CN102603991B - Environmental-friendly waterborne protective and decorative paint for inner cabin of ship - Google Patents
Environmental-friendly waterborne protective and decorative paint for inner cabin of ship Download PDFInfo
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Abstract
The invention relates to a formula and a preparation process of environmental-friendly waterborne protective and decorative paint. The preparation process comprises the following steps of: firstly, synthesizing acrylic acid modified alcohol acid emulsion with low VOC (volatile organic compounds) content, high stability and high drying speed; then mixing the emulsion serving as a base stock and pigments and auxiliaries; and processing by the processes of grinding, dispersing and the like to form the paint. The paint has low VOC content, does not contain benzene series, is non-toxic and non-inflammable, has no pollution to the environment, is harmless for physical health of constructors, can be constructed by adopting various methods of brushing, spraying, dip-coating and the like, has high drying speed and is safe and convenient to use. The environmental-friendly waterborne protective and decorative paint has high paint film mechanical strength, strong adhesive power and good decoration and is mainly used for a steel plate and the surface of a flexible package in an inner cabin of a ship as a protective and decorative coating. The environmental-friendly waterborne protective and decorative paint can also be used for protection and decoration of a steel iron material of facility parts such as a vehicle, a bridge, a storage tank, a pipeline, and mechanical equipment.
Description
Technical field
The present invention relates to a kind of environment-friendly type aqueous protected decoration formulation for coating material and preparation technology.Synthesized at first that VOC content is low, the acrylic modified alkyd emulsion of good stability, fast drying, be that base-material mixes with pigment, auxiliary agent with this emulsion again, be processed into coating through operations such as grinding, dispersions.This coating VOC content is low, does not contain the benzene series thing, and is nontoxic, do not fire, and environmentally safe is healthy harmless to the workmen, can adopt several different methods constructions such as brushing, spraying, dip-coating, and fast drying is safe and convenient to use.Paint film physical strength height, strong adhesion, good decorative property is mainly used in the interior cabin steel plate of boats and ships and Soft Roll and covers the surface as protection and decorative coveringn.The protection and the decoration that also can be used for facility spare ferrous materials such as the vehicles, bridge, basin, pipeline, mechanical means.
Background technology
Cabin lacquer in a large amount of the use is used for decoration and protection that interior cabin steel plate and Soft Roll cover the surface in the shipbuilding.Because space, interior cabin is narrow and small, the application operation is inconvenient, it is not smooth to ventilate, and has the hidden danger that is easy to produce accidents such as fire, poisoning in the lacquer construction of interior cabin.Using maximum interior cabin lacquers at present in the shipbuilding is the solvent-borne type alkyd paint.Because the solvent-borne type alkyd paint contains 50% the organic solvent of having an appointment, produce fire hazard when having construction and pollute in the cabin problem of environment.Particularly the insulation layer Soft Roll covers in the construction, coat cloth and be porous material with the insulation lagging material, to painting absorbed dose greatly and being easy to organic solvent is enclosed in porous substrate inside, cause in the cabin long-term existence paint smell, healthy also extremely harmful to the personnel that in the cabin, work and live.Therefore there is very exigence in domestic each big shipbuilding factory for cabin lacquer in environment-friendly type aqueous.Research and develop environment-friendly type aqueous interior cabin and coat with lacquer to eliminate fire and intoxication accident hidden danger in the lacquer construction of interior cabin, improve interior cabin living environment, all significant.
Traditional coating mostly is solvent-borne type, wherein contain a large amount of organic solvents, also often need to add organic solvent diluting during use, these solvents evaporate in the atmosphere in construction and drying varniss process, harmful and contaminate environment causes the danger of fire in addition to health of human body.Along with countries in the world environmental regulation increasingly stringent, the friendly type coating of development environment is the trend of the times material with replace solvents type coating.The solvent-borne type alkyd paint occupies suitable proportion with its excellent comprehensive performances in the traditional coating field always.Sound along with the raising of people's environmental consciousness and environmental regulation, exploitation can replace solvents type alkyd paint Water-borne alkyd coating be the striving direction of coating industry always.This has wherein experienced following three phases:
Fs is with the solvent-borne type alkyd emulsification with emulsifying agent.There are many drawbacks such as paint stability is bad, paint film water tolerance, ornamental difference in this method owing to add the influence of emulsifying agent.
