CN104530985A - Rosin metal salt resin as well as preparation method and application thereof - Google Patents
Rosin metal salt resin as well as preparation method and application thereof Download PDFInfo
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- CN104530985A CN104530985A CN201410811712.1A CN201410811712A CN104530985A CN 104530985 A CN104530985 A CN 104530985A CN 201410811712 A CN201410811712 A CN 201410811712A CN 104530985 A CN104530985 A CN 104530985A
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Abstract
The invention relates to rosin metal salt resin as well as a preparation method and application thereof. The rosin metal salt resin has a structural formula R-X--R1(I), wherein R represents an acid radical of colopholic acid, disproportionated colopholic acid or dimeric colopholic acid; X represents an ion Zn<2+>, Cu<2+>, Mg<2+> or Ca<2+>; R1 represents an acid radical of colopholic acid, disproportionated colopholic acid or dimeric colopholic acid. The rosin metal salt resin is environmentally friendly; compared with the existing rosin, the rosin metal salt resin can be used as a main film forming matter, can be well matched with other components in a coating formula, can be degraded, is good in film coating toughness, relatively excellent in self-polishing performance and long in antifouling period, meets the environment-friendly development tendency of antifouling coatings and has good application prospect.
Description
[technical field]
The invention belongs to organic compound technical field.More specifically, the present invention relates to a kind of rosin metal salt resin, also relate to the preparation method of described rosin metal salt resin, also relate to the purposes of described rosin metal salt resin in environmentally friendly self polishing copolymer antifouling paint.
[background technology]
The organotin self polishing copolymer antifouling paint of " special efficacy weapon " is described as from early stage contact-type antifouling paint to 20 century 70s, then new antifouling paint up till now, the performance of resin has very important impact to exploitation pollution resisting coating.Along with more and more deep to the understanding of Organotin antifouling paints toxic effect, the nontoxic multi-functional resins of development of new seems particularly important.
At present, rosin is one of maximum natural resin of worldwide production amount, and annual global output is approximately 1,100,000 tons.China is the main grown place of natural rosin, and the rosin overwhelming majority that China produces is sufficient gum resin, and nearly 300,000 tons of annual output, the highest time even can reach 40.6 ten thousand tons.Because rosin can make coating fast drying, bright in color, the smooth and difficult drop-off of paint film, so people are applied to rosin in coating very early.In recent years, people have been mixed with the much coating with specific function with rosin or derivatives thereof.The coating industry of China is one of industry that use rosin is maximum.According to statistics, nineteen eighty-three, China reaches 3.22 ten thousand tons for the production of the rosin of coating, accounts for 17.66% of the total consumption of domestic rosin.
Many antifouling paints of countries in the world all using rosin as film forming matter or auxiliary material, as in the antifouling paint of lysotype, in the seawater of pH=7.5 ~ 8.4, rosin slowly dissolves, and the constantly exposed coatingsurface made new advances, discharge the poison material such as Red copper oxide simultaneously, form the solution film that one deck is poisonous, kill the marine fouling organism or its larva that are adsorbed on coatingsurface.In contact-type antifouling paint, adding rosin is cost in order to reduce coating, and prevents poison material to run off fast and a large amount of wastes.Novel contact-type antifouling paint trends towards the content improving natural rosin, and the ratio of present resin and natural rosin reaches l.3 ~ 4.Exposure test recently about antifouling paint shows: antifouling paint that is highly toxic, high-content Red copper oxide must coordinate the natural rosin of high-content, just can receive comparatively ideal anti-fouling effect.
At present, the application of rosin in antifouling paint is mainly directly added in coating with rosin form, in order to improve the application performance of rosin, also the added value of rosin is improved, the carboxyl reaction of rosin is utilized to make rosin metal salt resin, not only increase the toughness of rosin, and rosin metal salt resin degradable, improve the physical property of simple rosin so to a great extent.Rosin metal salt resin is applied in antifouling paint as main film forming matter, can better merge mutually with other coating composition, promote the over-all properties of film, antifouling paint is not only had excellent from polishing performance but also have more outstanding environment friendly.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of rosin metal salt resin.
Another object of the present invention is to provide the preparation method of described rosin metal salt resin.
Another object of the present invention is to provide described rosin metal salt resin in environmentally friendly purposes in polishing marine antifouling coating.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of rosin metal salt resin.
This resin has following structural formula (I):
R——X——R
1(I)
In formula:
R represents the sour acid group of sylvic acid, nilox resin acid or dimerization colophonium;
X represents Zn
2+, Cu
2+, Mg
2+or Ca
2+metal ion;
R
1represent the acid group that sylvic acid, nilox resin acid or dimerization colophonium are sour.
A preferred embodiment of the invention, described rosin metal salt resin is rosin zinc resin, rosin resin of copper, rosin magnesium resin, rosin calcium resin, rosin-disproportionating rosin zinc resin, rosin-disproportionating rosin resin of copper, rosin-disproportionating rosin magnesium resin, rosin-disproportionating rosin calcium resin, rosin dimerization rosin zinc resin, rosin dimerization rosin resin of copper, rosin dimerization rosin magnesium resin, rosin dimerization rosin calcium resin, nilox resin zinc resin, nilox resin resin of copper, nilox resin magnesium resin, nilox resin calcium resin, nilox resin dimerization colophonium zinc resin, nilox resin dimerization colophonium resin of copper, nilox resin dimerization colophonium magnesium resin, nilox resin dimerization colophonium calcium resin, dimerization colophonium zinc resin, dimerization colophonium resin of copper, dimerization colophonium magnesium resin or dimerization colophonium calcium resin.
The invention still further relates to the preparation method of described rosin metal salt resin.
The step of this preparation method is as follows: by 80 ~ 99 weight parts, one or both are selected from rosin, the rosin based material of nilox resin or dimerization colophonium and solvent add outfit whipping appts, with in the reflux exchanger of oily-water seperating equipment and the reactor of thermometer, under the condition of temperature 30 ~ 85 DEG C, heating makes rosin based material dissolve completely, then oxyhydroxide or the oxide compound of 1 ~ 20 weight part divalent metal is added, the amount of described solvent is 0.2 ~ 9.0 times of reactant gross weight, then react 2 ~ 120 hours under the condition of temperature 50 ~ 180 DEG C, then being warming up to 100 ~ 130 DEG C carries out dewatering until anhydrously to distillate, so obtain described rosin metal salt resin.
According to another kind of preferred implementation of the present invention, described Divalent metal hydroxide is selected from zinc hydroxide, copper hydroxide, magnesium hydroxide or calcium hydroxide; Described bivalent metal oxide is selected from zinc oxide, cupric oxide, magnesium oxide or calcium oxide.
