CN102432802A - 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 with resin and compound method thereof, contain the biodegradation type antifouling paint compositions and the preparation method of this resin, belong to technical field of polymer materials.
Background technology
Along with " international control boats and ships system's pact of harmful antifouling end " (AFS pact) implementation with " about the Convention of Stockholm of persistence organic pollutant " (POPs pact); The antifouling paint that contains organotin, DDT is withdrawn from the market comprehensively, and the direction of the production forward heavy metal free of antifouling paint, Wuxi, low copper, no sterilant develops.It is imperative to research and develop ecological friendly antifouling paint.From polishing type antifouling paint is a developing direction, but still has some problems:
(1) antifouling paint of polishing type certainly of main flow is better for the marine antifouling effect that Gao Zaihang leads at present, and the speed of a ship or plane is high more, and obvious more from polishing action, anti-fouling effect is good more.But antifouling coating upgrades weak effect in the immobilized seawater, and to low speed, hang down at boat rate boats and ships especially warship, and the antifouling usefulness of Offshore Units is relatively poor relatively.Research and development are used for low speed, hang down in the boats and ships of boat rate and the supporting system of antifouling paint of Offshore Units and offshore structure targetedly, and extensive market prospects is arranged.
(2), the antifouling paint of main flow is the tin-free self-polishing antifouling paint on the market.Its matrix resin mainly is divided into three major types: zinc acrylate resin, acrylate resin and vinylformic acid silica alkane resin, antifouling basically toxic agent is a Red copper oxide.Antifouling paint relies on the purpose that reaches antifouling of oozing out of Red copper oxide; Little than the harm of organic tin antifouling paint; Though meet current environmental requirement; But still there is the potential environmental hazard in traditional acrylic acid or the like from polishing type antifouling paint, and is in the composition of tin-free self-polishing antifouling paint, especially very harmful to ocean environment with Red copper oxide in its color stuffing.
The biodegradated polymer materal large-scale development is used the existing recent two decades time, but because the problem of 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; At least aly react with containing through POLYMETHYLENE POLYPHENYLISOCYANATE, produce the material of biodegradable polyurethane from starch or treated starch, honey, polyose agricultural waste and the organic solvent that contains the plant component of selecting the modified vegetable oil of hydroxyl.Other has the document Japanese Unexamined Patent Publication No is that 6-65349 and one Chinese patent application CN200810185131.6 have reported that the use POLYMETHYLENE POLYPHENYLISOCYANATE makes starch combine 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 that obtains on starch or the treated starch and the reaction of isocyanic ester based products through graft polymerization obtain degradable resin and prepare starch-based coating.
Application number is the biodegradable resin combination of CN200480041278.8, comprises at least a biodegradable organic polymer, contains the flame-retardant additive of phosphorus compound and can suppress the hydrolysis inhibitor of this at least a organic polymer hydrolysis.As aliphatic polyester resin, use POLYACTIC ACID, polycaprolactone, polyhydroxybutyrate, gather hydroxypentanoic acid, polydiethylene glycol succinate, polybutylene succinate, poly adipate succinic acid ester, polymalic acid, mikrobe synthetic polyester or contain their at least a multipolymer.As polysaccharide, use Mierocrystalline cellulose, starch, chitin, chitosan, VISOSE, their any one verivate, or contain their at least a multipolymer.
Above patent documentation mainly is used for the Traditional Packing field of materials with biodegradated polymer materal.