Subordinate phase is that hydrophilic radical such as polyether segment, carboxyl etc. are introduced in the Synolac molecule, is scattered in to form water-dilutable alkyd in the alkaline aqueous solution under solubility promoter helps.Existing Water-borne alkyd coating is to be base-material with this resinoid mostly.There are shortcomings such as emulsion viscosity height, paint film poor water resistance, organic solvent content height in this method.
After the nineties, people begin to be devoted to the development of aqueous alkide resin of new generation, i.e. the emulsion of nucleocapsid structure, self-emulsifying.This emulsion does not add emulsifying agent owing to not containing, and has overcome to add the shortcoming that emulsifying agent causes; Because its emulsion particle is nucleocapsid structure, the whole acid number of resin is lower and need not add solubility promoter, has overcome some intrinsic shortcomings of s-generation alkyd again.This emulsion is microemulsion (median size can be little of 50-100nm) in addition, can prepare the finish paint of high gloss, high-decoration.For example, Austria dimension Novartis Co.,Ltd develops water-based acrylic acid modified alcoholic acid finish paint (AT9400711), it is to get copolymer A with unsaturated fatty acids and vinylformic acid mix monomer such as methacrylic acid, (methyl) polyalkylene glycol acrylate ester, other (methyl) vinylformic acid (ester) or vinyl monomer through radical polymerization respectively, get polymer B with unsaturated fatty acids, polyvalent alcohol, diprotic acid, the acid of (polynary) ring-type through esterification, make both reactions obtain the acrylic acid modified alkyd resin that acid number is 25-70 again, 80% methacrylic acid that derives from the copolymer A of its acid number.This resin is neutralized, adds the water stirring with alkali get final product self-emulsifying, obtain the acrylic modified alkyd emulsion.Be that base-material can prepare acrylic modified alkyd coating with this emulsion, be used for protection and the decoration of various metallic surfaces.US Patent No. 4996250 usefulness methacrylic acids and other vinyl are or/and (methyl) acrylic ester monomer and dryness lipid acid carry out free-radical polymerized, synthetic acid number is at 25～70 Synolac, wherein at least 80% acid number comes from methacrylic acid, forms water dilution type Synolac with the some or all of neutralization of alkali back.Mix with this Synolac and Malaysia carburetion or maleated fatty acids, add a kind of polymer emulsion of being formed by (methyl) acrylate or divinyl and cinnamic multipolymer again.Synthesized a kind of novel aqueous resin that can satisfy multiple requirement.US Patent No. 6489398 usefulness methacrylic acids-(methyl) acrylate-vinyl monomer and unsaturated fatty acids graft copolymerization, and then and polyol reaction to generate acid number be the multipolymer of 25-70, wherein 80% carboxyl derives from methacrylic acid.With in the ammonia and carboxyl, obtain water soluble alkyd resin.This resin is than general vinylformic acid, and the self-drying type Synolac has the storage time and many not second to general Synolac from the dryness energy.US Patent No. 0152830 is grafted to Acrylic Acid Monomer on the unsaturated fatty acids by radical polymerization, forms acrylic acid-grafted lipid acid, then with the pure acid-respons of terminal hydroxy group, and forms a kind of acrylic modified alkyd polymkeric substance of condensed type.The carboxyl of the acrylate moiety of this polymkeric substance can neutralize with amine, make shell part possess hydrophilic property, and pure acid moieties still keeps hydrophobic nature.The salt that generates can make polymer dispersed in water.In the nucleocapsid structure of this polymkeric substance, the alkyd of hydrolysis takes place easily as nuclear, the vinylformic acid of aqueous phase (anti-hydrolysis) is as shell, in the hope of obtaining better stability to hydrolysis.The coating of this new type resin preparation is after adding heat-storage several weeks, and every performance is not decline all.
The advantage of this class invention is emulsion mechanical stability height, can grind jointly with color stuffing, has simplified lacquer craftwork processed.Coating application performance, wet film levelling property are better, and the paint film physical strength is higher.One of shortcoming be the unsaturated fatty acids less, that price is higher of originating be that raw material and resin preparation process are complicated, raw material sources are limited, production cost is higher.It two is to contain the stronger polyethers of wetting ability (polyoxyethylene) group in the resin, influences the water tolerance of paint film.It three is to connect with ester bond between vinylformic acid and the alkyd, and stability in storage is undesirable.It four is emulsion particle diameter big (median sizes＞200 μ m), and gloss of film is on the low side.