According to another kind of preferred implementation of the present invention, described solvent is that one or more are selected from the solvent of toluene, dimethylbenzene, propyl carbinol, butylacetate, ethyl acetate or pimelinketone.
The invention still further relates to described rosin metal salt resin in environmentally friendly purposes in polishing marine antifouling coating.
The present invention relates to a kind of marine antifouling coating.
Described marine antifouling coating is made up of 20 ~ 60 weight part rosin metal salt resins, 1 ~ 20 weight part Red copper oxide, 1 ~ 20 parts by weight of plasticizer, 1 ~ 30 weight part stopping composition and 20 ~ 60 parts by weight solvent.
A preferred embodiment of the invention, described softening agent is that one or more are selected from the softening agent of clorafin, Vaseline, Ultra-low molecular weight polymethylmethacrylate or polymeric amide.
According to another kind of preferred implementation of the present invention, described stopping composition is that one or more are selected from the stopping composition of red iron oxide, aerosil, talcum powder, titanium dioxide or zinc oxide.
According to another kind of preferred implementation of the present invention, described solvent is that one or more are selected from the solvent of ethyl acetate, butylacetate, pimelinketone, dimethylbenzene, toluene or propyl carbinol.
In more detail the present invention will be described below.
The present invention relates to a kind of rosin metal salt resin.
This resin has following structural formula (I):
R——X——R
1(I)
In formula:
R represents the sour acid group of sylvic acid, nilox resin acid or dimerization colophonium;
X represents Zn
2+, Cu
2+, Mg
2+or Ca
2+ion;
R
1represent the acid group that sylvic acid, nilox resin acid or dimerization colophonium are sour.
Wherein said sylvic acid has following chemical formula:
It is a kind of tricyclic diterpene class oxygenatedchemicals, is a kind of most important resinous acid.It is water insoluble, is dissolved in common organic solvents and diluted sodium hydroxide solution, is dissolved in alcohol, benzene, chloroform, acetone, ether and dithiocarbonic anhydride.Industrial sylvic acid is yellow glassy solid, and fusing point can be low to moderate 85 DEG C sometimes.
Nilox resin is in the presence of a catalyst, and make a part for rosin oxidized by the effect of mineral acid and heat, another part is reduced, the product obtained by this disproportionation reaction.This disproportionation reaction essence is disproportionation process.Nilox resin is dehydroabietic acid (C
19h
27cOOH), dihydro sylvic acid (C
19h
31and tetrahydrogenated rosin acid (C COOH)
19h
33cOOH) mixture.
According to the present invention, described rosin metal salt resin is preferably rosin zinc resin, rosin resin of copper, rosin magnesium resin, rosin calcium resin, rosin-disproportionating rosin zinc resin, rosin-disproportionating rosin resin of copper, rosin-disproportionating rosin magnesium resin, rosin-disproportionating rosin calcium resin, rosin dimerization rosin zinc resin, rosin dimerization rosin resin of copper, rosin dimerization rosin magnesium resin, rosin dimerization rosin calcium resin, nilox resin zinc resin, nilox resin resin of copper, nilox resin magnesium resin, nilox resin calcium resin, nilox resin dimerization colophonium zinc resin, nilox resin dimerization colophonium resin of copper, nilox resin dimerization colophonium magnesium resin, nilox resin dimerization colophonium calcium resin, dimerization colophonium zinc resin, dimerization colophonium resin of copper, dimerization colophonium magnesium resin or dimerization colophonium calcium resin.
More preferably, described rosin metal salt resin is rosin zinc resin, rosin resin of copper, rosin magnesium resin, nilox resin zinc resin or dimerization colophonium zinc resin.
The invention still further relates to the preparation method of described rosin metal salt resin.
The step of this preparation method is as follows: by 80 ~ 99 weight parts, one or both are selected from rosin, the rosin based material of nilox resin or dimerization colophonium and solvent add outfit whipping appts, with in the reflux exchanger of oily-water seperating equipment and the reactor of thermometer, under the condition of temperature 30 ~ 85 DEG C, heating makes rosin based material dissolve completely, then oxyhydroxide or the oxide compound of 1 ~ 20 weight part divalent metal is added, the amount of described solvent is 0.2 ~ 9.0 times of reactant gross weight, then react 2 ~ 120 hours under the condition of temperature 50 ~ 180 DEG C, then being warming up to 100 ~ 130 DEG C carries out dewatering until anhydrously to distillate, so obtain described rosin metal salt resin.
The reaction of rosin based material and metal hydroxides or oxide compound is specific as follows:
or
The rosin that the present invention uses, nilox resin or dimerization colophonium are all product solds in the market, the rosin such as sold with trade(brand)name rosin by Zhengzhou Zhi Yuan Chemicals company limited, the nilox resin sold with trade(brand)name nilox resin by Beijing Lin Xinlong Chemicals company limited, the dimerization colophonium sold with trade(brand)name DMER-145 Gum Rosin by Jin Tenglong trade Co., Ltd of Shenzhen.
In the present invention, described Divalent metal hydroxide is selected from zinc hydroxide, copper hydroxide, magnesium hydroxide or calcium hydroxide.
Preferably, described Divalent metal hydroxide is selected from zinc hydroxide, copper hydroxide or calcium hydroxide.
Described bivalent metal oxide is selected from zinc oxide, cupric oxide, magnesium oxide or calcium oxide.
Preferably, described bivalent metal oxide is selected from zinc oxide, cupric oxide or calcium oxide.
According to the present invention, when the amount of rosin, nilox resin or dimerization colophonium is 80 ~ 99, if when the amount of Divalent metal hydroxide or oxide compound is less than 1, then can rosin metal salt resinous acid value too large; If when the amount of Divalent metal hydroxide or oxide compound is greater than 20, then can rosin metal salt resin not too transparent, out of order; Therefore, their weight ratio is 80 ~ 99:1 ~ 20 is rational, preferably 85 ~ 96:4 ~ 15, more preferably 88 ~ 92:8 ~ 12.
According to the present invention, described solvent is that one or more are selected from the solvent of toluene, dimethylbenzene, propyl carbinol, butylacetate, ethyl acetate or pimelinketone.
Preferably, described solvent is that one or more are selected from the solvent of toluene, dimethylbenzene, butylacetate or pimelinketone.