Document Development of poly (e-caprolaetone-co-L-lactide) and poly (e-caprolaetone-co-d-valerolactone) as new degradable binder used for antifouling paint [J] the .European Polymer Journal of report such as Fay F; 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; Catalysis synthesizing polyether multipolymer under the anhydrous and oxygen-free vacuum condition; This copolyether has appropriate solubility in the aromatic solvent that antifouling paint is used always; And in ocean environment, suitable hydrolysis/biological degradability can be arranged, the coating that is base-material based on these novel degradable resins has certain anti-fouling effect in the Atlantic Ocean through experiment confirm.In addition; Fay.F has also reported document Biodegradable poly (esteranhydride) for new antifouling coating [J] .Biomacromolecules; 2007; 8 (5): 1751-1758. synthesized one type have biological controlled degradation property, with coating weighting material consistency and certain persistent block polymer, use and to show and can effectively stop adhering to and growing of fouling organism.Yet, degrade fully through coating behind the sea water immersion in 10 weeks, need further to improve its weather resistance.According to people such as Fay.F, the reaction conditions that their synthetic resins adopted is under the 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.Be research about the laboratory degradation property of polyhydroxyalkanoate family macromolecule material.
Domestic 725 Xiamen branches of institute have reported " antifouling paint is with the study on the synthesis of 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; Antifouling paint as the resin binder preparation has preliminary anti-fouling effect; According to theirs; The raw material rac-Lactide, the hydroxy-terminated polybutadienes price that are adopted are very high, and reaction conditions needs 160-170 ℃ of reaction down of anhydrous and oxygen-free nitrogen protection.The performance data that the dissolution with solvents performance of the resin of gained and the preparation of other coating are relevant is less, and has only reported 25 days link plate data.
At present; The biodegradation type antifouling paint also exists: biodegradation type coating does not have commercially produced product in enormous quantities with macromolecular material; The cost of material of preparation 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, and sea water resistance soaks the problem that the bad and antifouling phase effect of performance need solve than weak point or the like many-side.
Summary of the invention
The purpose of this invention is to provide a kind of biodegradation type antifouling paint with resin, preparation method, and the antifouling paint compositions that contains this resin.
The objective 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 the esterifying catalyst effect by polylactic acid low polymer, soft segment, POLYMETHYLENE POLYPHENYLISOCYANATE.
Described polylactic acid low polymer, by lactic acid (monomer content 80-85%) and aromatic solvents, in negative pressure or the reaction of normal pressure refluxed, 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 YLENE is chosen one or more.
Described soft segment is meant 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: terepthaloyl moietie, and Ucar 35, butyleneglycol, pentanediol, USP Kosher, tetramethylolmethane, polyoxyethylene glycol PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-2000 etc. choose one or more.
Described polyester polyol is meant polycaprolactone polyol.
Described POLYMETHYLENE POLYPHENYLISOCYANATE is selected from tolylene diisocyanate, '-diphenylmethane diisocyanate, 1; Oneself two different acid esters of 6-, isoflurane chalcone diisocyanate, 4; The 4-dicyclohexyl methane diisocyanate, to tetramethyl for Ben Yajiaji vulcabond, vulcabond diformazan phenyl ester, trimethyl hexamethylene diisocyanate, choose wherein one or more.The consumption of POLYMETHYLENE POLYPHENYLISOCYANATE 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, in 130-150 ℃ of back flow reaction, water trap dewaters to anhydrous generation under negative pressure or normal pressure, obtains polylactic acid based many blocks prepolymer.
After the cooling of polylactic acid based many blocks prepolymer, add mixed solvent, POLYMETHYLENE POLYPHENYLISOCYANATE and catalyzer dibutyl tin laurate at 50-90 ℃ of heated and stirred stoichiometric number hour, obtain the final product multi-block polymer.
Described esterifying catalyst mainly is 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 is chosen above-mentioned one or several solvents.The mixed solvent consumption is pressed the 20-60% of lactic raw material massfraction, in order to the viscosity and the solid content of adjustment resin, improves the solvability and the stable homogeneous property of resin system.
Described aromatic solvents is selected from toluene, YLENE.
Described esters solvent is selected from butylacetate, ETHYLE 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 serve as the main segment of forming with the synthetic polylactic acid low polymer.The molecular weight control of polylactic acid low polymer is extremely important.The too high dissolution with solvents performance of segmented copolymer that then causes of molecular weight is poor, poor stability; It is the antifouling paint paint film property defective of base-material that it's low then causing with prepared resin is past molecular weight,, sea water resistance difference too soft like paint film etc.So the molecular weight ranges of polylactic acid low polymer of the present invention is better at 500-3500, better be 800-2500.