For overcoming the shortcoming of existing Water-borne alkyd coating, the present invention develops a kind of acrylic acid modified alkyd resin emulsion of novel nucleocapsid structure, i.e. synthetic macromolecule amount Synolac at first, prepare the acrylic acid-grafted Synolac that acid number is 20-40mgKOH/g with acrylic monomer and Synolac by radical polymerization again, this resin forms the good acrylic modified alkyd emulsion of stability in storage after adding water with the amine neutralization.Be that base-material and pigment, auxiliary agent are mixed and made into water-based acrylic acid modified alcoholic acid coating with this emulsion, its VOC content is low, does not contain formaldehyde and benzene series thing, and environmentally safe is healthy harmless to the workmen.Its workability, from dryness, paint film physical strength, the ornamental level that all reaches the solvent-borne type alkydpaints.Can replace the solvent-borne type alkyd paint, be used for the interior cabin iron and steel of boats and ships and Soft Roll and cover the surface, as protection and decorative coveringn.
Cabin lacquer coating decoration environment in enforcement of the present invention can significantly improve, protection construction and cabin work and life personnel health.This product also can promote the use of the vehicles such as automobile, rail vehicle, facilities such as petrochemical industry basin, pipeline, steel construction such as bridge, iron tower, a structure of an essay, protection and the decoration of ferrous materials in all kinds of mechanical means manufacturings and the maintenance, not only have remarkable economic efficiency, and have the huge social benefit.For the technical progress of paint industry, the protection environment for human survival has important meaning.
Summary of the invention
The present invention is in order to solve traditional alkyd paint organic solvent content height, there is pollution harmful and have the problem of disaster hidden-trouble to HUMAN HEALTH to environment, and existing Water-borne alkyd coating complicated process of preparation, cost is higher, dryness is relatively poor and stability in storage is undesirable shortcoming.
The present invention is that preparation two portions of the coating of base-material are formed by the preparation of acrylic modified alkyd emulsion with this emulsion.
The preparation of acrylic modified alkyd emulsion:
Technological line: at first prepare Synolac, earlier carry out alcoholysis reaction with vegetables oil and polyvalent alcohol, add dibasic alcohol, diprotic acid (acid anhydride) and eleostearic acid and alcoholysate again and carry out esterification, after acid number reached 5--10mgKOH/g or viscosity and reaches 4--6s, cooling obtained Synolac.Drip the Acrylic Acid Monomer of acid number (theoretical value) 40-60mgKOH/g and the mix monomer (containing initiator) of other unsaturated monomer then, insulation reaction for some time, after viscosity reaches 6-9s, cooling, in alkaline aqueous solution, carry out self-emulsifying, namely having made with hydrophobic Synolac is nuclear, is the emulsion of shell with hydrophilic acrylic resin.
Emulsion formulations:
Preparation technology:
1. vegetables oil, trivalent alcohol and the catalyzer with formula ratio adds 1
#Reaction vessel starts stirring, and logical nitrogen is warmed up to 230--240 ℃, be incubated about 1.5--2h, survey ethanol tolerance (95% ethanol, be terminal point at 1: 9), qualified after, cool to 180--190 ℃.
2. formula ratio dibasic alcohol, diprotic acid or dibasic acid anhydride and 3-5 part backflow dimethylbenzene are added 1
#Reaction vessel, 210--220 ℃ of reaction 1h.
3. add the formula ratio eleostearic acid, 230--240 ℃ of back flow reaction 2--3h surveys acid number, viscosity.During near terminal point, survey once every half an hour.When viscosity reaches 4--6s or acid number and reaches 5--8mgKOH/g, stop heating, cool to 120--130 ℃, put into 2
#Reaction vessel extracts backflow dimethylbenzene simultaneously.
4. formula ratio unsaturated monomer and initiator are mixed, enter the high-order groove that drips, under nitrogen protection, be added drop-wise to 2
#In the reaction vessel, about 3h of dropping time about 100--130 ℃ of insulation reaction 3h, when viscosity reaches 6-9s, cools to 70--80 ℃.
