distillating liquid becomes clarifying, cools to 70 DEG C, adds the refined rosin acids of 60g, is heated to boiling
It rises, divides water using oil water separator, until distillating liquid becomes clarifying, it is 80 hereinafter, being cooled to 60 DEG C to measure acid value, filtering,
Up to rosin acid modified polypropene acid resin zinc salt.
3)The preparation of sea environment-friendly anti-fouling type rosin acid modified polypropene acid resin zinc salt coating:To equipped with high speed dispersor
Coating material production tank in 1000g rosin acid modified polypropene acid resin zinc salts are added, add 45g mixing rust resisting pigment and 2g coating
Auxiliary agent, high speed dispersion survey fineness at 40 μm hereinafter, to obtain the final product.
Performance test:
Adhesive force(Grade):It is evaluated as 1 by GB/T1720-1989 standards;
Flexibility(mm):It is evaluated as 1 by GB/T1731-1993 standards;
Viscosity(Pa.s):It is evaluated as 35 ~ 50 by GB/T1723-1993 standards;
Impact strength(kg.cm):It is evaluated as 45 ± 5 by GB/T1732-1993 standards;
Artificial ageing resistance(600h):It is evaluated by GB/T1865-2009 standards, no blistering, peeling, crackle;
Salt spray test(1000h):By GB/T1771-2007 standards evaluate, it is no blistering, without cracking, without rust staining;
Hardening time (25C, relative humidity 70%):Biao Gan≤0.5h;The h of Shi Gan≤4;
Hanging test situation
It is hung through counterglow marine terminal using the environmentally friendly antifouling paint that rosin acid modified polypropene acid resin zinc salt is produced as base-material
Piece is tested 5 times, every 2 square metres of application, is stored 3 years, has no that microorganism adheres to, and is closed on maritime waters biology and is had no that growth is different
Often.
Embodiment 2:
1) rosin acid is refined:The ethyl alcohol 715ml that volume fraction is 85% is added in 300g rosin, adds 100ml's
1mol/L sodium hydrate aqueous solutions are heated to boiling, and return stirring reacts 3.5 hours, and 3g activated carbon decolorizings are added, and filter, filter
Liquid is cooled to 0 ~ 4 DEG C, is slowly dropped into 120ml 1mol/L aqueous hydrochloric acid solutions, filters again, obtains yellowish solid, be washed with water
To neutrality.
2) preparation method of rosin acid modified polypropene acid resin zinc salt is as follows:
A, the preparation of polyacrylic resin:By 60g ethyl acrylates, 600g methyl methacrylates, 60g methacrylic acid fourths
Monomer mixed solution is made in ester, 120g styrene, the premixing of 360g acrylic acid, by 18g peroxidized t-butyl perbenzoates and 100g bis-
Toluene is configured to initiator solution I, is added in the five mouthfuls of flasks of 3000ml for being equipped with mechanical agitator, condenser, thermometer
400ml dimethylbenzene after being heated to 115~125 DEG C, while being added dropwise monomer mixed solution and initiator solution I, added in 3h, so
After keep the temperature 1h, then the initiator solution II that 4g peroxidized t-butyl perbenzoates and 40g dimethylbenzene are configured to is added dropwise, 30min is added dropwise
It finishes, keeps the temperature 1h, then the initiator solution III that 2g peroxidized t-butyl perbenzoates are configured to 40g dimethylbenzene is added dropwise, then keep the temperature
After reacting 1.5h, the mixed liquor that 1.0g tert-dodecyl mercaptans are prepared with 220g butanol is added, is finally obtained by filtration after 60 DEG C of cooling
Polyacrylic resin.
B, the preparation of rosin acid modified polypropene acid resin zinc salt:It is being equipped with mechanical agitator, condenser, thermometer
200ml dimethylbenzene is added in five mouthfuls of flasks of 3000ml, 150g polyacrylic resins are then added, is heated with stirring to 85 DEG C, makes it
It is uniformly dissolved, the Macrogol 600 of 300g is then added, continues to stir, adds 36g zinc hydroxides, be warming up to boiling, use
Oil water separator divides water, until distillating liquid becomes clarifying, cools to 75 DEG C, adds the refined rosin acids of 60g, is heated to boiling
It rises, divides water using oil water separator, until distillating liquid becomes clarifying, it is 80 hereinafter, being cooled to 60 DEG C to measure acid value, filtering,
Up to rosin acid modified polypropene acid resin zinc salt.
3)The preparation of sea environment-friendly anti-fouling type rosin acid modified polypropene acid resin zinc salt coating:
900g rosin acid modified polypropene acid resin zinc salts are being added into sand mill, is adding 40g mixing rust resisting pigment and 1g is applied
Expect auxiliary agent, be sanded, survey fineness at 40 μm hereinafter, to obtain the final product.