The solvent that the present invention uses is all normally used product in chemical technology field, all product sold in the market, the toluene such as sold with trade(brand)name toluene by new Yongan, Qingdao Chemical Company, the propyl carbinol sold with trade(brand)name propyl carbinol by new Yongan, Qingdao Chemical Company, the pimelinketone sold with trade(brand)name pimelinketone by the new Yongan Chemical Company in Qingdao.
According to the present invention, the usage quantity of described solvent is reactant gross weight 0.2 ~ 9.0 times, if its solvent load exceedes this scope, rosin metal salt resin viscosity can be made excessive or too small, is unfavorable for using.Preferably 2.2 ~ 7.0 times, more preferably 3.2 ~ 5.8 times.
In the present invention, described temperature of reaction and described reaction times are vital, if temperature of reaction is lower than 50 DEG C, then reaction can be made to carry out; If temperature of reaction is higher than 180 DEG C, then metal-salt resin viscosity can be made to become large; Therefore, temperature of reaction is 50 ~ 180 DEG C is appropriate; Therefore, temperature of reaction is 50 ~ 180 DEG C is appropriate, preferably 75 ~ 150 DEG C, more preferably 90 ~ 130 DEG C.
If the reaction times is less than 2 hours, then can react incomplete; If the reaction times is longer than 120 hours, then can color can deepen by rosin metal salt resin, even blackening, affects resin state; Therefore, the reaction times is 2 ~ 120 hours is rational; Therefore, the reaction times is 2 ~ 120 hours is rational, preferably 20 ~ 100 hours, more preferably 40 ~ 80 hours.
According to the present invention, the reaction of rosin, nilox resin or dimerization colophonium and Divalent metal hydroxide or oxide compound carries out 2 ~ 120 hours under the condition of temperature 50 ~ 180 DEG C,
Preferably, the reaction of rosin, nilox resin or dimerization colophonium and Divalent metal hydroxide or oxide compound carries out 20 ~ 100 hours under the condition of temperature 70 ~ 160 DEG C.
More preferably, the reaction of rosin, nilox resin or dimerization colophonium and Divalent metal hydroxide or oxide compound carries out 40 ~ 80 hours under the condition of temperature 90 ~ 140 DEG C.
Adopt conventional method of infrared spectrophotometry to analyze the rosin metal salt resin that the present invention prepares, its analytical results lists in accompanying drawing 1-6.Can be found out by the result of accompanying drawing 1-6 and to contrast with rosin spectrogram, Fig. 1 can find out at 1460cm
-1there is the ν as absorption peak of COO-Zn in place, at 1409cm
-1there is the ν s absorption peak of COO-Zn in place; Fig. 2 can find out at 1460cm
-1there is the ν as absorption peak of COO-Cu in place, at 1397cm
-1there is the ν s absorption peak of COO-Cu in place; Fig. 3 can find out 1460cm
-1there is the ν as absorption peak of COO-Mg in place, at 1413cm
-1there is the ν s absorption peak of COO-Mg in place; Can find out at 1450cm in Fig. 4
-1there is the ν as absorption peak of COO-Zn in place, at 1418cm
-1there is the ν s absorption peak of COO-Zn in place; Can find out at 1460cm in Fig. 5
-1there is the ν as absorption peak of COO-Cu in place, at 1412cm
-1there is the ν s absorption peak of COO-Cu in place; Can find out at 1458.6cm in Fig. 6
-1there is the ν as absorption peak of COO-Ca in place, at 1416.9cm
-1there is the ν s absorption peak of COO-Ca in place; Illustrate that metal ion has successfully been received on the carboxyl of rosin and rosin derivative.
Can be confirmed by above-mentioned analytical results, the product adopting the inventive method to prepare is described rosin metal salt resin.
The invention still further relates to described rosin metal salt resin in environmentally friendly purposes in polishing marine antifouling coating.
According to the present invention, described should be appreciated that to be antifouling paint have from the resin of polishing performance for film forming matter with metal ion from polishing marine antifouling coating, sodium ion generation ion exchange reaction in metal ion and seawater, a kind of solubility " soap " is formed at coating surface, under the impact of current, coatingsurface can carry out from polishing, and stain control agent is released process equably from coating, thus plays from polishing antifouling effect.
The present invention relates to a kind of marine antifouling coating.
Described marine antifouling coating is made up of 20 ~ 60 weight part rosin metal salt resins, 1 ~ 20 weight part Red copper oxide, 1 ~ 20 parts by weight of plasticizer, 1 ~ 30 weight part stopping composition and 20 ~ 60 parts by weight solvent.
Rosin metal salt resin prepared by the present invention has good in polishing performance in the seawater, determined by marine panel experiment, compared with rosin, rosin metal salt resin has better snappiness, can be better with other components do match in formulation for coating material, this resinoid can be degraded and be produced such as degraded products such as sodium abietate, nilox resin acid sodium simultaneously, and they have environment friendly.
Rosin metal salt resin prepared by the present invention is mainly its film forming matter as antifouling paint in the effect in polishing marine antifouling coating, not only give antifouling paint excellent from polishing performance, and make antifouling paint have environment friendly.
Red copper oxide is cupprous oxide compound, is red or garnet octahedral isometric system crystalline powder.Red copper oxide can kill rudimentary marine animal and for the preparation of ship bottom anti-fouling paint.
In the effect of the present invention in polishing marine antifouling coating, described Red copper oxide is mainly that it is as stain control agent, be used for killing the lively thing in rudimentary ocean, reduce the adhesion of stained thing on antifouling paint surface.
The present invention's Red copper oxide used is sold in the market, the Red copper oxide that such as Beijing Heng Yezhongyuan Chemical Co., Ltd. sells with trade(brand)name Red copper oxide.
In the present invention, rosin metal salt resin is 20 ~ 60 weight parts, when the content of other component is in described scope, if the amount of Red copper oxide is lower than 1 weight part, then reduces the anti-fouling effect of antifouling paint; If the amount of Red copper oxide is higher than 20 weight parts, then the environment friendly of antifouling paint is made to reduce; Therefore, the amount of Red copper oxide is 1 ~ 20 weight part is desirable, preferably 4 ~ 16 weight parts, more preferably 8 ~ 12 weight parts.
Usually, softening agent a kind ofly adds the material that the plasticity of polymeric system can be made in polymeric system to increase to.The Main Function of softening agent is that the secondary valency weakened between polymer molecule is good for, i.e. Van der Waals force, thus increase the movability of polymer molecular chain, reduce the crystallinity of polymer molecular chain, namely polymer plastic is increased, it shows the hardness, modulus, softening temperature and the embrittlement temperature that are polymkeric substance and declines, and elongation, flexibility and snappiness improve.Softening agent is the industrial macromolecular material auxiliary agent be widely used.
