CN102432802B - Resin for biodegradable anti-fouling paint, synthetic method of the same, and anti-fouling paint composition containing the same - Google Patents
Resin for biodegradable anti-fouling paint, synthetic method of the same, and anti-fouling paint composition containing the same Download PDFInfo
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Abstract
The invention provides a resin for a biodegradable anti-fouling paint. The resin for the biodegradable anti-fouling paint is a polymer containing a multi-block structure, characterized in that: the resin is prepared by polymerizing by polylactic acid oligomer, flexible segments, polyisocyanates under the effect of catalysts, wherein, the polylactic acid oligomer is prepared by carrying out reflux reaction on lactic acid having a monomer content of 80-85 % and aromatic solvents under negative pressure or normal pressure until no water generates; the flexible segments comprises polyols or/and polyester polyols; and the amount of the flexible segments accounts for 5-30 % of the weight percentage of the lactic acid raw material; and the amount of polyisocyanates accounts for 10-30 % of the weight percentage of the lactic acid raw material. The invention further provides a biodegradable anti-fouling paint composition containing the resin as a matrix resin. The anti-fouling paint contains composite organic antifouling agent and contains no or little cuprous oxide, and has the advantages of low toxicity, environmental protection, and good anti-fouling effect.
Description
Technical field
The present invention relates to a kind of biodegradation type antifouling paint resin and synthetic method thereof, containing biodegradation type antifouling paint compositions and the preparation method of this resin, belong to technical field of polymer materials.
Background technology
Along with " the international system pact of harmful antifouling end of boats and ships of controlling " (AFS pact) and the implementation of " about the Convention of Stockholm of persistence organic pollutant " (POPs pact), antifouling paint containing organotin, DDT is withdrawn from the market comprehensively, the production forward heavy metal free of antifouling paint, Wuxi, low copper, without the future development of sterilant.Research and develop ecological friendly antifouling paint imperative.Be a developing direction from polishing type antifouling paint, but still have some problems:
(1) the marine antifouling effect leading for Gao Hang from polishing type antifouling paint of main flow is better at present, and the speed of a ship or plane is higher, and more obvious from polishing action, anti-fouling effect is better.But in static seawater, antifouling coating upgrades weak effect, and to low speed, low at especially warship of boat rate boats and ships, and the antifouling usefulness of Offshore Units is relatively poor.Research and development, for the antifouling paint matching system of low speed, the low boats and ships in boat rate and Offshore Units and offshore structure, have market outlook widely targetedly.
(2), on market, the antifouling paint of main flow is Tin-free Spc Anti-fouling Paint.Its matrix resin is mainly divided into three major types: zinc acrylate resin, acrylate resin and vinylformic acid silica alkane resin, substantially antifouling toxic agent is Red copper oxide.Antifouling paint relies on the object that reaches antifouling of oozing out of Red copper oxide, little compared with the harm of organic tin antifouling paint, although meet current environmental requirement, but still there is potential environmental hazard from polishing type antifouling paint in traditional acrylic acid or the like, in the composition of Tin-free Spc Anti-fouling Paint, especially very harmful to ocean environment with Red copper oxide in its color stuffing.
The existing recent two decades time of biodegradated polymer materal large-scale development application, still, due to the problem of the aspects such as its performance, price, its Application Areas is difficult to expand always.Biodegradated polymer materal is mainly used in medical material and non-returnable container material at present.The rare report of application in antifouling paint.
Japanese Unexamined Patent Publication No is 5-186556, react with the organic solvent that contains at least one plant component of selecting from starch or treated starch, honey, polyose agricultural waste and the modified vegetable oil that contains hydroxyl by polyisocyanates, produce the material of biodegradable polyurethane.Separately having document Japanese Unexamined Patent Publication No is that 6-65349 and Chinese Patent Application No. CN200810185131.6 have reported that use polyisocyanates makes starch be combined with hydroxy acryl acid resin.
Application number is that the patent about starch-based coating composition of CN200710143428.1 is ethene polymers to be bonded to the modified resin obtaining on starch or treated starch to react with isocyanic ester based products and obtain degradable resin and prepare starch-based coating through graft polymerization.
