CN108794703B - Preparation method of polyacrylate anticorrosive emulsion with excellent salt mist resistance function - Google Patents
Preparation method of polyacrylate anticorrosive emulsion with excellent salt mist resistance function Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention provides a preparation method of polyacrylate anticorrosive emulsion with excellent salt spray resistance, which comprises the steps of firstly carrying out esterification reaction on epoxy resin with medium and high molecular weight and linoleic acid with double bonds to prepare an epoxy ester intermediate, dropwise adding a mixture of acrylic acid and an acrylate monomer into the epoxy ester intermediate, adding an initiator into the epoxy ester intermediate, carrying out free radical copolymerization to obtain epoxy modified acrylic resin, adding a neutralizing agent into the epoxy modified acrylic resin, stirring to reach a required pH value, adding deionized water into the epoxy modified acrylic resin to form an epoxy modified acrylic resin aqueous dispersion, and then carrying out hot melting on the epoxy modified acrylic resin aqueous dispersion into common acrylic anticorrosive emulsion to improve the defect of film extrusion of emulsion molecules, so that the acrylic anticorrosive emulsion has better anticorrosive stability, and the anticorrosive performance of the acrylic emulsion is greatly improved.
Description
Technical Field
The invention belongs to the field of anticorrosive materials, and particularly relates to a preparation method of polyacrylate anticorrosive emulsion with an excellent salt spray resistance function.
Background
Because the film forming mode of the acrylic emulsion is that emulsion macromolecules approach each other and extrude to form a continuous film in the moisture volatilization process, the formed film is not compact enough, and the use of an emulsifier and the like in the emulsion synthesis process causes the film formed by the emulsion to have poor water resistance and salt spray resistance, particularly the poor salt spray resistance and the fatal defect of the acrylic anticorrosive emulsion.
In the prior art, a water-resistant auxiliary agent or a reactive emulsifier is adopted in the preparation process of the acrylic acid anticorrosive emulsion, the use of a water-soluble auxiliary agent is reduced as much as possible, and a functional monomer is added for modification, so that the emulsion has better water resistance and salt spray resistance, and the film forming property of the emulsion is improved. However, the addition of various auxiliary agents and functional monomers leads to higher cost, and the use of the auxiliary agents leads to the reduction of emulsion stability.
Disclosure of Invention
In order to solve the problems existing in the prior art: due to the reason that the formed film is not compact enough, the salt spray resistance of the water-based anticorrosive paint prepared by the existing acrylic anticorrosive emulsion is not good, so that the product cannot obtain a good anticorrosive effect, and the use of the auxiliary agent causes the technical problem of reduction of the emulsion stability.
The invention provides a preparation method of polyacrylate anticorrosive emulsion with excellent salt spray resistance, and the prepared anticorrosive emulsion improves gaps formed in the emulsion film forming process, so that the acrylate emulsion disclosed by the invention can form a complete and compact film, and the water resistance and salt spray resistance of the polyacrylate anticorrosive emulsion are improved.
The preparation method of the polyacrylate anticorrosive emulsion with the excellent salt mist resistance function comprises the following steps:
1. preparation of an epoxy-modified aqueous acrylic resin aqueous Dispersion
(1) Heating epoxy resin and linoleic acid with double bonds in a reaction kettle according to the mass ratio of 1:1-1:1.5, adding an esterification catalyst, starting stirring, and carrying out an esterification reaction at the temperature of 200-;
wherein, the epoxy resin is 1500-5000 medium and high molecular weight epoxy resin, the molecular chain length of the medium and high molecular weight epoxy resin is long, the side chain of the prepared modified acrylic resin aqueous dispersion has more hydrophobic groups, more reactive crosslinking groups and higher crosslinking degree, and macroscopically, the formed paint film has good water resistance, is more compact and has enhanced anti-corrosion performance.
The linoleic acid with double bonds is dry oleic acid oil which has enough conjugated carbon-carbon double bonds and can perform free radical copolymerization with acrylic acid and acrylate monomers.
The esterification catalyst is zinc oxide, and the dosage of the esterification catalyst is 0.04 percent of the total mass of the epoxy resin and the linoleic acid.