Embodiment 3:
Rosin acid refines:The ethyl alcohol 676ml that volume fraction is 90% is added in 300g rosin, adds the 3mol/L of 33ml
Sodium hydrate aqueous solution is heated to boiling, and return stirring reacts 3.5 hours, and 9g activated carbon decolorizings, filtering, filtrate cooling is added
To 0 ~ 4 DEG C, 40ml 3mol/L aqueous hydrochloric acid solutions are slowly dropped into, are filtered again, yellowish solid is obtained, is washed with water into
Property.
2) preparation method of rosin acid modified polypropene acid resin zinc salt is as follows:
A, the preparation of polyacrylic resin:By 60g ethyl acrylates, 600g methyl methacrylates, 60g methacrylic acid fourths
Monomer mixed solution is made in ester, 120g styrene, the premixing of 360g acrylic acid, by 18g peroxidized t-butyl perbenzoates and 100g bis-
Toluene is configured to initiator solution I, is added in the five mouthfuls of flasks of 3000ml for being equipped with mechanical agitator, condenser, thermometer
400ml dimethylbenzene after being heated to 115~125 DEG C, while being added dropwise monomer mixed solution and initiator solution I, added in 3h, so
After keep the temperature 1h, then the initiator solution II that 4g peroxidized t-butyl perbenzoates and 40g dimethylbenzene are configured to is added dropwise, 30min is added dropwise
It finishes, keeps the temperature 1h, then the initiator solution III that 2g peroxidized t-butyl perbenzoates are configured to 40g dimethylbenzene is added dropwise, then keep the temperature
After reacting 1.5h, the mixed liquor that 1.0g tert-dodecyl mercaptans are prepared with 220g butanol is added, is finally obtained by filtration after 60 DEG C of cooling
Polyacrylic resin.
B, the preparation of rosin acid modified polypropene acid resin zinc salt:It is being equipped with mechanical agitator, condenser, thermometer
The 200# solvent naphthas of 200ml are added in five mouthfuls of flasks of 3000ml, 150g polyacrylic resins are then added, are heated with stirring to 80
DEG C, it makes it dissolve uniformly, the cetomacrogol 1000 of 300g is then added, continues to stir, adds 36g zinc hydroxides, be warming up to
Boiling, divides water using oil water separator, slowly separates liquid, until distillating liquid becomes clarifying, cools to 70 DEG C, adds
Rosin acid refined 60g, is heated to boiling, separates liquid, and until distillating liquid is clarified, measurement acid value is 80 hereinafter, being cooled to
It 60 DEG C, filters to get rosin acid modified polypropene acid resin zinc salt.
3)The preparation of sea environment-friendly anti-fouling type rosin acid modified polypropene acid resin zinc salt coating:
1100g rosin acid modified polypropene acid resin zinc salts are added into the coating material production tank equipped with high speed dispersor, add 50g
Mix rust resisting pigment and 3g coating additives, high speed dispersion surveys fineness at 40 μm hereinafter, to obtain the final product.
In addition to technical characteristic described in specification, remaining technical characteristic is technology known to those skilled in the art.
Claims (4)
1. a kind of preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint, which is characterized in that in parts by weight
Meter, the rosin acid modified polypropene acid resin zinc salt antifouling paint it is composed of the following components:Rosin acid modified polyacrylic acid
900 ~ 1100 parts of resin zinc salt mixes 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive.
2. the preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint according to claim 1, feature
It is, is prepared by following processing steps:
Step 1:Rosin acid refines
Ethanol water is added in rosin, adds the aqueous solution of sodium hydroxide, is heated to boiling, return stirring reaction 3 ~ 4
Hour, activated carbon decolorizing, filtering is added, filtrate is cooled to 0 ~ 4 DEG C, is slowly dropped into the aqueous solution of hydrochloric acid, filters again, omited
Band yellow solid, be washed with water to neutrality to get.
Step 2:The preparation of rosin acid modified polypropene acid resin zinc salt
Solvent is added in reaction bulb, polyacrylic resin is then added, is heated to 80 ~ 85 DEG C, stirs to dissolve uniformly, so
After cosolvent is added, continue to stir, add zinc hydroxide, be warming up to boiling, divide water using oil water separator, until distilling out
Liquid become clarifying, be cooled to 70 ~ 75 DEG C, add refined rosin acid, be warming up to boiling, use oil water separator point
Water, until the liquid distilled out becomes clarifying, it is 80 hereinafter, being then cooled to 60 DEG C hereinafter, be washed with distilled water to measure acid value,
Filtering, is finally evaporated off solvent to get rosin acid modified polypropene acid resin zinc salt.
Step 3:The preparation of rosin acid modified polypropene acid resin zinc salt antifouling paint
By 900 ~ 1100 parts of the rosin acid modified polypropene acid resin zinc salt, mixing 40 ~ 50 parts of rust resisting pigment, coating additive 1 ~
3 parts, disperse or be sanded to granularity as 40 μm hereinafter, to obtain the final product.