Application number is the biodegradable resin combination of CN200480041278.8, comprises at least one biodegradable organic polymer, the flame-retardant additive that contains phosphorus compound and can suppress the hydrolysis inhibitor that this at least one organic polymer is hydrolyzed.As aliphatic polyester resin, at least one the multipolymer that uses the synthetic polyester of poly(lactic acid), polycaprolactone, polyhydroxybutyrate, poly-hydroxypentanoic acid, polydiethylene glycol succinate, polybutylene succinate, poly adipate succinic acid ester, polymalic acid, microorganism or contain them.As polysaccharide, use Mierocrystalline cellulose, starch, chitin, chitosan, dextran, their any one derivative, or at least one the multipolymer that contains them.
Above patent documentation is mainly used for Traditional Packing Material Field by biodegradated polymer materal.
Document Development of poly (e-caprolaetone-co-L-lactide) and poly (e-caprolaetone-co-d-valerolactone) the as new degradable binder used for antifouling paint[J of the report such as Fay F] .European Polymer Journal, 2007, 43 (11): 4800-4813. employing 6-caprolactone and rac-Lactide or 6-caprolactone and 6-valerolactone are in varing proportions at 240 ℃ of high temperature, under anhydrous and oxygen-free vacuum condition, catalyze and synthesize copolyether, this copolyether has suitable solvability in the conventional aromatic solvent of antifouling paint, and can there is suitable hydrolysis/biological degradability in ocean environment, the coating that is base-material based on these novel degradable resins confirms to have certain anti-fouling effect in the Atlantic Ocean through experiment.In addition, Fay.F has also reported document Biodegradable poly (esteranhydride) for new antifouling coating[J] .Biomacromolecules, 2007,8 (5): 1751-1758. synthesized a class have biological controlled degradation, with coating weighting material consistency and certain persistent block polymer, application show effectively to stop adhering to and growing of fouling organism.But coating degrades completely after the sea water immersion of 10 weeks, need further to improve its weather resistance.According to people such as Fay.F, the reaction conditions that their synthetic resins adopts, is under nitrogen protection, reaches anhydrous and oxygen-free, 240 ℃ of temperature of reaction, and vacuumize reaction conditions.Its reaction conditions requires more harsh.
Jian Yu has reported document Biodegradation-based Polymer Surface Erosion and Surface Renewal for Foul-release at Low Ship Speeds, Biofouling:The Journal of Bioadhesion and Biofilm Research, 2003,19:83-90.The research about the laboratory degradation property of polyhydroxyalkanoate family macromolecule material.
Domestic 725 Xiamen branches of institute have reported " study on the synthesis of antifouling paint degradable polyurethane resin binder ", " developing material and application ", 2009,24 (6) 19-23.They have synthesized the different degradable polyurethane resin of a series of compositions; the antifouling paint of preparing as resin binder has preliminary anti-fouling effect; according to theirs; the raw material rac-Lactide, the hydroxy-terminated polybutadienes price that adopt are very high, and reaction conditions needs reaction at 160-170 ℃ of anhydrous and oxygen-free nitrogen protection.It is less that the dissolution with solvents performance of the resin of gained and other coating are prepared relevant performance data, and only reported the link plate data of 25 days.
At present, biodegradation type antifouling paint also exists: biodegradation type coating uses macromolecular material without commercially produced product in enormous quantities, the cost of material of preparing macromolecular material is higher, most of synthetic biodegradation type resins solvability in the common solvent of antifouling paint is bad, the bad control of biodegradation rate, many-sided problem of solving of needing that bad and antifouling phase of sea water resistance improving soaking effect is shorter etc.
Summary of the invention
The object of this invention is to provide a kind of biodegradation type resin, preparation method for antifouling paint, and containing the antifouling paint compositions of this resin.
The object of the invention is to realize with following technical proposal:
Biodegradation type resin of the present invention is a kind of polymkeric substance that comprises many block structures, is polymerized under esterifying catalyst effect by polylactic acid low polymer, soft segment, polyisocyanates.