The popular response flow process: lactic acid (content 85%), aromatic solvent, negative pressure or the reaction of normal pressure refluxed obtain faint yellow polylactic acid low polymer to anhydrous generation.In system, add soft segment; One or several arbitrary proportion combination like butyleneglycol, PEG-200, PEG-400 etc. adds esterifying catalyst, and the same terms refluxed stoichiometric number is hour to anhydrous generation; Obtain the light brown resin, be polylactic acid based many blocks prepolymer.After the cooling, add mixed solvent, POLYMETHYLENE POLYPHENYLISOCYANATE 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 do not have the antifouling paint compositions of copper, is that matrix resin, compound low toxicity stain control agent, color stuffing, auxiliary agent are formed with the aforementioned biodegradation type resin that obtains.Prescription is (w/%) as follows
In the prescription of the present invention, owing to select the organic stain control agent of composite high-efficiency low-toxicity for use, copper class stain control agent consumption such as Red copper oxide is significantly reduced, perhaps not have copper fully.
In the formulation for coating material of the present invention, selectivity adds the Red copper oxide of lower aq as auxiliary collaborative stain control agent.
Selectivity adds rosin in the formulation for coating material of the present invention, is used for regulating stain control agent rate of release and paint film property.And, therefore can reduce the consumption of institute's synthetic biodegradable resin because the rosin price comparison is low.
The present invention selects compound organic stain control agent system of wide spectrum, efficient, low toxicity.For example pyrithione class (like CuPT), isothiazolinone (like S-211), pyridine phenyl boron class (like PTPB), triazines (like Irgarol1051).Concrete: cuprous thiocyanate (CuSCN); The tetramethyl thiuram disulfide commodity are called Thiram, and good fortune is two beautiful; Ethylenebis (curing carboxylamine) zinc, the trade(brand)name zineb; 4,5-dichloro--2-n-octyl-4-isothiazoline-3-ketone, trade(brand)name Sea-Nine211; Copper pyrithione, commodity are called Copper Omadine; Pyrithionc Zinc, ZPT, another name: Ao Maiding zinc; N-cyclopropyl-N '-(1, the 1-dimethyl ethyl)-6-(methyl sulfo-)-1,3,5-triazines-2, the 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, the 4-dichlorophenyl)-N, the commodity of N-dimethyl urea are called Preventol A6, Diuron; The pyridine triphenylborane; N-(2,4, the 6-trichlorophenyl) maleimide; 8-methyl-N-[(4-hydroxy 3-methoxybenzene base)-methyl]-(instead)-6-nonene base acid amides, chemical name: synthetic capsaicin, Vanillyl pelargonic amide; Polyhexamethylene guanidine phosphoric acid salt, SKYBIO1100; The hydrochloric acid MPU-295; 2-(thiocyanic acid methyl mercapto)-1,3 benzothiazole; 4-bromo-2-(4-chloro-phenyl-)-5-Trifluoromethyl-1 H-pyrroles-3-formonitrile HCN.Select one or more for use.
Described pigment is meant zinc oxide ZnO, red stone Fe2O3, and titanium white TiO2, and other common inorganic, pigment dyestuffs select one or more for use.
Described filler is meant talcum powder, and permanent white 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, for example stablizer, anti-settling agent, softening agent etc.Described auxiliary agent is meant wilkinite, and organic anti-settling agent is like A630 etc.
Described mixed solvent is selected from aromatic solvents, esters solvent, and alcoholic solvent, ketones solvent comprises but is not limited to the mixture of one or several solvents in the above solvent.
Described aromatic solvents is selected from toluene, YLENE.
Described esters solvent is selected from butylacetate, ETHYLE 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.