In the present invention, softening agent is mainly in the effect of the present invention in polishing marine antifouling coating the snappiness improving antifouling paint, reduces the fragility of film, prevents film premature rupture, comes off.
The softening agent that the present invention uses is that one or more are selected from the softening agent of clorafin, Vaseline, Ultra-low molecular weight polymethylmethacrylate or polymeric amide.
The softening agent that the present invention uses is all product sold in the market, the clorafin such as sold with trade(brand)name clorafin by Yangzhou Ke Li Chemical Co., Ltd., the Ultra-low molecular weight polymethylmethacrylate sold with trade(brand)name polymethylmethacrylate by Yun Bang bio tech ltd, Beijing, the polymeric amide sold with trade(brand)name polymeric amide by Shanghai Hao Hua Chemical Co., Ltd..
In the present invention, rosin metal salt resin is 20 ~ 60 weight parts, and when the content of other component is in described scope, if the amount of softening agent is lower than 1 weight part, then antifouling paint film easily bubbles, cracking; If the amount of softening agent is higher than 20 weight parts, then antifouling coating film is not easy drying, brushing time lengthening; Therefore, the amount of softening agent is 1 ~ 20 weight part is desirable, preferably 4 ~ 16 weight parts, more preferably 8 ~ 12 weight parts.
In the present invention, stopping composition is the gloss, quality, suspension, viscosity etc. that adjust antifouling paint at the Main Function of the present invention in polishing marine antifouling coating.
The stopping composition that the present invention uses is that one or more are selected from the stopping composition of red iron oxide, aerosil, talcum powder, titanium dioxide or zinc oxide.
The stopping composition that the present invention uses is all product sold in the market, the red iron oxide of such as being sold with trade(brand)name ferric oxide by Tianjin Chemical Co., Ltd.'s all generations, the aerosil sold with trade(brand)name silicon-dioxide by Tianjin Chemical Co., Ltd.'s all generations, the titanium dioxide sold with trade(brand)name titanium dioxide by Tianjin Chemical Co., Ltd.'s all generations.
In the present invention, rosin metal salt resin is 20 ~ 60 weight parts, and when the content of other component is in described scope, if the amount of stopping composition is lower than 1 weight part, then antifouling paint viscosity is too little, film tarnish, and time of drying is oversize; If the amount of stopping composition is higher than 30 weight parts, then antifouling paint viscosity is excessive, and film becomes fragile, and easily chaps; Therefore, the amount of stopping composition is 1 ~ 30 weight part is rational, preferably 6 ~ 24 weight parts, more preferably 12 ~ 18 weight parts.
In the present invention, solvent is the organic substance in dissolution of coatings at the Main Function of the present invention in polishing marine antifouling coating, regulates the viscosity of antifouling paint, makes coating be easy to construction and improve film performance.
The solvent that the present invention uses is that one or more are selected from the solvent of ethyl acetate, butylacetate, dimethylbenzene, toluene or propyl carbinol.
The solvent that the present invention uses is all product sold in the market.
In the present invention, rosin metal salt resin is 20 ~ 60 weight parts, and when the content of other component is in described scope, if the amount of solvent is lower than 20 weight parts, then the organic substance in coating can not dissolve completely, and paint viscosity is easily excessive, not easily constructs; If the amount of stopping composition is higher than 60 weight parts, then paint viscosity is too little, increases brushing difficulty, and a large amount of solvent evaporates is too fast, easily causes film cracking; Therefore, the amount of stopping composition is 20 ~ 60 weight parts is rational, preferably 28 ~ 50 weight parts, more preferably 36 ~ 42 weight parts.
Preferably, described marine antifouling coating is made up of 28 ~ 50 weight part rosin metal salt resins, 4 ~ 16 weight part Red copper oxide, 4 ~ 16 parts by weight of plasticizer, 6 ~ 24 weight part stopping composition and 28 ~ 50 parts by weight solvent.
More preferably, described marine antifouling coating is made up of 36 ~ 42 weight part rosin metal salt resins, 8 ~ 12 weight part Red copper oxide, 8 ~ 12 parts by weight of plasticizer, 12 ~ 18 weight part stopping composition and 36 ~ 42 parts by weight solvent.
Marine antifouling coating of the present invention can adopt conventional coating method to be coated with.
In sea area, wheat island, Qingdao City, test the antifouling property of the marine antifouling coating containing rosin metal salt resin of the present invention with reference to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).With usually use conventional propylene acid metal salt resin as compared with film forming matter in prior art, marine antifouling coating of the present invention discharges evenly in the seawater, smooth and the difficult drop-off of film, can better play antifouling property, makes the antifouling phase effect of antifouling paint reach more than 24 months.
[beneficial effect]
Beneficial effect of the present invention is as follows:
Rosin metal salt resin syntheses processes of the present invention is simple, and raw material is cheap and easy to get; Rosin metal salt resin of the present invention to environment without harm; Compared with existing rosin, rosin metal salt resin coating film good toughness of the present invention, can be used as main film forming matter to be used alone, can be better with other components do match in formulation for coating material, degradable, more excellent from polishing performance, and effect of antifouling phase is long, meet the development trend of antifouling paint, have a good application prospect.
[accompanying drawing explanation]
Fig. 1: the infrared spectrum of rosin zinc resin;
Fig. 2: the infrared spectrum of nilox resin resin of copper;
Fig. 3: the infrared spectrum of dimerization colophonium magnesium resin;
Fig. 4: the infrared spectrum of rosin-disproportionating rosin zinc;
Fig. 5: the infrared spectrum of nilox resin dimerization colophonium zinc;
Fig. 6: the infrared spectrum of rosin dimerization rosin calcium;
Fig. 7: the infrared spectrum of rosin;
Fig. 8: the antifouling test result figure of the real extra large link plate of metal-salt resin coating of the present invention;
Fig. 9: the antifouling test result figure of the real extra large link plate of marine antifouling coating of the present invention.
[embodiment]
The present invention can be understood better by following embodiment.
Embodiment 1: the preparation of rosin metal salt resin of the present invention
The implementation step of this embodiment is as follows:
The rosin sold 90 weight parts with trade(brand)name rosin by Zhengzhou Zhi Yuan Chemicals company limited of company and toluene solvant add in the reactor being equipped with whipping appts and thermometer, under the condition of temperature 85 DEG C, heating makes rosin dissolve completely, add the zinc hydroxide that 10 weight parts are sold with trade(brand)name zinc hydroxide by chemistry materials factory of Wenzhou City again, the amount of described toluene solvant is reactant gross weight 8 times, then react 45 hours under the condition of temperature 110 DEG C, connect and be warming up to 120 DEG C and carry out dewatering until exclusion distillates, terminate reaction, obtain described rosin zinc resin.