3. the preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint according to claim 2, feature
It is, in step 1:The volume fraction of the ethanol water is 75% ~ 90%, the sodium hydrate aqueous solution and hydrochloric acid water
The molar ratio of a concentration of 1 ~ 3mol/L of solution, the rosin, sodium hydroxide and hydrochloric acid are 10:1:1.2, the rosin, ethyl alcohol
Mass ratio with activated carbon is 100:150~170:1~3.
4. the preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint according to claim 2, feature
It is, in step 2:The solvent is one kind in toluene, dimethylbenzene, 200# solvent naphthas or butyl acetate, the cosolvent
For one or more mixing in polyethylene glycol 400, Macrogol 600, polyethylene glycol-800 or cetomacrogol 1000, polypropylene
Acid resin, cosolvent, zinc hydroxide and refined rosin acid weight ratio be 25:45~55:5~7:8~12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710610531.6A CN108690447A (en) | 2017-07-25 | 2017-07-25 | The preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710610531.6A CN108690447A (en) | 2017-07-25 | 2017-07-25 | The preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108690447A true CN108690447A (en) | 2018-10-23 |
Family
ID=63843730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710610531.6A Pending CN108690447A (en) | 2017-07-25 | 2017-07-25 | The preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690447A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110206632A1 (en) * | 2010-02-19 | 2011-08-25 | Kappock Paul S | Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound |
| CN105001358A (en) * | 2014-04-24 | 2015-10-28 | 浙江省海洋开发研究院 | Synthetic method of copper/zinc acrylate antifouling resin |
-
2017
- 2017-07-25 CN CN201710610531.6A patent/CN108690447A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110206632A1 (en) * | 2010-02-19 | 2011-08-25 | Kappock Paul S | Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound |
| CN105001358A (en) * | 2014-04-24 | 2015-10-28 | 浙江省海洋开发研究院 | Synthetic method of copper/zinc acrylate antifouling resin |
Non-Patent Citations (1)
| Title |
|---|
| 赵世民: "松香的精制和提纯", 《广西化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2009327936B2 (en) | Antifouling coating composition, antifouling coating film formed using the composition, coated object having the coating film on the surface, and method of antifouling treatment by formation of the coating film | |
| EP2975095B1 (en) | Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface | |
| AU646754B2 (en) | Antifouling coatings | |
| AU2009327937B2 (en) | Antifouling coating composition, antifouling coating film formed using the composition, coated object having the coating film on the surface, and method of antifouling treatment by formation of the coating film | |
| CN103897092B (en) | The preparation of acrylic acid zinc-type self polishing copolymer antifouling paint matrix resin and application | |
| KR101963670B1 (en) | Antifouling coating composition | |
| CN103289007B (en) | A kind of zinc acrylate resin/resin of copper preparation method of improvement | |
| CA2555054C (en) | Antifouling compositions comprising a polymer with salt groups | |
| AU2003250076B2 (en) | Acid-capped quaternised polymer and compositions comprising such polymer | |
| WO2005005516A9 (en) | Silyl ester copolymer compositions | |
| CN102807797B (en) | Efficient marine antifouling coating and broad-spectrum controlled-release antifouling agent for same | |
| CA2555057C (en) | Antifouling coating composition and its use on man made structures | |
| SG185477A1 (en) | Antifouling paint composition, antifouling coating film, and method for controlling hydrolysis rate of antifouling coating film | |
| DE60009449T2 (en) | NON-APPLICANT COMPOSITION | |
| CN105837733B (en) | [(12 acryloyl-oxy) dehydroabietic acid capsiate] acrylic copolymer and its preparation and application | |
| CN101121855A (en) | Tin-free self-polishing antifouling paint | |
| CN111253821B (en) | High-solid-content copper-free linear self-polishing marine antifouling paint | |
| CN108690447A (en) | The preparation method of rosin acid modified polypropene acid resin zinc salt antifouling paint | |
| CN118165594A (en) | Ship antifouling paint containing biological repellent and preparation method thereof | |
| CN108690473A (en) | The preparation method of rosin acid modified alkyd resin zinc salt antifouling paint | |
| JP6472934B2 (en) | Laminated antifouling coating, antifouling substrate and ship | |
| JP3824925B2 (en) | Antifouling paint composition, coating film comprising the composition, ship or underwater structure coated with the coating film, and antifouling method | |
| CN102125038B (en) | Anti-fouling agent containing paeonolum and nicotine structure and preparation method thereof | |
| CN110713604A (en) | A kind of preparation method of PAMAM composite antifouling material | |
| KR102704292B1 (en) | Antifouling coating composition and coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181023 |
|
| RJ01 | Rejection of invention patent application after publication |