Said antifouling paint compositions is a matrix resin with the biodegradation type resin.Hull-bottom antifouling coating biological degradation through the paint film top layer in seawater discharges stain control agent; And then the biology that coatingsurface adheres to breaks away from washing away under the abrasion of seawater with the coating of having degraded; Form slick hull bottom surface through 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: at the biodegradation type antifouling paint with in resin synthetic; According to people such as " antifouling paint is with the study on the synthesis of degradable polyurethane resin binder " and Fay.F institute; The resin building-up reactions system that they adopt needs anhydrous and oxygen-free; Nitrogen protection, and vacuum suction etc., reaction conditions requires high.The production technique synthesis reaction temperature that the present invention adopted lower (being generally 130-150 ℃), catalyst levels is low, need not nitrogen protection in the production process; Only need negative pressure or atmospheric pressure reflux; And by product has only water to generate, and does not have high poison, the generation of hazardness waste, and production process is environmental protection.Can accomplish that one kettle way is synthetic, the midbody prepolymer does not need purifying, reacts controlled, favorable reproducibility.
The initial feed that the present invention adopted is that content is the lactic acid monomer of 80-85%, and the price of the rac-Lactide that is adopted in " antifouling paint is with the study on the synthesis of degradable polyurethane resin binder " compared to prior art is lower.And valerolactone, rac-Lactide cost of material that people such as Fay adopt are also higher.Concrete; Valerolactone, rac-Lactide and hydroxy-terminated polybutadienes (HTPB) cost an arm and a leg; All above 100 yuan/kilogram; It all is common commercially available industrial goods that main raw material of the present invention contains 85% monomeric lactic acid, polyvalent alcohol, POLYMETHYLENE POLYPHENYLISOCYANATE and YLENE etc., and low price is similar with common common acrylic coating resin raw material price.
The route that the present invention adopts be earlier by the lactic acid auto-polymerization prepare polylactic acid low polymer again with the soft segment catalyzed polymerization; The rac-Lactide catalysis open loop of being adopted with aforementioned paper is also different fully, feasible more economically with hydroxy-terminated polybutadienes (HTPB) polymeric operational path.
The biodegradation type resin that prepared this of the present invention contains many block structures in the antifouling paint common solvent (like aromatic solvents such as YLENE; Esters solvents such as N-BUTYL ACETATE, alcoholic solvent) middle favorable solubility, can reach the solids content about 60%; And modest viscosity, good fluidity.Prepared filming can reach the progressively effect of degraded in seawater, and can keep certain mechanical property.With described biodegradation type resin is the antifouling paint sample of base-material preparation, has wherein had the sea water resistance that surpassed 8 months and comprised a marine life growth busy season to soak and antifouling property data (seeing embodiment accompanying drawing 1).
Be the biodegradation type antifouling paint of matrix resin preparation with this biodegradation type resin among the present invention, do not contain international and domestic forbidding toxic agent such as organotin, high toxicity agricultural chemicals.Be single-component coating, can reach about density 1.3g/cm3 that solids content meets or exceeds 60%, and is easy to use.Through test, time≤24 hour are done solid work in surface drying time≤2 of on the epoxy primer Ep-501 of Inst. of Marine Chemical Engineering production or Ep-507 intermediate coat, brushing 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, anti-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, the about 200 μ m of thickness; The existing sea water immersion data (seeing embodiment accompanying drawing 2) that surpassed 5 months and comprised a marine life growth busy season; Paint film is non-foaming not to ftracture, and does not have marine life and adhere to, and anti-fouling effect is good.
Biodegradation type antifouling paint of the present invention, have in the low flow velocity seawater from polishing performance, have good anti-fouling effect.Tentatively solved traditional self polishing copolymer antifouling paint to low in the boat rate or in the harbour the not high problem of the antifouling usefulness of long-time sitting duck oceangoing ship.Biodegradation type antifouling paint oxygen-freeization of the present invention is cuprous, or it is cuprous to contain small amounts, has solved existing main flow self polishing copolymer antifouling paint and has used metal species stain control agents such as Red copper oxide ocean environment to be had the defective of considerable damage in a large number.Real extra large link plate has had the anti-fouling effect above 8 months in the Qingdao Harbour, and following expection can reach longer antifouling varnish and imitate.