5. formula ratio softening water, neutralizing agent are joined 3
#In the reaction vessel, open stirring, with 2
#Material in the reaction vessel transfers to 3
#In the reaction vessel, stirring at low speed emulsification 1--3h, obtaining solids content is the acrylic modified alkyd emulsion of 30-50%.
Above-mentioned vegetables oil can be oleum lini, soya-bean oil or its mixture, and optimum amount is 40-60 part; Trivalent alcohol can be glycerine, TriMethylolPropane(TMP) or its mixture, and optimum amount is 5-10 part; Catalyzer is lithium hydroxide or calcium hydroxide; Dibasic alcohol can be butyleneglycol, neopentyl glycol or its mixture, and optimum amount is 5-10 part; Diprotic acid (acid anhydride) can be one or more in HHPA, m-phthalic acid, fumaric acid, (methyl) carbic anhydride, and preferred m-phthalic acid consumption is 6-20 part, preferably 10-20 part; (methyl) carbic anhydride consumption is 5-10 part; Unsaturated monomer comprises one or more in (methyl) vinylformic acid, methyl methacrylate, (methyl) butyl acrylate, vinylbenzene, dibutyl maleinate, the tertiary ethylene carbonate.Initiator is benzoyl peroxide, and optimum amount is 0.6-1.2 part; Neutralizing agent is ammoniacal liquor, AMP-95, N-ethylmorpholine, N, one or more in N dimethylethanolamine, the triethylamine.Softening water is deionized water or distilled water, and consumption is 120-180 part, requires the content of water-soluble substances wherein less than 100ppm, and specific conductivity is less than 20 μ s/cm.
The preparation of coating
Formulation for coating material:
Preparation technology
1. the softening water, auxiliary agent, the neutralizing agent that add formula ratio in joining the slurry container stir with adjustable high-speed dispersion machine (down together).
2. add the acrylic modified alkyd emulsion of 60% formula ratio, stir.
3. add pigment, the filler of formula ratio, stir.
4. add the thickening material of formula ratio 1/3, stir.
5. be ground to fineness with sand mill and reach below the 30 μ m, get mill base.
6. in the paint container, add the mill base that obtains, the acrylic modified alkyd emulsion of residue 40% formula ratio, the siccative of formula ratio, stir.
7. add residue formula ratio 2/3 thickening material, stir, filter, get finished product.
Above-mentioned softening water is deionized water or distilled water, and wherein the total amount of water-soluble substances is less than 100ppm, specific conductivity＜20 μ s/cm.
Neutralizing agent is one or more in ammoniacal liquor, triethylamine, dimethylethanolamine, N ethyl morpholine, the 2-amino-2-methyl-1-propanol.
Auxiliary agent is one or more in wetting agent, flow agent, defoamer, sanitas, the mould inhibitor.Wetting agent is selected polyether-modified alkynol for use, as SURFYNOL GA, the SURFYNOL TG of U.S. aerochemistry company; Flow agent can be selected fluorochemical surfactant or organic silicon modified by polyether type auxiliary agent for use, for example the Byk348 of German Bi Ke company, 307 or EFKA-3570, the SFL-50 of U.S. AJA company of Dutch EFKA company; Defoamer is mineral oil, polyethers, silicone resin and mixture thereof, for example SN1311 of NOPCO company, 1340, NXZ, the BYK024 of BYK company; Sanitas can be the KATHON LXE of east-Rhom and Hass, the PG520 of Korea S SK company; Mould inhibitor can be the SKANE M-8 of east-Rhom and Hass, the MA-21 of Korea S SK company;
Pigment can be one or more in red iron oxide, iron oxide black, iron oxide yellow, zirconium aluminium coating Rutile type Titanium Dioxide, BGS phthalocyanine blue (P.B.15:3), the carbon black; Filler can be process white, talcum powder or its mixture; Thickening material is caustic solubility ACRYLIC EMULSION class thickening material or polyether-polyurethane type thickening material, the TT935 thickening material of Beijing Orient-Rhom and Hass for example, this 420 thickening materials, R-278 thickening material of hamming, the 830W thickening material of French COATEX company, the preferred 0.5-1.0 part of consumption; Described siccative is to be the emulsion of effective ingredient with cobalt naphthenate, zirconium naphthenate, calcium naphthenate, zinc naphthenate etc., for example the VXW siccative of Austria's dimension Novartis Co.,Ltd.