(2) Dripping acrylic acid and an acrylate monomer mixture into the epoxy ester intermediate prepared in the step (1), adding a peroxide initiator TBPB into the mixture, and carrying out free radical copolymerization at the temperature of 120-130 ℃ to obtain epoxy modified acrylic resin;
wherein the mass ratio of the epoxy ester intermediate to the mixture of acrylic acid and acrylate monomers is 3:1-4:1, and the acrylic acid in the mixture accounts for 30% of the total mass of the acrylic acid and acrylate monomers; the amount of the peroxide initiator accounts for 3-4% of the total mass of the acrylic acid and acrylate ester monomers.
The acrylic acid is added to neutralize with a neutralizer to form a water-based group at a later stage, so that the resin has water solubility, the acrylic ester monomer is added to endow a side chain of the resin with some groups, the functions of water resistance, paint film gloss increase and the like are achieved, the type of the acrylic ester monomer is the same as that of the acrylic ester monomer of the emulsion at the later stage, the integral polarity difference of chain segments is small, the acrylic ester monomer is similar and compatible, better miscibility with the emulsion is provided, pores formed due to incompact extrusion film forming of emulsion macromolecules are automatically filled in the film forming process of the emulsion, the emulsion forms a complete and compact film, the defect of film forming by emulsion molecule extrusion is overcome, the acrylic acid anticorrosive emulsion has better anticorrosive stability, the anticorrosive performance of the product is greatly improved, and particularly the salt spray resistance is greatly.
The resin obtained by the test has the optimal performance under the condition of the dosage proportion.
(3) And (3) adding a neutralizing agent into the epoxy modified acrylic resin obtained in the step (2), stirring to reach a required pH value, and adding deionized water to form the epoxy modified acrylic resin aqueous dispersion.
Wherein the neutralizer is organic amine or ammonia water, the pH value is adjusted to 7-9, and deionized water is added to form stable epoxy modified acrylic resin aqueous dispersion, wherein the solid content of the epoxy modified acrylic resin is 40%.
The aqueous group obtained after the neutralization of the resin by adding the neutralizing agent has a greatly increased viscosity, which is inconvenient for the use in the later step.
2. Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and vinylsulfonate reactive emulsifier with the mass fraction accounting for 30 percent of the total dosage of the emulsifier into a reaction kettle;
(2) adding deionized water, acrylic acid, acrylate monomers, functional monomers and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
wherein, the functional monomer is phosphate functional monomer, the dosage of which accounts for 1.0-1.5 percent of the total mass of the acrylic acid and acrylate monomer, the acrylic acid accounts for 30 percent of the total mass of the acrylic acid and acrylate monomer, and the total dosage of the emulsifier accounts for 1.2-1.5 percent of the total mass of the acrylic acid and acrylate monomer.
(3) After pre-emulsification is finished, persulfate initiators accounting for 0.1-0.15% and 0.3-0.45% of the total mass of the acrylic acid and acrylate monomers are respectively added into an emulsification kettle and a reaction kettle, the reaction kettle is started to stir, and the temperature is increased to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed, carrying out free radical polymerization reaction at the temperature of 80 +/-5 ℃, and adding ammonia water to neutralize until the pH value is 7-9 to prepare the acrylic acid anticorrosive emulsion.
3. Modification of acrylic acid antiseptic emulsion
Adding epoxy modified acrylic resin aqueous dispersion accounting for 5-10% of the weight of the prepared acrylic acid anticorrosive emulsion into the prepared acrylic acid anticorrosive emulsion, stirring, keeping the temperature at 80 ℃ for 1 hour, and cooling to obtain the anticorrosive emulsion.
Because the viscosity of the epoxy modified acrylic resin aqueous dispersion is higher, the epoxy modified acrylic resin aqueous dispersion is not easy to disperse when being directly added into emulsion without heating, and can form the phenomena of agglomeration, agglomeration and the like, and a uniform mixture can not be formed. The invention has high hot melting temperature at 80 ℃, the viscosity of the resin is reduced, and the epoxy modified acrylic resin aqueous dispersion is easier to disperse in the emulsion through the action of mechanical stirring.