Description of drawings
Fig. 1 is that antifouling paint of the present invention is at the anti-fouling effect that is coated with application on priming paint and the 1 road intermediate coat standard jig of (adding up to thickness 150-200 μ m), the about 200 μ m of antifouling paint thickness.
The position is corresponding as follows on embodiment and the plate
Fig. 2 is the anti-fouling effect of antifouling paint of the present invention application on the standard jig that only is coated with 2 road anti-corrosion primers (thickness 100-150 μ m), the about 200 μ m of antifouling paint thickness.
The position is corresponding as follows on embodiment and the plate
| 11 | 12 | 16 | 7 | Blank |
| 13 | 14 | 17 | 20 | 10 |
Embodiment
Embodiment 1:
Add 200g lactic acid (containing monomer 85%) successively whipping appts, TM, water trap, prolong being installed and connecing in the 500ml four-hole bottle of vacuum pump; 100g toluene and YLENE were by 1: 1 mixed solvent; Under negative pressure in 130-140 ℃ of back flow reaction; Water trap dewaters to anhydrous generation, obtains yellow POLYACTIC ACID prepolymer.Add soft segment: butyleneglycol 15g and 15g PEG-200; Esterifying catalyst 0.2g1: inferior tin (SnCl2.2H2O) of 1 two hydration dichloros and p-methyl benzenesulfonic acid (TSA); Under negative pressure in 130-140 ℃ of back flow reaction 10 hours to anhydrous generation; Obtain the light brown resin, be polylactic acid based many blocks prepolymer.After the cooling; Add the 80g mixed solvent: 1: 1 YLENE and N-BUTYL ACETATE, 45g POLYMETHYLENE POLYPHENYLISOCYANATE such as ratio are 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:
Add 200g lactic acid (content 85%) successively whipping appts, TM, water trap, prolong being installed and connecing in the 500ml four-hole bottle of vacuum pump; 1: 1 mixed solvent of 100g toluene and YLENE; Under negative pressure in 130-140 ℃ of back flow reaction; Water trap dewaters to anhydrous generation, obtains yellow POLYACTIC ACID prepolymer.Add soft segment such as 3g Ucar 35, the 5g butyleneglycol, 25gPEG-400, the stannous octoate of catalyzer such as 0.2g with embodiment 1 the same terms refluxed reaction extremely anhydrous generation in 8 hours, obtains the light brown resin, is polylactic acid based many blocks prepolymer.After the cooling, add the 100g mixed solvent like 1: 1 N-BUTYL ACETATE and MIBK, 47g POLYMETHYLENE POLYPHENYLISOCYANATE such as l, oneself two different acid esters of 6-, the 0.1g dibutyl tin laurate, 80 ℃ of heated and stirred reactions 4 hours obtain final many blocks biodegradation type resin.
Embodiment 3:
, the 500ml four-hole bottle of whipping appts, TM, water trap, prolong adds 200g lactic acid (containing monomer 85%) in being installed successively; 100g aromatic solvent such as YLENE; The reaction of normal pressure refluxed, water trap dewaters to anhydrous generation, obtains faint yellow polylactic acid low polymer.Adding soft segment such as 10g pentanediol, 10gPEG-200,15g molecular weight are 1000 polycaprolactone polyol; The tetrabutyl titanate that adds catalyzer such as 0.2g; Hour extremely anhydrous generation of atmospheric pressure reflux stoichiometric number obtains the light brown resin, is polylactic acid based many blocks prepolymer.After the cooling; In system, add the 100g mixed solvent like 1: 1 YLENE and N-BUTYL ACETATE; The dibutyl tin laurate of 50g POLYMETHYLENE POLYPHENYLISOCYANATE such as tolylene diisocyanate, 0.1g, 80 ℃ of heated and stirred were reacted 4 hours, obtained final many blocks biodegradation type resin.