Salt unsaturated carboxylic acid, composition are amine (or ammonium) salt of unsaturated carboxylic acid, (methyl) acrylate and vinyl unsaturated monomer multipolymer.Its preparation technology is as follows:
1. 1
#Add 25-35 part propylene glycol monomethyl ether in the reaction vessel, start stirring, logical nitrogen is warmed up to 110--120 ℃, keeps slight boiling condition;
2. 30-50 part unsaturated carboxylic acid monomer, 20-30 part (methyl) acrylate monomer and 20-30 part vinyl monomer and 2-3 part initiator are mixed, and enter the high-order groove that drips, and under nitrogen protection, are added drop-wise to 1
#In the reaction vessel, about 3-4h of dropping time adds the back in 110-120 ℃ of insulation reaction 1-2h.
3. cool to 60-70 ℃, add 20-25 part neutralizing agent.Add water gradually and stir, obtaining solid content is the unsaturated carboxylic salt of 35-40%.
Wherein unsaturated carboxylic acid is one or more in vinylformic acid, methacrylic acid, the MALEIC ANHYDRIDE; (methyl) acrylate can be one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate; Vinyl monomer can be one or more in vinylbenzene, maleic anhydride bibutylester, vinyl acetate, the uncle's vinyl acetate; Initiator is benzoyl peroxide; Neutralizing agent is N, N dimethylethanolamine or 2-amino-2-methyl-1-propanol.
Beneficial effect of the present invention:
Waterborne acrylic modified alkyd resins of the present invention replaces phthalic anhydride with m-phthalic acid and tetrahydrophthalic anhydride, introduce dibasic alcohol in Esterification Stage, it is even that the molecular resin amount is tending towards, the molecule regularity improves greatly, the crystallinity tendency significantly increases, thereby not only significantly improved the problem of facing the poor storage stability that a hydrolysis effect causes that traditional aqueous alkide resin adopts phthalic anhydride, and significantly improved the rate of drying of paint film, adopt water-based that emulsion of the present invention makes to decorate protection finish paint surface drying rapidly after the construction of cabin in boats and ships, significantly reduce paint film by the probability that dust stains, significantly improved operating efficiency and paint film is ornamental.
Compare with existing Water-borne alkyd coating with traditional solvent-borne type alkyd paint, there is following advantage in the cabin with environment-friendly type aqueous coating in the boats and ships of the present invention: 1. safe and convenient to use.This coating is dispersion medium with water, does not contain solubility promoter, VOC content low (≤150g/L), smell is little, has improved construction environment, has avoided disaster hidden-trouble.2. good decorative property.The base-material of this coating is self-emulsifying acrylic modified alkyd emulsion, emulsion particle diameter little (median size has only 50-70nm), and good film-forming property can prepare the finish paint of high gloss, high-decoration.3. paint film property is good.The base-material of this coating is the acrylic modified alkyd emulsion of nucleocapsid structure, and its nuclear is for Synolac, shell is acrylic resin, both kept Synolac good from dryness, good sticking power and snappiness, possess the weathering resistance of acrylic resin excellence again.4. stability in storage is good.Adopt m-phthalic acid to replace phthalic anhydride, improved the resin anti-hydrolytic performance; Introduce the methyl carbic anhydride, improved the percentage of grafting of acrylic resin on the Synolac chain, resin machinery stability in storage and thermostability all are significantly increased, and are convenient to colored paint and grind, and have prolonged the storage period of coating greatly.5. have a extensive future.The every index of this coating all meets or exceeds solvent-borne type alkydpaints level, can replace the solvent-borne type alkydpaints fully, verified this coating has good result of use aspect the decoration of steel and iron member and the protection in the facilities such as cabin, goods train carriage, automobile chassis and compartment, pipeline, basin in boats and ships.With water alcohol acid paint replacement solvent-borne type alkydpaints, can save energy, the protection environment has important social benefit and huge economic benefit.
Embodiment
Below list the synthetic embodiment of several emulsions, but the present invention is not limited in these examples.The emulsion preparation prescription sees Table 1.
Table 1 emulsion is synthesized embodiment
The emulsion synthetic technological condition sees Table 2.
Table 2 emulsion synthetic technological condition
| Project | Temperature (℃) | Time (h) |
| Alcoholysis | 230-250 | 1.5-2 |
| Esterification | 220-230 | 3-4 |
| Radical polymerization adds monomer | 100-130 | 3-4 |
| The radical polymerization insulation | 100-130 | 1-2 |
| Self-emulsifying | 40-60 | 1-2 |
Emulsion property sees Table 3.