Has the advantages that: according to the invention, the epoxy modified acrylic resin aqueous dispersion is hot-melted into the common anticorrosive emulsion, and the dispersion has better miscibility with emulsion molecules according to a similar compatibility principle due to small polarity difference of macromolecular chain segments, so that pores formed by incompact extrusion film forming of emulsion macromolecules are automatically filled in the emulsion in the film forming process, the emulsion forms a complete and compact film, and the defect of extrusion film forming of emulsion molecules is improved, so that the acrylic anticorrosive emulsion has better anticorrosive stability, the anticorrosive performance of the product is greatly improved, and especially the salt spray resistance is greatly improved.
In addition, the esterification catalyst is less in dosage and can be neglected when added into the emulsion. The rest of the initiator and the reactive emulsifier participate in the reaction process, and cannot be dissociated in a resin system, so that the film forming cannot be influenced.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
1. Preparation of epoxy-modified aqueous acrylic dispersions
(1) Heating medium and high molecular weight epoxy resin with the molecular weight of 1500-5000 and linoleic acid with double bonds in a reaction kettle according to the mass ratio of 1:1.2, adding zinc oxide which is 0.04 percent of the total mass of the epoxy resin and the linoleic acid and is used as an esterification catalyst, starting stirring, and carrying out esterification reaction at 200 ℃ to graft the epoxy resin on carboxylic acid molecules to prepare an epoxy ester intermediate;
(2) dripping acrylic acid and an acrylate monomer mixture into the epoxy ester intermediate prepared in the step (1), wherein the mass ratio of the intermediate to the acrylic acid and acrylate monomer mixture is 3:1, the acrylic acid accounts for 30% of the total mass of the acrylic acid and acrylate monomer, adding benzoyl peroxide tert-butyl ester (TBPB) into the mixture, the amount of the benzoyl peroxide tert-butyl ester accounts for 3% of the total mass of the acrylic acid and acrylate monomer, and carrying out free radical copolymerization at the temperature of 120 ℃ to obtain epoxy modified acrylic resin;
(3) adding dimethylethanolamine into the epoxy modified acrylic resin obtained in the step (2), stirring until the pH value of the system reaches 8, and adding deionized water to form the epoxy modified acrylic resin aqueous dispersion.
2. Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and a sodium vinylsulfonate emulsifier with the mass fraction accounting for 30 percent of the total dosage of the emulsifier into a reaction kettle;
(2) adding ionized water, acrylic acid, an acrylate monomer, a PAM-100 functional monomer and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, wherein the using amount of the functional monomer accounts for 1.5% of the total mass of the acrylic acid and the acrylate monomer, the using amount of the acrylic acid accounts for 30% of the total mass of the acrylic acid and the acrylate monomer, the total using amount of the emulsifier accounts for 1.3% of the total mass of the acrylic acid and the acrylate monomer, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
(3) after pre-emulsification is finished, respectively adding ammonium persulfate initiators accounting for 0.1 percent and 0.3 percent of the total mass of acrylic acid and acrylate monomers into an emulsifying kettle and a reaction kettle, starting the reaction kettle to stir, and heating to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed for 3h, preserving the heat for 2h, carrying out a free radical polymerization reaction process at the temperature of 80 +/-5 ℃, and after the reaction is finished, adding ammonia water to neutralize until the pH value is 7-9, thus obtaining the acrylic acid anticorrosive emulsion.
3. Modification of acrylic acid antiseptic emulsion
And (3) adding the resin obtained in the step (1) with the mass of 5% of that of the emulsion into the emulsion prepared in the step (2), preserving the heat for 1 hour at the temperature of 80 ℃, and cooling to obtain the anticorrosive emulsion.