Adopt conventional infrared spectroscopy to use to fly by Sai Mo the infrared spectrometer that your science and technology (China) company limited of generation sells with trade(brand)name infrared spectrometer and carry out INFRARED SPECTRUM mensuration to the rosin zinc resin that the present embodiment prepares, its infrared measurement the results are shown in accompanying drawing 1.
Rosin zinc resin prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 8.
Embodiment 2: the preparation of rosin metal salt resin of the present invention
The implementation step of this embodiment is as follows:
The nilox resin sold 80 weight parts with trade(brand)name nilox resin by Beijing Lin Xinlong Chemicals company limited and xylene solvent add in the reactor being equipped with whipping appts and thermometer, under the condition of temperature 80 DEG C, heating makes nilox resin dissolve completely, add the copper hydroxide that 1 weight part is sold with trade(brand)name copper hydroxide by Chinasun Specialty Products Co., Ltd again, the amount of described xylene solvent is reactant gross weight 0.2 times, then react 90 hours under the condition of temperature 80 DEG C, then be warming up to 120 DEG C to carry out dewatering until exclusion distillates, terminate reaction, obtain described nilox resin resin of copper.
Adopt the same method described with embodiment 1 to carry out INFRARED SPECTRUM mensuration to the nilox resin resin of copper that the present embodiment prepares, its infrared measurement the results are shown in accompanying drawing 2.
Nilox resin resin of copper prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 8.
Embodiment 3: the preparation of rosin metal salt resin of the present invention
The implementation step of this embodiment is as follows:
The dimerization colophonium sold 85 weight parts with trade(brand)name DMER-145 Gum Rosin by Jin Tenglong trade Co., Ltd of Shenzhen and n-butanol solvent add in the reactor being equipped with whipping appts and thermometer, under the condition of temperature 75 DEG C, heating makes dimerization colophonium dissolve completely, add the magnesium hydroxide that 5 weight parts are sold with trade(brand)name magnesium hydroxide by Yixing City lark Fine Chemical Co., Ltd again, the amount of described n-butanol solvent is reactant gross weight 2 times, then react 60 hours under the condition of temperature 100 DEG C, then be warming up to 120 DEG C to carry out dewatering until exclusion distillates, terminate reaction, obtain described dimerization colophonium magnesium resin.
Adopt the same method described with embodiment 1 to carry out INFRARED SPECTRUM mensuration to the dimerization colophonium magnesium resin that the present embodiment prepares, its infrared measurement the results are shown in accompanying drawing 3.
Dimerization colophonium magnesium resin prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 8.
Embodiment 4: the preparation of rosin metal salt resin of the present invention
The implementation step of this embodiment is as follows:
The rosin that 99 weight parts are sold with trade(brand)name rosin by Zhengzhou Zhi Yuan Chemicals company limited is added in the reactor being equipped with whipping appts and thermometer with the nilox resin mixture (weight ratio 1:1) sold with trade(brand)name nilox resin by the prosperous limited department of imperial Chemicals of public Beijing woods with butyl acetate solvent, under the condition of temperature 85 DEG C, heating makes rosin and nilox resin mixture dissolve completely, add the zinc oxide that 8 weight parts are sold with trade(brand)name zinc oxide by Changzhou Ya Lang Chemical Co., Ltd. again, the amount of described butyl acetate solvent is reactant gross weight 4 times, then react 120 hours under the condition of temperature 50 C, then be warming up to 120 DEG C to carry out dewatering until exclusion distillates, terminate reaction, obtain described rosin-disproportionating rosin zinc resin.
Adopt the same method described with embodiment 1 to carry out INFRARED SPECTRUM mensuration to the rosin-disproportionating rosin zinc resin that the present embodiment prepares, its infrared measurement the results are shown in accompanying drawing 4.
Rosin-disproportionating rosin zinc resin prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 8.
Embodiment 5: the preparation of rosin metal salt resin of the present invention
The implementation step of this embodiment is as follows:
The nilox resin that 90 weight parts are sold with trade(brand)name nilox resin by Beijing Lin Xinlong Chemicals company limited and the dimerization colophonium mixture (weight ratio 1:3) sold with trade(brand)name name DMER-145 Gum Rosin by Jin Tenglong trade Co., Ltd of Shenzhen and propyl carbinol, butylacetate and cyclohexanone mixture (weight ratio 2:1:3) solvent add in the reactor being equipped with whipping appts and thermometer, under the condition of temperature 80 DEG C, heating makes nilox resin and dimerization colophonium mixture dissolve completely, add the cupric oxide that 15 weight parts are sold with trade(brand)name cupric oxide by upper sea green source Fine Chemical Works again, the amount of described cyclohexanone solvent is reactant gross weight 6 times, then react 30 hours under the condition of temperature 140 DEG C, then temperature adjustment to 120 DEG C is carried out dewatering until exclusion distillates, terminate reaction, obtain described nilox resin dimerization colophonium resin of copper.
Adopt the same method described with embodiment 1 to carry out INFRARED SPECTRUM mensuration to the nilox resin dimerization colophonium resin of copper that the present embodiment prepares, its infrared measurement the results are shown in accompanying drawing 5.
Nilox resin dimerization colophonium resin of copper prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 8.
Embodiment 6: the preparation of rosin metal salt resin of the present invention
The implementation step of this embodiment is as follows:
The rosin that 95 weight parts are sold with trade(brand)name rosin by Zhengzhou Zhi Yuan Chemicals company limited and the dimerization colophonium mixture (weight ratio 3:2) sold with trade(brand)name DMER-145 Gum Rosin by Jin Tenglong trade Co., Ltd of Shenzhen and toluene, dimethylbenzene and propyl carbinol mixture (weight ratio 1:2:1) solvent add in the reactor being equipped with whipping appts and thermometer, under the condition of temperature 75 DEG C, heating makes rosin and dimerization colophonium mixture dissolve completely, add 20 weight parts again to be stablized the country the calcium oxide that Gai Ye company limited sells with trade(brand)name calcium oxide by Zhejiang, the amount of described admixture solvent is reactant gross weight 9 times, then react 2 hours under the condition of temperature 180 DEG C, then temperature adjustment to 120 DEG C is carried out dewatering until exclusion distillates, terminate reaction, obtain described rosin dimerization rosin calcium resin.
