CN108690473A - The preparation method of rosin acid modified alkyd resin zinc salt antifouling paint - Google Patents

The preparation method of rosin acid modified alkyd resin zinc salt antifouling paint Download PDF

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Publication number
CN108690473A
CN108690473A CN201710610532.0A CN201710610532A CN108690473A CN 108690473 A CN108690473 A CN 108690473A CN 201710610532 A CN201710610532 A CN 201710610532A CN 108690473 A CN108690473 A CN 108690473A
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zinc salt
alkyd resin
rosin acid
modified alkyd
rosin
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CN201710610532.0A
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CN108690473B (en
Inventor
王树礼
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Chemical Co Ltd Shandong Branch Yao
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Chemical Co Ltd Shandong Branch Yao
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46Polyesters chemically modified by esterification
    • C08G63/48Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1606Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662Synthetic film-forming substance

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to coating preparation field, more particularly to a kind of preparation method of rosin acid modified alkyd resin zinc salt antifouling paint is counted, the rosin acid modified alkyd resin zinc salt antifouling paint is composed of the following components in parts by weight:900 ~ 1100 parts of rosin acid modified alkyd resin zinc salt, mix 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive, the above components carry out high speed dispersion or obtain rosin acid modified alkyd resin zinc salt antifouling paint after being sanded in the agitator tank equipped with high speed disperser or in sand mill.Introduce modified rosin acid structure in the present invention has the characteristics that strong adhesive force, flexibility are good, cohesive performance is excellent, quick-drying, and minimum to the pollution of marine environment compared with general coating, more environmentally friendly.Displacement property ionization reaction will occur in the seawater for coating containing zinc salt, dissociate and generate the sodium salt and zinc ion of rosin acid, have inhibition growth to ocean small parasitic biology, also have obvious cleaning protection to ship, dyke, bank base.