Table 3 emulsion property
As can be seen from the above embodiments, water-base resin package stability of the present invention significantly improves, obviously shorten time of drying, and water tolerance also has clear improvement.
Below illustrate preparation method for coating, but the present invention is not limited in the following example, prescription sees Table 4:
Table 4 formulation examples
Annotate: go up in the table prescription and make 1 by oneself
#-3
#, 9
#Emulsion is respectively the synthetic embodiment 1-3 of emulsion and Comparative Examples 9 gained emulsions.
The AC-261 emulsion is Beijing Orient in the Comparative Examples 2--the ACRYLIC EMULSION of Rhom and Hass.
The AY-396 emulsion is the acrylic modified alkyd emulsion of Austria dimension Novartis Co.,Ltd in the Comparative Examples 3.
Coating property sees Table 5
Table 5. coating property
Claims (5)
1. the acrylic modified alkyd nanoemulsions of a nucleocapsid structure, it is synthetic by following prescription:
The preparation method of the acrylic modified alkyd nanoemulsions of wherein said nucleocapsid structure is:
1. vegetables oil, trivalent alcohol and the catalyzer with formula ratio adds 1
#Reaction vessel starts stirring, and logical nitrogen is warmed up to 230--240 ℃, and insulation 1.5--2h surveys the ethanol tolerance, and with 95% ethanol, 1:9 is terminal point, qualified after, cool to 180--190 ℃;
2. formula ratio dibasic alcohol, diprotic acid or dibasic acid anhydride and 3-5 part backflow dimethylbenzene are added 1
#Reaction vessel, 210--220 ℃ of reaction 1h;
3. add the formula ratio eleostearic acid, 230--240 ℃ of back flow reaction 2--3h surveys acid number, viscosity, during near terminal point, surveys once every half an hour, when viscosity reaches 4--6s or acid number and reaches 5--8mgKOH/g, stops heating, cools to 120--130 ℃, puts into 2
#Reaction vessel extracts backflow dimethylbenzene simultaneously;
4. formula ratio unsaturated monomer and initiator are mixed, enter the high-order groove that drips, under nitrogen protection, be added drop-wise to 2
#In the reaction vessel, drip time 3h, 100--130 ℃ of insulation reaction 3h when viscosity reaches 6-9s, cools to 70--80 ℃;
5. formula ratio softening water, neutralizing agent are joined 3
#In the reaction vessel, open stirring, with 2
#Material in the reaction vessel transfers to 3
#In the reaction vessel, stirring at low speed emulsification 1--3h, obtaining solids content is the acrylic modified alkyd emulsion of 30-50%;
Described vegetables oil is oleum lini, soya-bean oil or its mixture; Described trivalent alcohol is glycerine, TriMethylolPropane(TMP) or its mixture; Described dibasic alcohol is butyleneglycol, neopentyl glycol or its mixture; Described diprotic acid or binary acid anhydride are one or more in HHPA, m-phthalic acid, fumaric acid, (methyl) carbic anhydride; Described unsaturated monomer is one or more in (methyl) vinylformic acid, methyl methacrylate, (methyl) butyl acrylate.
2. the acrylic modified alkyd nanoemulsions of nucleocapsid structure according to claim 1 is characterized in that, described initiator is benzoyl peroxide; Described neutralizing agent is ammoniacal liquor, AMP-95, N-ethylmorpholine, N, and one or more in N-dimethylethanolamine, the triethylamine, described softening water are deionized water or distilled water; Described catalyzer is lithium hydroxide or calcium hydroxide.