Adopt the same method described with embodiment 1 to carry out INFRARED SPECTRUM mensuration to the rosin calcium resin that the present embodiment prepares, its infrared measurement the results are shown in accompanying drawing 6.
Rosin dimerization rosin calcium resin prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 8.
The infrared spectrum of embodiment 1-6 is analyzed as follows: analyze in contrast with the spectrogram of simple rosin, and rosin spectrogram is see Fig. 7.Rosin, owing to depositing hydrogen bond between carboxyl, gives electronics mutually, so than normal carbonyl stretching absorbance peak 1715cm
-1wave number low, at 1695cm
-1place produces absorption peak, because the hydrogen bond formed is identical, identical on the stretching vibration impact of carbonyl, only produces an absorption peak, the characteristic peak 2650cm of hydrogen bond between carboxylic acid molecules
-1and 2540cm
-1also clearly.Contrast with rosin spectrogram, Fig. 1 can find out at 1460cm
-1there is the ν as absorption peak of COO-Zn in place, at 1409cm
-1there is the ν s absorption peak of COO-Zn in place; Fig. 2 can find out at 1460cm
-1there is the ν as absorption peak of COO-Cu in place, at 1397cm
-1there is the ν s absorption peak of COO-Cu in place; Fig. 3 can find out 1460cm
-1there is the ν as absorption peak of COO-Mg in place, at 1413cm
-1there is the ν s absorption peak of COO-Mg in place; Can find out at 1450cm in Fig. 4
-1there is the ν as absorption peak of COO-Zn in place, at 1418cm
-1there is the ν s absorption peak of COO-Zn in place; Can find out at 1460cm in Fig. 5
-1there is the ν as absorption peak of COO-Cu in place, at 1412cm
-1there is the ν s absorption peak of COO-Cu in place; Can find out at 1458.6cm in Fig. 6
-1there is the ν as absorption peak of COO-Ca in place, at 1416.9cm
-1there is the ν s absorption peak of COO-Ca in place; Illustrate that metal ion has successfully been received on the carboxyl of rosin and rosin derivative.
Embodiment 7: the preparation of marine antifouling coating of the present invention
The implementation step of this embodiment is as follows:
The red iron oxide stopping composition that chlorinated paraffin plasticizer, 26 weight parts that Red copper oxide, 20 weight parts that the rosin metal salt resin prepared by embodiment 1 by 50 weight parts, 6 weight parts are sold with trade(brand)name Red copper oxide by Beijing Heng Yezhongyuan Chemical Co., Ltd. are sold with trade(brand)name clorafin by Yangzhou Ke Li Chemical Co., Ltd. are sold with trade(brand)name ferric oxide by Tianjin Chemical Co., Ltd.'s all generations and 52 weight part of ethylacetate solvents fully grind, then use 100 order strainers to filter, the filtrate obtained is marine antifouling coating of the present invention.
Marine antifouling coating prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 9.
Embodiment 8: the preparation of marine antifouling coating of the present invention
The implementation step of this embodiment is as follows:
The aerosil stopping composition that Vaseline softening agent, 1 weight part that Red copper oxide, 8 weight parts that the rosin metal salt resin prepared by embodiment 2 by 20 weight parts, 1 weight part are sold with trade(brand)name Red copper oxide by Beijing Heng Yezhongyuan Chemical Co., Ltd. are sold with trade(brand)name Vaseline by Beijing Heng Yezhongyuan Chemical Co., Ltd. are sold with trade(brand)name silicon-dioxide by Tianjin Chemical Co., Ltd.'s all generations and 20 weight part butyl acetate solvent are fully ground, then use 100 order strainers to filter, the filtrate obtained is marine antifouling coating of the present invention.
Marine antifouling coating prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 9.
Embodiment 9: the preparation of marine antifouling coating of the present invention
The implementation step of this embodiment is as follows:
The rosin metal salt resin that 40 weight parts are prepared by embodiment 3, the Red copper oxide that 10 weight parts are sold with trade(brand)name Red copper oxide by Beijing Heng Yezhongyuan Chemical Co., Ltd., the Ultra-low molecular weight polymethylmethacrylate softening agent that 10 weight parts are sold with trade(brand)name polymethylmethacrylate by Yun Bang bio tech ltd, Beijing, the talc material that 15 weight parts are sold with trade(brand)name talcum powder by the magnificent talcum powder development corporation, Ltd. of LONGSHENG IN GUANGXI and 38 parts by weight of xylene solvents fully grind, then 100 order strainers are used to filter, the filtrate obtained is marine antifouling coating of the present invention.
Marine antifouling coating prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 9.
Embodiment 10: the preparation of marine antifouling coating of the present invention
The implementation step of this embodiment is as follows:
The rosin metal salt resin that 45 weight parts are prepared by embodiment 4, the Red copper oxide that 20 weight parts are sold with trade(brand)name Red copper oxide by Beijing Heng Yezhongyuan Chemical Co., Ltd., the polyamide plasticizers that 14 weight parts are sold with trade(brand)name polymeric amide by Shanghai Hao Hua Chemical Co., Ltd., the titanium dioxide stopping composition that 30 weight parts are sold with trade(brand)name titanium dioxide by Tianjin Chemical Co., Ltd.'s all generations and 42 part by weight of n-butanol solvents fully grind, then the 100 order strainers sold with trade(brand)name basket filter by Zibo Xu Long petrochemical equipment company limited are used to filter, the filtrate obtained is marine antifouling coating of the present invention.
Marine antifouling coating prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 9.
Embodiment 11: the preparation of marine antifouling coating of the present invention
The implementation step of this embodiment is as follows:
The rosin metal salt resin that 60 weight parts are prepared by embodiment 5, the Red copper oxide that 12 weight parts are sold with trade(brand)name Red copper oxide by Beijing Heng Yezhongyuan Chemical Co., Ltd., 1 the weight part clorafin sold with trade(brand)name clorafin by Yangzhou Ke Li Chemical Co., Ltd. and Ultra-low molecular weight polymethyl acrylate blend (weight ratio 1:1) softening agent sold with trade(brand)name polymethylmethacrylate by Yun Bang bio tech ltd, Beijing, the titanium dioxide stopping composition that 8 weight parts are sold with trade(brand)name titanium dioxide by Tianjin Chemical Co., Ltd.'s all generations and 60 weight part of ethylacetate, dimethylbenzene and propyl carbinol mixture (weight ratio 1:1:1) solvent fully grind, then the 100 order strainers sold with trade(brand)name basket filter by Zibo Xu Long petrochemical equipment company limited are used to filter, the filtrate obtained is marine antifouling coating of the present invention.