Example 2
1. Preparation of epoxy-modified aqueous acrylic dispersions
(1) Heating medium and high molecular weight epoxy resin with the molecular weight of 1500-5000 and linoleic acid with double bonds in a reaction kettle according to the mass ratio of 1:1.3, adding zinc oxide which is 0.04 percent of the total mass of the epoxy resin and the linoleic acid and is used as an esterification catalyst, starting stirring, and carrying out esterification reaction at 205 ℃ to graft the epoxy resin on carboxylic acid molecules to prepare an epoxy ester intermediate;
(2) dripping acrylic acid and an acrylate monomer mixture into the epoxy ester intermediate prepared in the step (1), wherein the mass ratio of the intermediate to the acrylic acid and acrylate monomer mixture is 3.5:1, the acrylic acid accounts for 30% of the total mass of the acrylic acid and acrylate monomer, adding benzoyl peroxide tert-butyl ester (TBPB) into the mixture, the amount of the benzoyl peroxide tert-butyl ester accounts for 3% of the total mass of the acrylic acid and acrylate monomer, and carrying out free radical copolymerization at the temperature of 120 ℃ to obtain epoxy modified acrylic resin;
(3) adding dimethylethanolamine into the epoxy modified acrylic resin obtained in the step (2), stirring until the pH value of the system reaches 8, and adding deionized water to form the epoxy modified acrylic resin aqueous dispersion.
2. Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and a sodium vinylsulfonate emulsifier with the mass fraction accounting for 30 percent of the total dosage of the emulsifier into a reaction kettle;
(2) adding ionized water, acrylic acid, an acrylate monomer, a PAM-100 functional monomer and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, wherein the using amount of the functional monomer accounts for 1.0% of the total mass of the acrylic acid and the acrylate monomer, the using amount of the acrylic acid accounts for 30% of the total mass of the acrylic acid and the acrylate monomer, the total using amount of the emulsifier accounts for 1.2% of the total mass of the acrylic acid and the acrylate monomer, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
(3) after pre-emulsification is finished, respectively adding ammonium persulfate initiators accounting for 0.1 percent and 0.3 percent of the total mass of acrylic acid and acrylate monomers into an emulsifying kettle and a reaction kettle, starting the reaction kettle to stir, and heating to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed for 3h, preserving the heat for 2h, carrying out a free radical polymerization reaction process at the temperature of 80 +/-5 ℃, and after the reaction is finished, adding ammonia water to neutralize until the pH value is 7-9, thus obtaining the acrylic acid anticorrosive emulsion.
3. Modification of acrylic acid antiseptic emulsion
And (3) adding the resin obtained in the step (1) with the mass of 5-10% of that of the emulsion into the emulsion prepared in the step (2), preserving the heat for 1 hour at the temperature of 80 ℃, and cooling to obtain the anticorrosive emulsion.
Example 3
1. Preparation of epoxy-modified aqueous acrylic dispersions
(1) Heating medium and high molecular weight epoxy resin with the molecular weight of 1500-5000 and linoleic acid with double bonds in a reaction kettle according to the mass ratio of 1:1.5, adding zinc oxide which is 0.04 percent of the total mass of the epoxy resin and the linoleic acid and is used as an esterification catalyst, starting stirring, and carrying out esterification reaction at 210 ℃ to graft the epoxy resin on carboxylic acid molecules to prepare an epoxy ester intermediate;
(2) dropwise adding an acrylic acid and acrylate monomer mixture into the epoxy ester intermediate prepared in the step (1), wherein the mass ratio of the intermediate to the acrylic acid and acrylate monomer mixture is 4:1, the acrylic acid accounts for 30% of the total mass of the acrylic acid and acrylate monomer, adding a tert-butyl peroxybenzoate (TBPB) initiator into the mixture, the amount of the TBPB initiator accounts for 3.5% of the total mass of the acrylic acid and acrylate monomer, and carrying out free radical copolymerization at the temperature of 125 ℃ to obtain epoxy modified acrylic resin;
(3) and (3) adding ammonia water into the epoxy modified acrylic resin obtained in the step (2), stirring until the pH value of the system reaches 7, and adding deionized water to form the epoxy modified acrylic resin aqueous dispersion.
2. Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and a sodium vinylsulfonate emulsifier with the mass fraction accounting for 30 percent of the total dosage into a reaction kettle;
(2) adding ionized water, acrylic acid, an acrylate monomer, a PAM-100 functional monomer and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, wherein the using amount of the functional monomer accounts for 1.5% of the total mass of the acrylic acid and the acrylate monomer, the using amount of the acrylic acid accounts for 30% of the total mass of the acrylic acid and the acrylate monomer, the total using amount of the emulsifier accounts for 1.5% of the total mass of the acrylic acid and the acrylate monomer, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
(3) after pre-emulsification is finished, respectively adding ammonium persulfate initiators accounting for 0.15 percent and 0.4 percent of the total mass of acrylic acid and acrylate monomers into an emulsifying kettle and a reaction kettle, starting the reaction kettle to stir, and heating to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed for 3h, preserving the heat for 2h, carrying out a free radical polymerization reaction process at the temperature of 80 +/-5 ℃, and after the reaction is finished, adding ammonia water to neutralize until the pH value is 7-9, thus obtaining the acrylic acid anticorrosive emulsion.
3. Modification of acrylic acid antiseptic emulsion
And (3) adding the resin obtained in the step (1) with the mass of 5-10% of that of the emulsion into the emulsion prepared in the step (2), preserving the heat for 1 hour at the temperature of 80 ℃, and cooling to obtain the anticorrosive emulsion.
Comparative example 1
1. Preparation of epoxy-modified aqueous acrylic dispersions
(1) Heating medium and high molecular weight epoxy resin with the molecular weight of 1500-5000 and soya-bean oil acid with double bonds in a reaction kettle according to the mass ratio of 1:1.2, adding zinc oxide accounting for 0.04 percent of the total mass of the epoxy resin and the linoleic acid as an esterification catalyst, starting stirring, and carrying out esterification reaction at 200 ℃ to graft the epoxy resin on carboxylic acid molecules to obtain an epoxy ester intermediate;
(2) dropwise adding an acrylic acid and acrylate monomer mixture into the epoxy ester intermediate prepared in the step (1), wherein the mass ratio of the intermediate to the acrylic acid and acrylate monomer mixture is 3:1, the acrylic acid accounts for 30% of the total mass of the acrylic acid and acrylate monomer, adding a tert-butyl peroxybenzoate (TBPB) initiator into the mixture, the amount of the TBPB initiator accounts for 3% of the total mass of the acrylic acid and acrylate monomer, and carrying out free radical copolymerization at the temperature of 120 ℃ to obtain epoxy modified acrylic resin;
(3) adding dimethylethanolamine into the epoxy modified acrylic resin obtained in the step (2), stirring until the pH value of the system reaches 8, and adding deionized water to form the epoxy modified acrylic resin aqueous dispersion.
2. Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and a sodium vinylsulfonate emulsifier with the mass fraction accounting for 30 percent of the total dosage into a reaction kettle;
(2) adding ionized water, acrylic acid, an acrylate monomer, a PAM-100 functional monomer and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, wherein the using amount of the functional monomer accounts for 1.5% of the total mass of the acrylic acid and the acrylate monomer, the using amount of the acrylic acid accounts for 30% of the total mass of the acrylic acid and the acrylate monomer, the total using amount of the emulsifier accounts for 1.3% of the total mass of the acrylic acid and the acrylate monomer, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
(3) after pre-emulsification is finished, respectively adding ammonium persulfate initiators accounting for 0.1 percent and 0.3 percent of the total mass of acrylic acid and acrylate monomers into an emulsifying kettle and a reaction kettle, starting the reaction kettle to stir, and heating to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed for 3h, preserving the heat for 2h, carrying out a free radical polymerization reaction process at the temperature of 80 +/-5 ℃, and after the reaction is finished, adding ammonia water to neutralize until the pH value is 7-9, thus obtaining the acrylic acid anticorrosive emulsion.
3. Modification of acrylic acid antiseptic emulsion
And (3) adding the resin obtained in the step (1) with the mass of 5% of that of the emulsion into the emulsion prepared in the step (2), preserving the heat for 1 hour at the temperature of 80 ℃, and cooling to obtain the anticorrosive emulsion.