Description

The preparation method of rosin acid modified alkyd resin zinc salt antifouling paint
Technical field
The present invention relates to coating preparation field, more particularly to a kind of system of rosin acid modified alkyd resin zinc salt antifouling paint Preparation Method.
Background technology
Hull, harbour, drilling platforms etc. are located at the attachment that the part under water line is vulnerable to bacterium and marine organisms at present It is stained, a large amount of waste that adheres to not only increases the dead weight of ship, reduces the load-carrying of ship, while the resistance that will greatly increase hull Power causes the speed of a ship or plane of ship to reduce the increase with fuel consumption.And fall off after fouling organism death, it is also possible to be inhaled into equipment Pipeline in, cause the blocking of pipeline.The breeding of fouling organism can also cause the corrosion protective layer of ship or off-shore structure Damage, accelerates the corrosion of metal component, reduces the service life of ship and marine structure.Usually all it is to be applied in these parts Antifouling paint prevents marine organisms from adhering to, the marine antifouling coating of traditional tin system due to marine eco-environment pollution compared with Greatly, it has been forbidden to use.Rosin is widely used in soap, papermaking, paint and rubber etc. as a kind of important industrial chemicals Industry.The modification of rosin, the reaction active groups such as general conjugated double bond, carboxyl using in rosin molecular structure, by addition, Hydrogenation, polymerization, ammonolysis, at reactions such as salt, esterifications maleic rosin, disproportionated rosin, hydrogenated rosin, newtrex, pine is made in disproportionation The deep processed products such as fragrant amine, abietate and various rosin esters.
Invention content
In order to make up the above deficiency, the present invention discloses a kind of preparation side of rosin acid modified alkyd resin zinc salt antifouling paint Method, rosin modified alkyd resin refers to the addition modifying agent rosin in the preparation process of alkyd resin, made of chemical reaction Modified resin.Due to the modification of rosin, the resin is made to be soluble in esters solvent, the adhesive force of paint film can be increased, reduced paint film and rise Wrinkle improves durability, alkali resistance and the gloss of paint film, reduces viscosity;Paint film release solvent is also very fast, does rate and improves, parches and adding Soon, and to the less pollution of marine environment.
The present invention is achieved through the following technical solutions:A kind of system of rosin acid modified alkyd resin zinc salt antifouling paint Preparation Method, which is characterized in that count in parts by weight, the rosin acid modified alkyd resin zinc salt antifouling paint is by following components group At:900 ~ 1100 parts of rosin acid acid modified alcoholic tree zinc salt mixes 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive.
Preferably, it is prepared by following processing steps:
Step 1:Rosin acid refines
Ethanol water is added in rosin, adds the aqueous solution of sodium hydroxide, is heated to boiling, return stirring reaction 3 ~ 4 Hour, activated carbon decolorizing, filtering is added, filtrate is cooled to 0 ~ 4 DEG C, is slowly dropped into aqueous hydrochloric acid solution, filters again, obtain slightly Yellow solid is washed with water to neutrality.
Step 2:The preparation of rosin acid modified alkyd resin zinc salt
Refined rosin acid, polyalcohol, substance and solvent containing oleic acid are added in a kettle, is warming up to 90 ~ 100 DEG C, instead 0.5 ~ 1h is answered, alkyl dicarboxylic aid then is added and dry oxidation zinc stirs evenly, is heated to boiling, dehydration 1h;Increase temperature Degree reacts 2 ~ 4h to 210 ~ 220 DEG C, measures acid value as 80 hereinafter, up to rosin acid modified alkyd resin zinc salt.
Step 3:The preparation of rosin acid modified alkyd resin zinc salt antifouling paint
By 900 ~ 1100 parts of the rosin acid modified alkyd resin zinc salt, 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive are mixed, Dispersion is sanded to 40 μm of granularity hereinafter, to obtain the final product.
Preferably, in step 1:The volume fraction of the ethyl alcohol is 75% ~ 90%, and the sodium hydroxide is water-soluble The concentration of liquid and hydrochloric acid is 1 ~ 3mol/L, and the molar ratio of the rosin, sodium hydroxide and hydrochloric acid is 10:1:1.2, rosin, ethyl alcohol Mass ratio with activated carbon is 100:150~170:1~3.
Preferably, in step 2:The solvent is one kind in toluene or n-butanol, and the polyalcohol is season One kind in penta tetrol, glycerine or trihydroxy methyl propane, the substance containing oleic acid are behenic acid, castor oil, sunflower seeds One kind in oil, palm oil, cottonseed oil or rapeseed oil, the alkyl dicarboxylic aid are in succinic acid, maleic acid, fumaric acid or oxalic acid It is one or more;The rosin acid, polyalcohol, the substance containing oleic acid, alkyl dicarboxylic aid and dry oxidation zinc weight ratio be 100:35~45:45~55:25~35:0.02~0.03.
The beneficial effects of the invention are as follows:Modified rosin acid structure is introduced in the present invention, and compared with general coating, there is attachment The features such as power is strong, flexibility is good, cohesive performance is excellent, quick-drying, and it is minimum to the pollution of marine environment, it is more environmentally friendly.Containing zinc salt Displacement property ionization reaction will occur in the seawater for coating, dissociate and generate the sodium salt and zinc ion of rosin acid, small to ocean to post Raw biology has inhibition growth, also has obvious cleaning protection to ship, dyke, bank base.