Embodiment 4:
, the 500ml four-hole bottle of whipping appts, TM, water trap, prolong adds the mixed solvent that 200g lactic acid (containing monomer 85%), 100g toluene and YLENE were pressed 1: 1 in being installed successively; The reaction of normal pressure refluxed; Water trap dewaters to anhydrous generation, obtains faint yellow polylactic acid low polymer.Add soft segment such as 15g butyleneglycol, 15gPEG-200,15gPEG-600, add the tetrabutyl titanate of 0.2g, back flow reaction obtained the light brown resin to anhydrous generation in 10 hours, was polylactic acid based many blocks prepolymer.After the cooling, in system, add the 100g N-BUTYL ACETATE, 50g POLYMETHYLENE POLYPHENYLISOCYANATE such as tolylene diisocyanate, 0.2g catalyzer dibutyl tin laurate, 80 ℃ of heated and stirred were reacted 4 hours, obtained final many blocks biodegradation type resin.
The resulting biodegradation type resin of embodiment 1-4; Change kind and the Ucar 35 of soft segment such as polyoxyethylene glycol PEG-200, PEG-400, PEG-600, butyleneglycol, pentanediol; USP Kosher; The kind of polycaprolactone polyol, and the consumption of POLYMETHYLENE POLYPHENYLISOCYANATE and proportioning can obtain a series of biodegradation type segmented copolymers.
Embodiment 5-20
Respectively with the resulting biodegradation type resin of embodiment 1-4; Preparation antifouling paint A series prescription (totally 4 embodiment), B series prescription (totally 4 embodiment), C series prescription (totally 4 embodiment), D series prescription (totally 4 embodiment); Resulting embodiment is designated as 5-20, and the series prescription sees the following form one.
Table one: biodegradation type antifouling paint series prescription
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 the Qingdao Harbour, with each item performance, the especially antifouling property of checking biodegradation type antifouling paint.
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.The position is corresponding as follows on embodiment and the plate.
| 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, and are also underway.Observe embodiment 19 and occur bubbling, only there are a small amount of active sludge or antifouling microbial film in the surface that most embodiment coat with lacquer appearance, and overall antifouling property is good, and the antifouling varnish that has surpassed 8 months is imitated.The framework font that contrasts with it, especially the blank model on embodiment 9 tops all 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 only is coated with 2 road priming paint.The position is corresponding as follows on embodiment and the plate.
| 11 | 12 | 16 | 7 | Blank |
| 13 | 14 | 17 | 20 | 10 |
The link plate in the Qingdao Harbour, 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, and is also underway.It is thus clear that overall anti-fouling effect is good, only there is the antifouling microbial film of one deck on the antifouling paint surface, and a small amount of active sludge, the existing antifouling phase effect that surpasses 5 months.The immersion of paint film sea water resistance has also reached non-foaming more than 5 months and has not ftractureed.The white space on embodiment 10 tops that contrast with it has a large amount of pollution by sea living.
Claims (10)
1. a biodegradable resin that comprises many block structures is characterized in that, it is polymerized under the esterifying catalyst effect by polylactic acid low polymer, soft segment, POLYMETHYLENE POLYPHENYLISOCYANATE;
Described polylactic acid low polymer by lactic acid and the aromatic solvents of monomer content 80-85%, in negative pressure or extremely anhydrous generation of normal pressure refluxed reaction, obtains polylactic acid low polymer;
Described aromatic solvents is selected from toluene and/or YLENE, and consumption is pressed the 30-60% massfraction of lactic acid production;
Described soft segment is meant polyvalent alcohol or/and polyester polyol, and consumption is with the 5-30% of lactic raw material massfraction;
The consumption of described POLYMETHYLENE POLYPHENYLISOCYANATE is with the 10-30% of lactic raw material massfraction;
Described esterifying catalyst is selected from SnCl4, TiCl4, SbF3, SnCl2-2H2O, SnCl4-H2O, tosic acid (TSA), tetrabutyl titanate, dibutyl tin laurate, stannous octoate; Choose one or several combination, 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; In 130-150 ℃ of back flow reaction, water trap dewaters to anhydrous generation under negative pressure or normal pressure, obtains polylactic acid based many blocks prepolymer; After this prepolymer cooling, add mixed solvent, POLYMETHYLENE POLYPHENYLISOCYANATE and catalyzer dibutyl tin laurate, obtain 50-90 ℃ of heated and stirred reaction.