Described polylactic acid low polymer, by lactic acid (monomer content 80-85%) and aromatic solvents, back flow reaction under negative pressure or normal pressure, water trap dewaters to anhydrous generation, obtains polylactic acid low polymer.
Described aromatic solvents is as azeotropy dehydrant and solvent, with the moisture in the system of removing.The consumption of described aromatic solvents is pressed the 30-60% massfraction of lactic raw material massfraction.
Described aromatic solvents, is selected from toluene, and dimethylbenzene is chosen one or more.
Described soft segment refers to polyvalent alcohol or/and polyester polyol, and consumption is advisable by the 5-30% of lactic raw material massfraction.
Described polyvalent alcohol is selected from: ethylene glycol, and propylene glycol, butyleneglycol, pentanediol, glycerol, tetramethylolmethane, polyoxyethylene glycol PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-2000 etc., choose one or more.
Described polyester polyol refers to polycaprolactone polyol.
Described polyisocyanates is selected from tolylene diisocyanate, '-diphenylmethane diisocyanate, 1, oneself two different acid esters of 6-, isoflurane chalcone diisocyanate, 4,4-dicyclohexyl methane diisocyanate, to tetramethyl for α-tolylene vulcabond, vulcabond diformazan phenyl ester, trimethyl hexamethylene diisocyanate, choose wherein one or more.The consumption of polyisocyanates is pressed the 10-30% of lactic raw material massfraction.
The preparation method of described multi-block polymer is:
In above-mentioned polylactic acid low polymer, add soft segment, add esterifying catalyst, under negative pressure or normal pressure, in 130-150 ℃ of back flow reaction, water trap dewaters to anhydrous generation, obtains polylactic acid based many blocks prepolymer.
After cooling polylactic acid based many blocks prepolymer, add mixed solvent, polyisocyanates and catalyzer dibutyl tin laurate, at 50-90 ℃ of heated and stirred stoichiometric number hour, obtain final product multi-block polymer.
Described esterifying catalyst is mainly but is not limited only to organo-metallic catalyst, be selected from SnCl4, TiCl4, SbF3, SnCl2-2H2O, SnCl4-H20, tosic acid (TSA), tetrabutyl titanate, dibutyl tin laurate, stannous octoate, choose one or several combination.The add-on of catalyzer is pressed the 0.1-0.2% of lactic raw material massfraction.
Described mixed solvent, is selected from aromatic solvents, esters solvent, and alcoholic solvent, ketones solvent, chooses above-mentioned one or several solvents.Mixed solvent consumption is pressed the 20-60% of lactic raw material massfraction, in order to adjust viscosity and the solid content of resin, improves solvability and the stable homogeneous of resin system.
Described aromatic solvents, is selected from toluene, dimethylbenzene.
Described esters solvent, is selected from butylacetate, ethyl acetate, 1-Methoxy-2-propyl acetate.
Described alcoholic solvent, is selected from butanols, propyl alcohol, propylene glycol monomethyl ether.
Described ketones solvent, is selected from pimelinketone, toluene pimelinketone, acetone, espeleton, mibk.
The biodegradation type resin that the present invention is prepared, its many block structures, take the polylactic acid low polymer that synthesizes as chief component segment.The molecular weight control of polylactic acid low polymer is extremely important.The too high dissolution with solvents performance of segmented copolymer that causes of molecular weight is poor, poor stability; The too low antifouling paint paint film property defect causing take prepared resin as base-material of molecular weight, as too soft in paint film, sea water resistance is poor etc.So the molecular weight ranges of polylactic acid low polymer of the present invention is better at 500-3500, more preferably 800-2500.
Popular response flow process: lactic acid (content 85%), aromatic solvent, under negative pressure or normal pressure, back flow reaction, to anhydrous generation, obtains faint yellow polylactic acid low polymer.In system, add soft segment, as one or several the arbitrary proportion combination of butyleneglycol, PEG-200, PEG-400 etc., add esterifying catalyst, the stoichiometric number that refluxes under the same terms is hour to anhydrous generation, obtain light brown resin, be polylactic acid based many blocks prepolymer.After cooling, add mixed solvent, polyisocyanates and catalyzer dibutyl tin laurate, 50-90 ℃ of heated and stirred stoichiometric number hour, obtains final product.