Marine antifouling coating prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 9.
Embodiment 12: the preparation of marine antifouling coating of the present invention
The implementation step of this embodiment is as follows:
The rosin metal salt resin that 30 weight parts are prepared by embodiment 6, the Red copper oxide that 16 weight parts are sold with trade(brand)name Red copper oxide by Beijing Heng Yezhongyuan Chemical Co., Ltd., the polyamide plasticizers that 18 weight parts are sold with trade(brand)name polymeric amide by Shanghai Hao Hua Chemical Co., Ltd., the zinc oxide stopping composition that 20 weight parts are sold with trade(brand)name zinc oxide by Weifang Hengfeng Chemical Co., Ltd. and 28 weight part butylacetates, toluene and propyl carbinol mixture (weight ratio 1:2:2) solvent fully grind, then 100 order strainers are used to filter, the filtrate obtained is marine antifouling coating of the present invention.
Marine antifouling coating prepared by the present embodiment adopts conventional coating method to be coated with, and tests its antifouling property according to national standard " antifouling varnish model shallow sea soak test method " (GB/T 5370-2007).Its test result is shown in accompanying drawing 9.
The marine anti-pollution the performance test results of rosin metal salt resin of the present invention is as follows:
Marine anti-pollution performance test has been carried out to rosin metal salt resin prepared by embodiment 1-6, its test result is listed in Fig. 8, they are represent with R1-R6 respectively, and carried out corresponding test with rosin xylene solution in contrast to blank, they are that R7 and R0 represents respectively simultaneously.
Test duration selectes the late March 18 totally months of marine organism growth vigorous late September to 2013 of 2011 year, wherein divide 3 time periods to investigate marine organisms coverage conditions, first time period is leaching sea 6 months, second time period be 12 months, the 3rd time period of leaching sea is 18 months, leaching sea.
As seen from Figure 8, in leaching sea after 6 months, blank model is covered by marine organisms (as micro-algae) and biological mucosa completely, be that the surface attachment of coating has a small amount of micro-algae, microorganism mucous membrane and mud with rosin solution, and resin prepared by embodiment of the present invention 1-6 is only attached with the mud of minute quantity.
Leaching sea is after 12 months, blank model is covered by a large amount of marine organisms (as marine alga, mussel etc.) completely, and thickness increases, be that the surface of coating is except being coated with a large amount of microorganism mucous membranes and mud with rosin solution, also be coated with a small amount of marine alga, and resin prepared by embodiment of the present invention 1-6 is still only attached with a small amount of mud.
Leaching sea is after 18 months, blank model is covered by a large amount of ocean macro-organisms (as mussel, Ascidian etc.) completely, and thickness increases, with rosin solution be the surface of coating except being coated with a small amount of marine organisms, and resin prepared by embodiment of the present invention 1-6 is only attached with a small amount of mud and biological mucosa.
Can real extra large board experiment result be found out by above-mentioned, compare with simple rosin solution coating, rosin of the present invention and rosin derivative metal-salt resin have excellent antifouling activity, and antifouling phase effect reaches more than 18 months.
The marine anti-pollution the performance test results of antifouling paint is as follows:
Respectively marine anti-pollution performance test is carried out to the antifouling paint (representing with D1 in Fig. 9) prepared for film forming matter with conventional acrylic zinc resin, the antifouling paint (representing with D2 in Fig. 9) prepared for film forming matter with conventional acrylic resin of copper and blank (being called for short D0).
Wherein the preparation method of conventional acrylic zinc resin is as follows:
Add in 500mL there-necked flask by 8g vinylformic acid, 15g methyl methacrylate, 15g n-butyl acrylate, 0.8g Diisopropyl azodicarboxylate, 30g dimethylbenzene and 10g propyl carbinol when the temperature 100 DEG C, after reinforced, insulation obtains acrylic resin in 2 hours.10g zinc hydroxide, 12g naphthenic acid, 20g dimethylbenzene and 20g propyl carbinol are added in aforesaid propylene acid resin system, react 5 hours at temperature 80 DEG C, then be warming up to 120 DEG C of dehydrations, be sure of that exclusion distillates rear end reaction, obtain conventional acrylic zinc resin.
The preparation method of conventional acrylic resin of copper is as follows:
Add in 500mL there-necked flask by 8g vinylformic acid, 15g methyl methacrylate, 15g n-butyl acrylate, 0.8g Diisopropyl azodicarboxylate, 30g dimethylbenzene and 10g propyl carbinol when the temperature 100 DEG C, after reinforced, insulation obtains acrylic resin in 2 hours.10g copper hydroxide, 12g naphthenic acid, 20g dimethylbenzene and 20g propyl carbinol are added in aforesaid propylene acid resin system, react 5 hours at temperature 80 DEG C, then be warming up to 120 DEG C of dehydrations, be sure of that exclusion distillates rear end reaction, obtain conventional acrylic resin of copper.
As follows with the antifouling paint preparation method that conventional acrylic zinc resin is film forming matter:
By conventional acrylic zinc resin, clorafin, Red copper oxide, red iron oxide, dimethylbenzene according to after weight part 45,5,5,5,40 fully grinding, filter with 100 order strainers, the marine antifouling coating that its filtrate is is film forming matter with conventional acrylic zinc resin.
The antifouling paint preparation method being film forming matter with conventional acrylic resin of copper is as follows:
The conventional acrylic resin of copper of the above-mentioned preparation of 45 weight part, 5 weight part clorafins, 5 weight part Red copper oxide, 5 weight part red iron oxides and 40 parts by weight of xylene are fully ground according to weight part, then filter with 100 order strainers, the marine antifouling coating that its filtrate is is film forming matter with conventional acrylic resin of copper.
Antifouling paint prepared by embodiment 7,8,9,10,11,12 is tested, and wherein the antifouling paint of each embodiment represents with A, B, C, D, E, F in fig .9 respectively successively.
In Fig. 9, the examination phase of test piece antifouling property is more than 24 totally months late September of marine organism growth vigorous late September to 2013 of 2011 year.Being divided into 3 time periods tests, wherein first time period for leaching sea 8 months, second time period for leaching sea 16 months, the 3rd time period is leaching sea 24 months.
Found out by Fig. 9, leaching sea is after 8 months, blank model is covered completely by a large amount of ocean macro-organisms (as marine alga, mussel etc.), have microorganism mucous membrane, mud with the antifouling paint surface attachment that conventional acrylic zinc resin, conventional acrylic resin of copper are prepared for film forming matter, and antifouling paint prepared by the embodiment of the present invention 7,8,9,10,11,12 is only attached with the mud of minute quantity.