2. according to the biodegradable resin of claim 1, it is characterized in that described polyvalent alcohol is selected from: terepthaloyl moietie, Ucar 35; Butyleneglycol, pentanediol, USP Kosher, tetramethylolmethane; Polyoxyethylene glycol PEG-200, PEG-400, PEG-600, PEG-800; PEG-1000, PEG-2000 chooses one or more.
3. according to the biodegradable resin of claim 1, it is characterized in that described polyester polyol is a polycaprolactone polyol.
4. according to the biodegradation type resin of claim 1; It is characterized in that; Described POLYMETHYLENE POLYPHENYLISOCYANATE is selected from tolylene diisocyanate, '-diphenylmethane diisocyanate, 1; Oneself two different acid esters of 6-, isoflurane chalcone diisocyanate, 4, the 4-dicyclohexyl methane diisocyanate, to tetramethyl for Ben Yajiaji vulcabond, vulcabond diformazan phenyl ester, trimethyl hexamethylene diisocyanate, choose wherein one or more.
5. according to the biodegradable resin of claim 1, it is characterized in that described back flow reaction temperature is 130-150 ℃.
6. according to the biodegradable resin of claim 1, it is characterized in that described mixed solvent is selected from aromatic solvents; Esters solvent, alcoholic solvent, ketones solvent; Choose above-mentioned one or several solvents, the mixed solvent consumption is with the 20-60% of lactic raw material massfraction.
7. according to the biodegradable resin of claim 1, it is characterized in that the molecular weight ranges of described polylactic acid low polymer is at 500-3500.
8. an antifouling paint compositions is characterized in that, is matrix resin with the biodegradable resin of claim 1, and its prescription is (w/%) as follows:
Raw material is formed w/%
Biodegradation type resin: 30～50
Rosin 0-10
Red copper oxide 0～6
Compound organic stain control agent 5-15
Pigment: 10～25
Filler: 15～30
Auxiliary agent: 1～4
Mixed solvent: 10～20.
9. according to Claim 8 antifouling paint compositions is characterized in that described compound organic stain control agent is pyrithione class, isothiazolinone, pyridine phenyl boron class, triazines, chooses one or more.
10. according to the antifouling paint compositions of claim 9, it is characterized in that described compound organic stain control agent is: cuprous thiocyanate (CuSCN); The tetramethyl thiuram disulfide commodity are called Thiram, and good fortune is two beautiful; Ethylenebis (curing carboxylamine) zinc, the trade(brand)name zineb; 4,5-dichloro--2-n-octyl-4-isothiazoline-3-ketone, trade(brand)name Sea-Nine211; Copper pyrithione, commodity are called Copper Omadine; Pyrithionc Zinc, ZPT, another name: Ao Maiding zinc; N-cyclopropyl-N'-(1, the 1-dimethyl ethyl)-6-(methyl sulfo-)-1,3,5-triazines-2, the 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, the 4-dichlorophenyl)-N, the commodity of N-dimethyl urea are called Preventol A6, Diuron; The pyridine triphenylborane; N-(2,4, the 6-trichlorophenyl) maleimide; 8-methyl-N-[(4-hydroxy 3-methoxybenzene base)-methyl]-(instead)-6-nonene base acid amides, chemical name: synthetic capsaicin, Vanillyl pelargonic amide; Polyhexamethylene guanidine phosphoric acid salt, SKYBIO1100; The hydrochloric acid MPU-295; 2-(thiocyanic acid methyl mercapto)-1,3 benzothiazole; 4-bromo-2-(4-chloro-phenyl-)-5-Trifluoromethyl-1 H-pyrroles-3-formonitrile HCN selects one or more for use.
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