The present invention is to provide a kind of low copper or the antifouling paint compositions without copper, take the aforementioned biodegradation type resin obtaining as matrix resin, compound low toxicity stain control agent, color stuffing, auxiliary agent composition.Formula following (w/%)
In formula of the present invention, owing to selecting the organic stain control agent of composite high-efficiency low-toxicity, can make the copper class stain control agent consumptions such as Red copper oxide greatly reduce, or completely without copper.
In formulation for coating material of the present invention, selectivity adds the Red copper oxide of lower aq as auxiliary collaborative stain control agent.
In formulation for coating material of the present invention, selectivity adds rosin, is used for regulating stain control agent rate of release and paint film property.And because rosin price comparison is low, therefore can reduce the consumption of the biodegradable resin of synthesized.
The present invention selects compound organic stain control agent system of wide spectrum, efficient, low toxicity.For example pyrithione class (as CuPT), isothiazolinone (as S-211), pyridine phenyl boron class (as PTPB), triazines (as Irgarol1051).Concrete: cuprous thiocyanate (CuSCN); Tetramethyl thiuram disulfide commodity are called Thiram, and good fortune is two beautiful; Ethylenebis (curing carboxylamine) zinc, trade(brand)name zineb; 4,5-dichloro--Kathon, trade(brand)name Sea-Nine211; Copper pyrithione, commodity are called Copper Omadine; Pyrithionc Zinc, ZPT, another name: Pyrithionc Zinc; N-cyclopropyl-N '-(1,1-dimethyl ethyl)-6-(methyl sulfo-)-1,3,5-triazines-2,4-diamines, trade(brand)name Irgarol 1051; 2,4,5,6-daconil M, trade(brand)name m-tetrachlorophthalodinitrile; N, N-dimethyl-N '-dichloro fluorine methylthio group-N '-phenyl sulphamide, trade(brand)name Preventol A4-S, Pecudin; N, N-dimethyl-N '-(4-tolyl)-N '-(dichloro fluorine methylthio group) sulphonamide, commodity are called Preventol A5-S, tolylfluanid; N '-(3,4-dichlorophenyl)-N, the commodity Preventol A6 by name of N-dimethyl urea, Diuron; Pyridine triphenylborane; N-(2,4,6-trichlorophenyl) maleimide; 8-methyl-N-[(4-hydroxy 3-methoxybenzene base)-methyl]-(instead)-6-alkenyl amide in the ninth of the ten Heavenly Stems, chemical name: synthetic capsaicin, Vanillyl pelargonic amide; Polyhexamethylene guanidine phosphoric acid salt, SKYBIO1100; Hydrochloric acid dexmedetomidine; 2-(Extraction kinetics sulfydryl)-1,3 benzothiazole; The bromo-2-of 4-(4-chloro-phenyl-)-5-Trifluoromethyl-1 H-pyrroles-3-formonitrile HCN.Select one or more.
Described pigment refers to zinc oxide ZnO, ferric oxide Fe2O3, and titanium white TiO2, and other common inorganic, pigment dyestuffs, select one or more.
Described filler refers to talcum powder, and barium sulfate etc. are chosen one or more.
The present invention adds various usual auxiliaries to improve the over-all properties of antifouling paint and paint film, such as stablizer, anti-settling agent, softening agent etc.Described auxiliary agent refers to wilkinite, and organic anti-settling agent, as A630 etc.
Described mixed solvent, is selected from aromatic solvents, esters solvent, and alcoholic solvent, ketones solvent, including but not limited to the mixture of one or several solvents in the above solvent.
Described aromatic solvents, is selected from toluene, dimethylbenzene.
Described esters solvent, is selected from butylacetate, ethyl acetate, 1-Methoxy-2-propyl acetate.
Described alcoholic solvent, is selected from butanols, propyl alcohol, propylene glycol monomethyl ether.
Described ketones solvent, is selected from pimelinketone, toluene pimelinketone, acetone, espeleton, mibk.