Leaching sea is after 16 months, the ocean macro-organism layer thickness that blank model covers increases the weight of, surperficial except being coated with a large amount of microorganism mucous membranes and mud with the antifouling paint that conventional acrylic zinc resin, conventional acrylic resin of copper are prepared for film forming matter, also be coated with a large amount of micro-algaes, and antifouling paint prepared by the embodiment of the present invention 7,8,9,10,11,12 is still only attached with a small amount of mud.
Leaching sea is after 24 months, covered completely by biological mucosa and a large amount of micro-algae with the antifouling paint surface that conventional acrylic zinc resin, conventional acrylic resin of copper are prepared for film forming matter, and antifouling paint prepared by the embodiment of the present invention 7,8,9,10,11,12 is only attached with a small amount of mud and microorganism mucous membrane, still there is good antifouling property.
Total solid extra large board experiment result is found out, compared with blank test, with conventional acrylic zinc/resin of copper for antifouling paint prepared by film forming matter has good antifouling property, the present invention is that antifouling paint prepared by film forming matter has more excellent antifouling activity with the rosin based material metal-salt resin containing general formula (I) structure, and antifouling phase effect reaches more than 24 months.
Claims (10)
1. a rosin metal salt resin, is characterized in that this resin has following structural formula (I):
R-X-R
1(I)
In formula:
R represents the sour acid group of sylvic acid, nilox resin acid or dimerization colophonium;
X represents Zn
2+, Cu
2+, Mg
2+or Ca
2+metal ion;
R
1represent the acid group that sylvic acid, nilox resin acid or dimerization colophonium are sour.
2. rosin metal salt resin according to claim 1, it is characterized in that described rosin metal salt resin is rosin zinc resin, rosin resin of copper, rosin magnesium resin, rosin calcium resin, rosin-disproportionating rosin zinc resin, rosin-disproportionating rosin resin of copper, rosin-disproportionating rosin magnesium resin, rosin-disproportionating rosin calcium resin, rosin dimerization rosin zinc resin, rosin dimerization rosin resin of copper, rosin dimerization rosin magnesium resin, rosin dimerization rosin calcium resin, nilox resin zinc resin, nilox resin resin of copper, nilox resin magnesium resin, nilox resin calcium resin, nilox resin dimerization colophonium zinc resin, nilox resin dimerization colophonium resin of copper, nilox resin dimerization colophonium magnesium resin, nilox resin dimerization colophonium calcium resin, dimerization colophonium zinc resin, dimerization colophonium resin of copper, dimerization colophonium magnesium resin or dimerization colophonium calcium resin.
3. the preparation method of rosin metal salt resin according to claim 1, is characterized in that the step of this preparation method is as follows:
By 80 ~ 99 weight parts, one or both are selected from rosin, the rosin based material of nilox resin or dimerization colophonium and solvent add outfit whipping appts, with in the reflux exchanger of oily-water seperating equipment and the reactor of thermometer, under the condition of temperature 30 ~ 85 DEG C, heating makes rosin based material dissolve completely, then oxyhydroxide or the oxide compound of 1 ~ 20 weight part divalent metal is added, the amount of described solvent is 0.2 ~ 9.0 times of reactant gross weight, then react 2 ~ 120 hours under the condition of temperature 50 ~ 180 DEG C, then being warming up to 100 ~ 130 DEG C carries out dewatering until anhydrously to distillate, so obtain described rosin metal salt resin.
4. preparation method according to claim 3, is characterized in that described Divalent metal hydroxide is selected from zinc hydroxide, copper hydroxide, magnesium hydroxide or calcium hydroxide; Described bivalent metal oxide is selected from zinc oxide, cupric oxide, magnesium oxide or calcium oxide.
5. preparation method according to claim 3, is characterized in that described solvent is that one or more are selected from the solvent of toluene, dimethylbenzene, propyl carbinol, butylacetate, ethyl acetate or pimelinketone.
6. rosin metal salt resin according to claim 1 is in environmentally friendly purposes in polishing marine antifouling coating.
7. a marine antifouling coating, is characterized in that described marine antifouling coating is made up of 20 ~ 60 weight part rosin metal salt resins, 1 ~ 20 weight part Red copper oxide, 1 ~ 20 parts by weight of plasticizer, 1 ~ 30 weight part stopping composition and 20 ~ 60 parts by weight solvent.
8. marine antifouling coating according to claim 7, is characterized in that described softening agent is that one or more are selected from the softening agent of clorafin, Vaseline, Ultra-low molecular weight polymethylmethacrylate or polymeric amide.
9. marine antifouling coating according to claim 8, is characterized in that described stopping composition is that one or more are selected from the stopping composition of red iron oxide, aerosil, talcum powder, titanium dioxide or zinc oxide.
10. marine antifouling coating according to claim 8, is characterized in that described solvent is that one or more are selected from the solvent of ethyl acetate, butylacetate, pimelinketone, dimethylbenzene, toluene or propyl carbinol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106120362A (en) * | 2016-08-30 | 2016-11-16 | 苏州瑞高新材料有限公司 | A kind of medical synthetic leather and preparation method thereof |
| CN108912921A (en) * | 2017-07-25 | 2018-11-30 | 山东科耀化工有限公司 | The preparation method of Self-leveling, self-polishing marine antifouling paint |
| CN114395332A (en) * | 2022-01-29 | 2022-04-26 | 广东植物龙生物技术股份有限公司 | Rosin-based metal complex and application thereof |
-
2014
- 2014-12-23 CN CN201410811712.1A patent/CN104530985A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106120362A (en) * | 2016-08-30 | 2016-11-16 | 苏州瑞高新材料有限公司 | A kind of medical synthetic leather and preparation method thereof |
| CN108912921A (en) * | 2017-07-25 | 2018-11-30 | 山东科耀化工有限公司 | The preparation method of Self-leveling, self-polishing marine antifouling paint |
| CN108912921B (en) * | 2017-07-25 | 2021-05-04 | 山东科耀化工有限公司 | Preparation method of self-leveling and self-polishing type marine antifouling paint |
| CN114395332A (en) * | 2022-01-29 | 2022-04-26 | 广东植物龙生物技术股份有限公司 | Rosin-based metal complex and application thereof |
| CN114395332B (en) * | 2022-01-29 | 2024-01-26 | 广东植物龙生物技术股份有限公司 | Rosin-based metal complex and application thereof |
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