Description of the drawings
Fig. 1 is the hanging test of the embodiment of the present invention 1.
Specific implementation mode
Below by embodiment, the present invention will be further described, but the scope of the invention is not limited.
Embodiment 1:
Rosin acid refines:The ethyl alcohol 800ml that volume fraction is 75% is added in 300g rosin, adds the 2mol/L of 50ml Sodium hydrate aqueous solution is heated to boiling, and return stirring reacts 3.5 hours, and 6g activated carbon decolorizings, filtering, filtrate cooling is added To 0 ~ 4 DEG C, 60ml 2mol/L aqueous hydrochloric acid solutions are slowly dropped into, are filtered again, yellowish solid is obtained, are washed with water to neutrality.
The preparation of rosin acid modified alkyd resin zinc salt:To equipped with blender, thermometer, straight pipe condensation pipe, water-oil separating 1013g rosin acids, 421g glycerine and 506g behenic acids are added in the reaction kettle of device, is warming up to 95 DEG C, reacts 35 minutes, then 320g fumaric acid, 2.3g oxalic acid and 0.253g dry oxidation zinc is added to stir evenly, is heated to boiling, dehydration 1h;It increases Temperature is to 220 DEG C, then reacts 3h, measures acid value as 80 hereinafter, up to rosin acid modified alkyd resin zinc salt.
The preparation of rosin acid modified alkyd resin zinc salt antifouling paint:
Rosin acid modified alkyd resin zinc salt 1000g is added into the coating material production tank equipped with high speed dispersor, mixes antirust face Expect 45g, coating additive 2g, carry out high speed dispersion, survey fineness at 40 μm hereinafter, to obtain the final product.
Performance test:
Adhesive force(Grade):It is evaluated as 1 by GB/T1720-1989 standards;
Flexibility(mm):It is evaluated as 1 by GB/T1731-1993 standards;
Viscosity(Pa.s):It is evaluated as 40 ~ 50 by GB/T1723-1993 standards;
Impact strength(kg.cm):It is evaluated as 45 ± 5 by GB/T1732-1993 standards;
Artificial ageing resistance(600h):It is evaluated by GB/T1865-2009 standards, no blistering, peeling, crackle;
Salt spray test(1000h):By GB/T1771-2007 standards evaluate, it is no blistering, without cracking, without rust staining;
Hardening time (25C, relative humidity 70%):Biao Gan≤0.5h;The h of Shi Gan≤4;
Hanging test situation
As shown in Figure 1, the environmentally friendly antifouling paint produced as base-material using modified rosin acid zinc salt composite polypropylene acid resin was passed through to day Hanging test is done according to marine terminal 7 times, and every 2 square metres of application is stored 3 years, is had no that microorganism adheres to, is closed on maritime waters Biology has no growth failure.
Embodiment 2:
Rosin acid refines:The ethyl alcohol 715ml that volume fraction is 85% is added in 300g rosin, adds the 1mol/L of 100ml Sodium hydrate aqueous solution is heated to boiling, and return stirring reacts 3 hours, and 3g activated carbon decolorizings, filtering is added, and filtrate is cooled to 0 ~ 4 DEG C, the 1mol/L aqueous hydrochloric acid solutions of 120ml are slowly dropped into, are filtered again, yellowish solid is obtained, are washed with water to neutrality.
The preparation of rosin acid modified alkyd resin zinc salt:To equipped with blender, thermometer, straight pipe condensation pipe, water-oil separating 1013g rosin acids, 355g glycerine and 456g castor oil are added in the reaction kettle of device, is warming up to 90 DEG C, reacts 30 minutes, then 304g maleic acids are added and 0.203g dry oxidation zinc stirs evenly, are heated to boiling, dehydration 1h;Temperature is increased to 210 DEG C, then 2h is reacted, acid value is measured as 80 hereinafter, up to rosin acid modified alkyd resin zinc salt.
The preparation of rosin acid modified alkyd resin zinc salt antifouling paint:
Rosin acid modified alkyd resin zinc salt 900g is added into sand mill, mixes rust resisting pigment 40g, coating additive 1g, carries out It is sanded, surveys fineness at 40 μm hereinafter, to obtain the final product.
Embodiment 3:
Rosin acid refines:The ethyl alcohol 676ml that volume fraction is 90% is added in 300g rosin, adds the 3mol/L of 33ml Sodium hydrate aqueous solution is heated to boiling, and return stirring reacts 4 hours, and 9g activated carbon decolorizings, filtering is added, and filtrate is cooled to 0 ~ 4 DEG C, the 3mol/L aqueous hydrochloric acid solutions of 40ml are slowly dropped into, are filtered again, yellowish solid is obtained, are washed with water to neutrality.
The preparation of rosin acid modified alkyd resin zinc salt:To equipped with blender, thermometer, straight pipe condensation pipe, water-oil separating 1013g rosin acids, 455g trihydroxy methyls propane and 557g rapeseed oils are added in the reaction kettle of device, is warming up to 100 DEG C, reaction Then 1h is added 354g succinic acid and 0.304g dry oxidation zinc stirs evenly, is heated to boiling, dehydration 1h;Increase temperature Degree is to 215 DEG C, then reacts 4h, measures acid value as 80 hereinafter, up to rosin acid modified alkyd resin zinc salt.
The preparation of rosin acid modified alkyd resin zinc salt antifouling paint:
Rosin acid acid modified alcoholic resin zinc salt 1100g is added into the coating material production tank equipped with high speed dispersor, mixes antirust face Expect 50g, coating additive 3g, carry out high speed dispersion, survey fineness at 40 μm hereinafter, to obtain the final product.
In addition to technical characteristic described in specification, remaining technical characteristic is technology known to those skilled in the art.