Described antifouling paint compositions is take biodegradation type resin as matrix resin.Hull-bottom antifouling coating biological degradation by paint film top layer in seawater discharges stain control agent, and then the biology that adheres to of coatingsurface and the coating of degrading seawater wash away under abrasion together with depart from, form smooth hull bottom surface by continuous biological degradation/erosion process, thereby reach the anti-fouling effect that prevents that top layer passivation and marine life from adhering to.
Beneficial effect of the present invention: use in synthesizing of resin at biodegradation type antifouling paint; according to people institutes such as " study on the synthesis of degradable polyurethane resin binder for antifouling paint " and Fay.F; the resin building-up reactions system that they adopt needs anhydrous and oxygen-free; nitrogen protection; and vacuum suction etc., reaction conditions requires high.Production technique synthesis reaction temperature of the present invention lower (being generally 130-150 ℃); catalyst levels is low; in production process without nitrogen protection; only need negative pressure or atmospheric pressure reflux; and by product only has water to generate; generate without high poison, hazardness waste, production process is environmental protection.Can accomplish that one kettle way is synthetic, intermediate prepolymer does not need purifying, reacts controlled, favorable reproducibility.
Initial feed of the present invention is that content is the lactic acid monomer of 80-85%, and the price of the rac-Lactide adopting in " study on the synthesis of degradable polyurethane resin binder for antifouling paint " is compared to prior art lower.And valerolactone, rac-Lactide cost of material that the people such as Fay adopt are also higher.Concrete, (HTPB) is expensive for valerolactone, rac-Lactide and hydroxy-terminated polybutadienes, all exceed 100 yuan/kilogram, main raw material of the present invention is all common commercially available industrial goods containing lactic acid, polyvalent alcohol, polyisocyanates and the dimethylbenzene etc. of 85% monomer, low price, similar to common common acrylic coating resin raw material price.
The route that the present invention adopts be first by lactic acid auto-polymerization prepare polylactic acid low polymer again with soft segment catalyzed polymerization, the rac-Lactide catalysis open loop adopting from aforementioned paper is also completely different, feasible more economically with the operational path of hydroxy-terminated polybutadienes (HTPB) polymerization.
The prepared this biodegradation type resin containing many block structures of the present invention in antifouling paint common solvent (as aromatic solvents such as dimethylbenzene, the esters solvents such as N-BUTYL ACETATE, alcoholic solvent) middle favorable solubility, can reach the solids content of 60% left and right, and modest viscosity, good fluidity.Prepared film can reach the progressively effect of degraded in seawater, and can keep certain mechanical property.The antifouling paint sample of preparing take described biodegradation type resin as base-material, has wherein had the sea water resistance that exceedes 8 months and comprise a marine life growth busy season to soak and antifouling property data (seeing embodiment accompanying drawing 1).
The biodegradation type antifouling paint of preparing take this biodegradation type resin as matrix resin in the present invention, containing international and domestic forbidding toxic agent such as organotin, high toxicity agricultural chemicals.Be single-component coating, can reach density 1.3g/cm3 left and right, solids content meets or exceeds 60%, easy to use.After tested, surface drying time≤2 hour of brushing on the epoxy primer Ep-501 producing at Inst. of Marine Chemical Engineering or Ep-507 intermediate coat, do solid work time≤24 hour.On epoxy primer Ep-501 or intermediate coat Ep-507, apply, coating thickness 30-50um, cross-hatching test adhesion results is 0 grade.On epoxy primer Ep-501 or intermediate coat Ep-507, apply, resistance to freshwater soaking, 48 hours are non-foaming, do not ftracture.Think at present can be directly and priming paint supporting, omit intermediate coat, save engineering time and difficulty.At spraying 2 road epoxy primer Ep-501, on the model of total film thickness 100-150 μ m, directly brush twice biodegradation type antifouling paint of the present invention, thickness approximately 200 μ m, the existing sea water immersion data (seeing embodiment accompanying drawing 2) that exceed 5 months and comprise a marine life growth busy season, paint film is non-foaming not to ftracture, and adheres to without marine life, and anti-fouling effect is good.