3. the cabin is characterized in that with environment-friendly type aqueous protected decoration coating this system component is in the boats and ships of making as base-material with the acrylic modified alkyd nanoemulsions of the nucleocapsid structure of claim 1:
Described salt unsaturated carboxylic acid prepares by the following method:
1. 1
#Add 25-35 part propylene glycol monomethyl ether in the reaction vessel, start stirring, logical nitrogen is warmed up to 110--120 ℃, keeps slight boiling condition;
2. one or more in 30-50 part vinylformic acid, methacrylic acid, the MALEIC ANHYDRIDE, 20-30 part (methyl) acrylate monomer and 20-30 part vinyl monomer and 2-3 part initiator are mixed, and enter the high-order groove that drips, and under nitrogen protection, are added drop-wise to 1
#In the reaction vessel, drip time 3-4h, add the back in 110-120 ℃ of insulation reaction 1-2h;
3. cool to 60-70 ℃, add 20-25 part neutralizing agent; Add water gradually and stir, obtain the salt unsaturated carboxylic acid that solid content is 35-40%;
Described pigment is one or more in iron oxide black, red iron oxide, iron oxide yellow, titanium dioxide, phthalocyanine blue, the carbon black; Described filler is process white, talcum powder or its mixture; Described siccative is that cobalt naphthenate, zirconium naphthenate, zinc naphthenate, calcium naphthenate are the emulsion of effective ingredient; Described thickening material is caustic solubility ACRYLIC EMULSION class or polyether-polyurethane class thickening material; Described auxiliary agent is one or more in wetting agent, flow agent, defoamer, sanitas, the mould inhibitor; Described neutralizing agent is one or more in ammoniacal liquor, triethylamine, dimethylethanolamine, N ethyl morpholine, the 2-amino-2-methyl-1-propanol; Described softening water is deionized water or distilled water.
4. the cabin is with environment-friendly type aqueous protected decoration coating in the boats and ships according to claim 3, and its preparation method is:
1. in joining the slurry container, add softening water, auxiliary agent, the neutralizing agent of formula ratio, stir with the adjustable high-speed dispersion machine;
2. add the acrylic modified alkyd emulsion of 60% formula ratio, stir;
3. add pigment, the filler of formula ratio, stir;
4. add the thickening material of formula ratio 1/3, stir;
5. be ground to fineness with sand mill and reach below the 30 μ m, get mill base;
6. in the paint container, add the mill base that obtains, the acrylic modified alkyd emulsion of residue 40% formula ratio, the siccative of formula ratio, stir;
7. add residue formula ratio 2/3 thickening material, stir, filter, get finished product.
In the boats and ships according to claim 4 the cabin with environment-friendly type aqueous protected decoration coating, it is characterized in that described (methyl) acrylate is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate; Vinyl monomer is vinylbenzene, vinyl acetate or its mixture; Initiator is benzoyl peroxide; Neutralizing agent is N, N dimethylethanolamine or 2-amino-2-methyl-1-propanol.
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| CN104178000A (en) * | 2013-05-23 | 2014-12-03 | 海安县国力化工有限公司 | Emulsion paint |
| CN103709885B (en) * | 2013-12-27 | 2015-11-04 | 青岛乐化科技有限公司 | A kind of aqueous environments friendly acid modified alcoholic wood lacquer |
| CN104497819A (en) * | 2014-12-10 | 2015-04-08 | 成都拜迪新材料有限公司 | Preparation method of waterborne alkyd enamel |
| CN105367718B (en) * | 2015-11-27 | 2018-01-09 | 海洋化工研究院有限公司 | Environment-friendly type air dry water anticorrosive paint |
| CN105602388B (en) * | 2016-01-20 | 2018-04-13 | 华南理工大学 | A kind of alkyd resin modified acroleic acid anticorrosive paint of core shell structure and preparation method thereof |
| CN105566578B (en) * | 2016-02-04 | 2018-01-05 | 武汉双虎涂料有限公司 | A kind of air drying type acrylic acid alkyd hybridisation emulsion and preparation method thereof |
| CN109627936B (en) * | 2018-12-17 | 2021-01-22 | 厦门双瑞船舶涂料有限公司 | Long-acting water-based ship inner cabin paint and preparation method thereof |
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| ATE287935T1 (en) * | 1999-06-25 | 2005-02-15 | Resolution Specialty Materials | QUICK-DRYING COATING AGENT WITH HIGH SOLIDS CONTENT BASED ON MODIFIED ALKYD RESINS |
| CN1161437C (en) * | 2001-03-15 | 2004-08-11 | 海洋化工研究院 | Acrylic acid modified high-performance water-thinned alkyd enamal |
| CN101307137B (en) * | 2007-05-17 | 2011-04-06 | 上海涂料有限公司技术中心 | Water dispersion of self-drying acrylic modified alkyd resin and industrial topcoat using the water dispersion as base |
-
2012
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