Claims (4)

1. a kind of preparation method of rosin acid modified alkyd resin zinc salt antifouling paint, which is characterized in that count in parts by weight, institute It is composed of the following components to state rosin acid modified alkyd resin zinc salt antifouling paint:Rosin acid modified alkyd resin zinc salt 900 ~ 1100 Part, mix 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive.
2. the preparation method of rosin acid modified alkyd resin zinc salt antifouling paint according to claim 1, which is characterized in that It is prepared by following processing steps:
Step 1:Rosin acid refines
Ethanol water is added in rosin, adds the aqueous solution of sodium hydroxide, is heated to boiling, return stirring reaction 3 ~ 4 Hour, activated carbon decolorizing, filtering is added, filtrate is cooled to 0 ~ 4 DEG C, instills aqueous hydrochloric acid solution, filters again, obtain yellowish Solid, be washed with water to neutrality to get.
Step 2:The preparation of rosin acid modified alkyd resin zinc salt
Refined rosin acid, polyalcohol, substance and solvent containing oleic acid are added into reaction kettle, is warming up to 90 ~ 100 DEG C, instead 0.5 ~ 1h is answered, alkyl dicarboxylic aid then is added and dry oxidation zinc stirs evenly, is heated to boiling, dehydration 1h, then increase Temperature reacts 2 ~ 4h to 210 ~ 220 DEG C, measures acid value as 80 hereinafter, up to rosin acid modified alkyd resin zinc salt.
Step 3:The preparation of rosin acid modified alkyd resin zinc salt antifouling paint
By 900 ~ 1100 parts of the rosin acid modified alkyd resin zinc salt, 40 ~ 50 parts of rust resisting pigment, 1 ~ 3 part of coating additive are mixed, Dispersion is sanded to 40 μm of granularity hereinafter, to obtain the final product.
3. the preparation method of rosin acid modified alkyd resin zinc salt antifouling paint according to claim 2, which is characterized in that In step 1:The volume fraction of the ethanol water is 75% ~ 90%, the sodium hydrate aqueous solution and aqueous hydrochloric acid solution Concentration is 1 ~ 3mol/L, and the molar ratio of the rosin, sodium hydroxide and hydrochloric acid is 10:1:1.2, rosin, ethyl alcohol and activated carbon Mass ratio is 100:150~170:1~3.
4. the preparation method of rosin acid modified alkyd resin zinc salt antifouling paint according to claim 2, which is characterized in that In step 2:The solvent is one kind in toluene or n-butanol, and the polyalcohol is pentaerythrite, glycerine or trihydroxy One kind in methylpropane, the substance containing oleic acid are behenic acid, castor oil, sunflower oil, palm oil, cottonseed oil or vegetable seed One kind in oil, the alkyl dicarboxylic aid are one or more in succinic acid, maleic acid, fumaric acid or oxalic acid;The rosin Acid, polyalcohol, the substance containing oleic acid, alkyl dicarboxylic aid and dry oxidation zinc weight ratio be 100:35~45:45~55:25~35: 0.02~0.03。
CN201710610532.0A 2017-07-25 2017-07-25 Preparation method of rosin acid modified alkyd resin zinc salt antifouling paint Active CN108690473B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409896A (en) * 2020-12-04 2021-02-26 广西民族大学 Preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential
CN114479582A (en) * 2020-10-27 2022-05-13 中石化石油工程技术服务有限公司 Copper-free antifouling paint for coastal oil and gas pipeline in static environment and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1396154A (en) * 2001-07-16 2003-02-12 中国医药研究开发中心 Sulfonated dehydroabietate and its preparing process and application
JP2005255873A (en) * 2004-03-12 2005-09-22 Harima Chem Inc Varnish composition for gravure printing ink
CN103881576A (en) * 2013-10-29 2014-06-25 东南大学 Anti-fouling paint
CN105949447A (en) * 2016-06-03 2016-09-21 滁州市龙飞化工有限公司 Alkyd resin for polyurethane paint
CN106008937A (en) * 2016-06-28 2016-10-12 石媛 Production method of light-colored rosin modified alkyd resin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1396154A (en) * 2001-07-16 2003-02-12 中国医药研究开发中心 Sulfonated dehydroabietate and its preparing process and application
JP2005255873A (en) * 2004-03-12 2005-09-22 Harima Chem Inc Varnish composition for gravure printing ink
CN103881576A (en) * 2013-10-29 2014-06-25 东南大学 Anti-fouling paint
CN105949447A (en) * 2016-06-03 2016-09-21 滁州市龙飞化工有限公司 Alkyd resin for polyurethane paint
CN106008937A (en) * 2016-06-28 2016-10-12 石媛 Production method of light-colored rosin modified alkyd resin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114479582A (en) * 2020-10-27 2022-05-13 中石化石油工程技术服务有限公司 Copper-free antifouling paint for coastal oil and gas pipeline in static environment and preparation method thereof
CN114479582B (en) * 2020-10-27 2023-08-11 中石化石油工程技术服务有限公司 Copper-free antifouling paint for use in static environment of offshore oil and gas pipeline and preparation method thereof
CN112409896A (en) * 2020-12-04 2021-02-26 广西民族大学 Preparation method of long-oil alkyd resin anticorrosive enamel with high corrosion potential

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