Biodegradation type antifouling paint of the present invention, have in low flow velocity seawater from polishing performance, there is good anti-fouling effect.Tentatively solved traditional self polishing copolymer antifouling paint to low in boat rate or in harbour the not high problem of the antifouling usefulness of long-time sitting duck oceangoing ship.Oxygen-freeization of biodegradation type antifouling paint of the present invention is cuprous, or containing a small amount of Red copper oxide, has solved existing main flow self polishing copolymer antifouling paint and used in a large number the metal species stain control agents such as Red copper oxide ocean environment to be had to the defect of considerable damage.In Qingdao Harbour, real extra large link plate has had the anti-fouling effect that exceedes 8 months, and following expection can reach longer antifouling varnish effect.
Accompanying drawing explanation
Fig. 1 is that antifouling paint of the present invention is being coated with priming paint and 1 road intermediate coat (anti-fouling effect of application on total thickness 150-200 μ standard jig m), antifouling paint thickness approximately 200 μ m.
Embodiment is corresponding with position on plate as follows
Fig. 2 is that antifouling paint of the present invention is only being coated with 2 road anti-corrosion primers (anti-fouling effect of application on thickness 100-150 μ standard jig m), antifouling paint thickness approximately 200 μ m.
Embodiment is corresponding with position on plate as follows
| 11 | 12 | 16 | 7 | Blank |
| 13 | 14 | 17 | 20 | 10 |
Embodiment
Embodiment 1:
In whipping appts, thermometer, water trap, prolong being installed and connecing the 500ml four-hole bottle of vacuum pump, add successively 200g lactic acid (containing monomer 85%), 100g toluene and dimethylbenzene were by 1: 1 mixed solvent, under negative pressure in 130-140 ℃ of back flow reaction, water trap dewaters to anhydrous generation, obtains yellow poly(lactic acid) prepolymer.Add soft segment: butyleneglycol 15g and 15g PEG-200, esterifying catalyst 0.2g1: 1 two hydration dichloros sub-tin (SnCl2.2H2O) and p-methyl benzenesulfonic acid (TSA), under negative pressure in 130-140 ℃ of back flow reaction 10 hours to anhydrous generation, obtain light brown resin, be polylactic acid based many blocks prepolymer.After cooling, add 80g mixed solvent: the dimethylbenzene of 1: 1 and N-BUTYL ACETATE, 45g polyisocyanates as ratio be 2: 1 tolylene diisocyanates and 1, oneself two different acid esters of 6-, catalyzer dibutyl tin laurate 0.1g, heating, 80 ℃ of stirring reactions 4 hours, obtains final many blocks biodegradation type resin.
Embodiment 2:
In whipping appts, thermometer, water trap, prolong being installed and connecing the 500ml four-hole bottle of vacuum pump, add successively 200g lactic acid (content 85%), 1: 1 mixed solvent of 100g toluene and dimethylbenzene, under negative pressure in 130-140 ℃ of back flow reaction, water trap dewaters to anhydrous generation, obtains yellow poly(lactic acid) prepolymer.Add soft segment as 3g propylene glycol, 5g butyleneglycol, 25gPEG-400, catalyzer, as the stannous octoate of 0.2g, with the extremely anhydrous generation in 8 hours of back flow reaction under embodiment 1 the same terms, obtains light brown resin, is polylactic acid based many blocks prepolymer.After cooling, add 100g mixed solvent as 1: 1 N-BUTYL ACETATE and methyl iso-butyl ketone (MIBK), 47g polyisocyanates is as l, oneself two different acid esters of 6-, and 0.1g dibutyl tin laurate, 80 ℃ of heated and stirred reactions 4 hours, obtain final many blocks biodegradation type resin.