Comparative example 2
1. Preparation of epoxy-modified aqueous acrylic dispersions
(1) Heating low molecular weight epoxy resin with the molecular weight of 500-1000 and linoleic acid with double bonds in a reaction kettle according to the mass ratio of 1:1.2, adding zinc oxide which is 0.04 percent of the total mass of the epoxy resin and the linoleic acid and is used as an esterification catalyst, starting stirring, and carrying out esterification reaction at 200 ℃ to graft the epoxy resin on carboxylic acid molecules to prepare an epoxy ester intermediate;
(2) dripping a mixture of acrylic acid and acrylate monomers into the epoxy ester intermediate prepared in the step (1), wherein the mass ratio of the intermediate to the mixture of the acrylic acid and the acrylate monomers is 3:1, adding a benzoyl peroxide tert-butyl ester (TBPB) initiator into the mixture, and carrying out free radical copolymerization at the temperature of 120 ℃ to obtain epoxy modified acrylic resin;
(3) adding dimethylethanolamine into the epoxy modified acrylic resin obtained in the step (2), stirring until the pH value of the system reaches 8, and adding deionized water to form the epoxy modified acrylic resin aqueous dispersion.
2. Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and a sodium vinylsulfonate emulsifier with the mass fraction accounting for 30 percent of the total dosage into a reaction kettle;
(2) adding ionized water, acrylic acid, an acrylate monomer, a PAM-100 functional monomer and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, wherein the using amount of the functional monomer accounts for 1.5% of the total mass of the acrylic acid and the acrylate monomer, the using amount of the acrylic acid accounts for 30% of the total mass of the acrylic acid and the acrylate monomer, the total using amount of the emulsifier accounts for 1.3% of the total mass of the acrylic acid and the acrylate monomer, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
(3) after pre-emulsification is finished, respectively adding ammonium persulfate initiators accounting for 0.1 percent and 0.3 percent of the total mass of acrylic acid and acrylate monomers into an emulsifying kettle and a reaction kettle, starting the reaction kettle to stir, and heating to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed for 3h, preserving the heat for 2h, carrying out a free radical polymerization reaction process at the temperature of 80 +/-5 ℃, and after the reaction is finished, adding ammonia water to neutralize until the pH value is 7-9, thus obtaining the acrylic acid anticorrosive emulsion.
3. Modification of acrylic acid antiseptic emulsion
And (3) adding the resin obtained in the step (1) with the mass of 5% of that of the emulsion into the emulsion prepared in the step (2), preserving the heat for 1 hour at the temperature of 80 ℃, and cooling to obtain the anticorrosive emulsion.
Comparative example 3
Preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and a sodium vinylsulfonate emulsifier with the mass fraction accounting for 30 percent of the total dosage into a reaction kettle;
(2) adding ionized water, acrylic acid, an acrylate monomer, a PAM-100 functional monomer and the rest 70% of the emulsifier in the step (1) into an emulsifying kettle, wherein the using amount of the functional monomer accounts for 1.5% of the total mass of the acrylic acid and the acrylate monomer, the using amount of the acrylic acid accounts for 30% of the total mass of the acrylic acid and the acrylate monomer, the total using amount of the emulsifier accounts for 1.3% of the total mass of the acrylic acid and the acrylate monomer, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
(3) after pre-emulsification is finished, respectively adding ammonium persulfate initiators accounting for 0.1 percent and 0.3 percent of the total mass of acrylic acid and acrylate monomers into an emulsifying kettle and a reaction kettle, starting the reaction kettle to stir, and heating to 80 +/-5 ℃;
(4) and after the temperature of the reaction kettle reaches, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed for 3h, preserving the heat for 2h, carrying out a free radical polymerization reaction process at the temperature of 80 +/-5 ℃, and after the reaction is finished, adding ammonia water to neutralize until the pH value is 7-9, thus obtaining the acrylic acid anticorrosive emulsion.
The performance data of the anti-corrosion emulsion prepared by the invention are shown in table 1, 5 mass percent of alcohol ester is added into the prepared emulsion, the emulsion is brushed on a rectangular tin plate by a 50-micrometer wire bar, the emulsion is placed at normal temperature for 7 days to form a film, and the performance of the film is tested as shown in table 2.