Embodiment 3:
In the 500ml four-hole bottle that whipping appts, thermometer, water trap, prolong are installed, add successively 200g lactic acid (containing monomer 85%), 100g aromatic solvent is as dimethylbenzene, back flow reaction under normal pressure, water trap dewaters to anhydrous generation, obtains faint yellow polylactic acid low polymer.Add the polycaprolactone polyol that soft segment is 1000 as 10g pentanediol, 10gPEG-200,15g molecular weight, add catalyzer as the tetrabutyl titanate of 0.2g, hour extremely anhydrous generation of atmospheric pressure reflux stoichiometric number, obtains light brown resin, is polylactic acid based many blocks prepolymer.After cooling, in system, add 100g mixed solvent as dimethylbenzene and the N-BUTYL ACETATE of 1: 1,50g polyisocyanates is as the dibutyl tin laurate of tolylene diisocyanate, 0.1g, and 80 ℃ of heated and stirred are reacted 4 hours, obtain final many blocks biodegradation type resin.
Embodiment 4:
In the 500ml four-hole bottle that whipping appts, thermometer, water trap, prolong are installed, add successively 200g lactic acid (containing monomer 85%), 100g toluene and dimethylbenzene by the mixed solvent of 1: 1, back flow reaction under normal pressure, water trap dewaters to anhydrous generation, obtains faint yellow polylactic acid low polymer.Add soft segment as 15g butyleneglycol, 15gPEG-200,15gPEG-600, add the tetrabutyl titanate of 0.2g, back flow reaction obtains light brown resin to anhydrous generation in 10 hours, is polylactic acid based many blocks prepolymer.After cooling, add 100g N-BUTYL ACETATE in system, 50g polyisocyanates is as tolylene diisocyanate, 0.2g catalyzer dibutyl tin laurate, and 80 ℃ of heated and stirred reactions 4 hours, obtain final many blocks biodegradation type resin.
The biodegradation type resin that embodiment 1-4 obtains, change soft segment as the kind of polyoxyethylene glycol PEG-200, PEG-400, PEG-600 and propylene glycol, butyleneglycol, pentanediol, glycerol, the kind of polycaprolactone polyol, and the consumption of polyisocyanates and proportioning, can obtain a series of biodegradation type segmented copolymers.
Embodiment 5-20
The biodegradation type resin respectively embodiment 1-4 being obtained, prepare antifouling paint A series formula (totally 4 embodiment), B series formula (totally 4 embodiment), C series formula (totally 4 embodiment), D series formula (totally 4 embodiment), the embodiment obtaining is designated as 5-20, and series formula sees the following form one.
Table one: biodegradation type antifouling paint series formula
Table two: embodiment 5-20 calendar
The standard jig that antifouling paint embodiment 5-20 is brushed carries out the test of reality sea in Qingdao Harbour, to verify the properties of biodegradation type antifouling paint, especially antifouling property.
Fig. 1 is the effect of antifouling paint of the present invention application on the standard jig that is coated with priming paint and 1 road intermediate coat.Embodiment is corresponding with position on plate as follows.
| 5 | 6 | 7 | 8 | Blank |
| 9 | ||||
| 18 | 12 | 15 | 19 | 13 |
The link plate time is on December 16th, 2010, and looking into the plate time is on August 29th, 2011, and experimental period 8 wheat harvesting periods also comprise a marine life growth busy season, also underway.Observe embodiment 19 and occur bubbling, only there are a small amount of active sludge or antifouling microbial film in the surface of most embodiment paint samples, and overall antifouling property is good, has exceeded the antifouling varnish effect of 8 months.In contrast framework font, especially the blank model on embodiment 9 tops has a large amount of pollution by sea living.
Fig. 2 is biodegradation type antifouling paint of the present invention application on the standard jig that is only coated with 2 road priming paint.Embodiment is corresponding with position on plate as follows.
| 11 | 12 | 16 | 7 | Blank |
| 13 | 14 | 17 | 20 | 10 |
At Qingdao Harbour link plate, the link plate time is on March 21st, 2011, and looking into the plate time is on August 29th, 2011, and experimental period 5 months also comprises a marine life growth busy season, also underway.Visible overall anti-fouling effect is good, and only there is the antifouling microbial film of one deck on antifouling paint surface, and a small amount of active sludge, the existing antifouling phase effect that exceedes 5 months.Paint film sea water resistance is non-foaming more than soaking and also having reached 5 months not to ftracture.The white space on embodiment 10 tops in contrast has a large amount of pollution by sea living.
Claims (2)
1. an antifouling paint compositions, is characterized in that, fills a prescription as follows:
Described biodegradable resin is polymerized under esterifying catalyst effect by polylactic acid low polymer, soft segment, polyisocyanates;
Described polylactic acid low polymer, by lactic acid and the aromatic solvents of monomer content 80-85%, under negative pressure or normal pressure, back flow reaction, to anhydrous generation, obtains polylactic acid low polymer;
Described aromatic solvents, is selected from toluene and/or dimethylbenzene, and consumption is pressed the 30-60% massfraction of lactic acid production;
Described soft segment is polyester polyol, and consumption is with the 5-30% of lactic raw material massfraction;
The consumption of described polyisocyanates is with the 10-30% of lactic raw material massfraction;
Described esterifying catalyst is selected from SnCl
4, TiCl
4, SbF
3, SnCl
2-2H
2o, SnCl
4-H
2o, tosic acid, tetrabutyl titanate, dibutyl tin laurate, stannous octoate, choose one or several combination, and the add-on of catalyzer is with the 0.1-0.2% of lactic raw material massfraction;
The preparation method of described biodegradable resin is: in polylactic acid low polymer, add soft segment, add esterifying catalyst, under negative pressure or normal pressure, in 130-150 ℃ of back flow reaction, water trap dewaters to anhydrous generation, obtains polylactic acid based many blocks prepolymer; After cooling this prepolymer, add mixed solvent, polyisocyanates and catalyzer dibutyl tin laurate, obtain 50-90 ℃ of heated and stirred reaction;
Mixed solvent used in the preparation of biodegradable resin is selected from aromatic solvents, esters solvent, and alcoholic solvent, ketones solvent, chooses above-mentioned several solvent, and mixed solvent consumption is with the 20-60% of lactic raw material massfraction;
The molecular weight ranges of described polylactic acid low polymer is at 500-3500;
Described back flow reaction temperature is 130-150 ℃.
2. antifouling paint compositions according to claim 1, is characterized in that, described compound organic stain control agent is: cuprous thiocyanate (CuSCN); Tetramethyl thiuram disulfide commodity are called Thiram, and good fortune is two beautiful; Ethylenebis (curing carboxylamine) zinc, trade(brand)name zineb; 4,5-dichloro--Kathon, trade(brand)name Sea-Nine211; Copper pyrithione, commodity are called Copper Omadine; Zinc Pyrithione Pyrithionc Zinc, ZPT, another name: Pyrithionc Zinc; N-cyclopropyl-N'-(1,1-dimethyl ethyl)-6-(methyl sulfo-)-1,3,5-triazines-2,4-diamines, trade(brand)name Irgarol1051; 2,4,5,6-daconil M, trade(brand)name m-tetrachlorophthalodinitrile; N, N-dimethyl-N ＇-dichloro fluorine methylthio group-N ＇-phenyl sulphamide, trade(brand)name Preventol A4-S, Pecudin; N, N-dimethyl-N ＇-(4-tolyl)-N ＇-(dichloro fluorine methylthio group) sulphonamide, commodity are called Preventol A5-S, tolylfluanid; N ＇-(3,4-dichlorophenyl)-N, the commodity Preventol A6 by name of N-dimethyl urea, Diuron; Pyridine triphenylborane; N-(2,4,6-trichlorophenyl) maleimide; 8-methyl-N-[(4-hydroxy 3-methoxybenzene base)-methyl]-(instead)-6-alkenyl amide in the ninth of the ten Heavenly Stems, chemical name: synthetic capsaicin, Vanillyl pelargonic amide; Polyhexamethylene guanidine phosphoric acid salt, SKYBIO1100; Hydrochloric acid dexmedetomidine; 2-(Extraction kinetics sulfydryl)-1,3 benzothiazole; The bromo-2-of 4-(4-chloro-phenyl-)-5-Trifluoromethyl-1 H-pyrroles-3-formonitrile HCN, chooses two or more.
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