TABLE 1 emulsion Properties
TABLE 2 paint film Properties
Claims (5)
1. A preparation method of polyacrylate anticorrosive emulsion with excellent salt mist resistance is characterized by comprising the following steps: the preparation method comprises the following steps:
preparation of epoxy modified aqueous acrylic acid dispersoid
(1) Heating epoxy resin and linoleic acid with double bonds in a reaction kettle according to the mass ratio of 1:1-1:1.5, adding an esterification catalyst, starting stirring, and carrying out an esterification reaction at the temperature of 200-;
the epoxy resin is 1500-5000-containing medium-high molecular weight epoxy resin, the esterification catalyst is zinc oxide, and the dosage of the zinc oxide is as follows: the total mass of the epoxy resin and the linoleic acid is 0.04 percent;
(2) dripping acrylic acid and acrylate monomer mixture into the epoxy ester intermediate prepared in the step (1), adding peroxide initiator into the mixture, and carrying out free radical copolymerization at the temperature of 120-130 ℃ to obtain epoxy modified acrylic resin;
(3) adding a neutralizing agent into the epoxy modified acrylic resin obtained in the step (2), stirring to reach a required pH value, and adding deionized water to form an epoxy modified aqueous acrylic dispersion;
preparation of acrylic acid antiseptic emulsion
(1) Adding deionized water and vinylsulfonate reactive emulsifier with the mass fraction accounting for 30 percent of the total dosage of the emulsifier into a reaction kettle;
(2) adding deionized water, acrylic acid, acrylate monomer, functional monomer and the rest 70% of vinylsulfonate reactive emulsifier into an emulsifying kettle, stirring, and pre-emulsifying at the rotating speed of more than 120rpm for 2 hours to obtain a pre-emulsion;
the functional monomer is phosphate functional monomer, and the using amount of the functional monomer accounts for 1.0-1.5% of the total mass of the acrylic acid and acrylate monomers;
(3) after pre-emulsification is finished, respectively adding persulfate initiators into an emulsification kettle and a reaction kettle, starting the reaction kettle for stirring, and heating to 80 +/-5 ℃;
(4) after the temperature of the reaction kettle reaches 80 +/-5 ℃, dropwise adding the pre-emulsion in the emulsifying kettle into the reaction kettle at a constant speed, carrying out free radical polymerization reaction, and adding ammonia water for neutralization after the reaction is finished to prepare the acrylic acid anticorrosive emulsion;
third, modification of acrylic acid antiseptic emulsion
And adding epoxy modified aqueous acrylic acid dispersoid accounting for 5-10 percent of the weight of the emulsion into the prepared acrylic acid anticorrosive emulsion, stirring, keeping the temperature at 80 ℃ for 1 hour, and cooling to obtain the anticorrosive emulsion.
2. The method for preparing the polyacrylate anticorrosive emulsion having excellent salt spray resistance as claimed in claim 1, wherein: in the process of preparing the epoxy modified aqueous acrylic acid dispersion, the mass ratio of the epoxy ester intermediate in the step (2) to the mixture of acrylic acid and acrylic ester monomers is 3:1-4:1, the acrylic acid in the mixture accounts for 30% of the total mass of the acrylic acid and acrylic ester monomers, and the using amount of the peroxide initiator accounts for 3-4% of the total mass of the acrylic acid and acrylic ester monomers.
3. The method for preparing the polyacrylate anticorrosive emulsion having excellent salt spray resistance as claimed in claim 1, wherein: in the process of preparing the epoxy modified aqueous acrylic acid dispersion, the neutralizing agent in the step (3) is organic amine or ammonia water, and the pH is adjusted to 7-9.
4. The method for preparing the polyacrylate anticorrosive emulsion having excellent salt spray resistance as claimed in claim 1, wherein: in the preparation process of the acrylic acid anticorrosive emulsion, the acrylic acid in the step (2) accounts for 30% of the total mass of the acrylic acid and acrylate ester monomers, and the total using amount of the emulsifier accounts for 1.2% -1.5% of the total mass of the acrylic acid and acrylate ester monomers.
5. The method for preparing the polyacrylate anticorrosive emulsion having excellent salt spray resistance as claimed in claim 1, wherein: in the preparation process of the acrylic acid anticorrosive emulsion, the initiators added into the emulsifying kettle and the reaction kettle in the step (3) respectively account for 0.1-0.15% and 0.3-0.45% of the total mass of acrylic acid and acrylate ester monomers.
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