CN108794703A - A kind of preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function - Google Patents
A kind of preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function Download PDFInfo
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- CN108794703A CN108794703A CN201810677723.3A CN201810677723A CN108794703A CN 108794703 A CN108794703 A CN 108794703A CN 201810677723 A CN201810677723 A CN 201810677723A CN 108794703 A CN108794703 A CN 108794703A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The present invention provides a kind of preparation methods of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function, the epoxy resin of middle high molecular weight and the linolenic acid with double bond are subjected to esterification first, epoxy-ester intermediate is made, acrylic acid and acrylate monomer blend are added dropwise thereto, and initiator is added, it carries out free-radical polymerized, obtain epoxy modified acrylic resin, add neutralizer stirring, reach required pH value, deionized water is added and forms epoxy-modified acrylic acid resin aqueous dispersion, then it is heated in conventional acrylic anti-corrosion lotion, improve the defect that lotion molecule squeezes film forming, to make acrylic acid anti-corrosion lotion that there is better anti-corrosion stability, greatly improve the antiseptic property of acrylic emulsion.
Description
Technical field
The invention belongs to anti-corrosion material field, more particularly to a kind of polyacrylate anti-corrosion with excellent salt spray resistance function
The preparation method of lotion.
Background technology
Due to the thin film-forming method of acrylic emulsions is close to each other during moisture evaporation for lotion macromolecular, squeeze and
Continuous film is formed, therefore inevitably there is a problem of being formed by film not enough densification, along in lotion building-up process
The use of emulsifier etc. causes the film water resistance salt spray resistance that lotion is formed bad, and it is even more third that especially salt fog resistance is bad
The critical defect of olefin(e) acid class anti-corrosion lotion.
Acrylic compounds anti-corrosion lotion in the prior art uses water resistance auxiliary agent or reactive emulsifier in preparation process,
It reduces the use of ready water-solubility auxiliary agent to the greatest extent, while being modified by adding function monomer, so that lotion is had preferably water-fast
Salt spray resistance improves its filming performance.But due to the addition of various auxiliary agents and function monomer, cause cost higher, auxiliary agent
Use cause stability of emulsion to reduce.
Invention content
It is existing in the prior art in order to solve：Due to the not enough densification that forms a film, the existing anti-fermented bean curd of acrylic compounds
Aqueous anticorrosion paint salt spray resistance prepared by liquid is bad, causes product that cannot obtain good anti-corrosion effect, the use of auxiliary agent
The technical issues of causing stability of emulsion to reduce.
The present invention provides a kind of preparation methods of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function, are made
Anti-corrosion lotion improve the gap formed during emulsion film forming, keep the acrylic acid ester emulsion film forming of the present invention complete fine and close,
So as to improve the water-fast salt spray resistance of polyacrylate anti-corrosion lotion.
The present invention have excellent salt spray resistance function polyacrylate anti-corrosion lotion preparation method include but not limited to
Lower content:
1, epoxy modified aqueous acrylic acid resin water dispersion is prepared
(1) according to 1:1-1:1.5 mass ratio heats epoxy resin and the linolenic acid with double bond in a kettle, adds
Enter esterification catalyst, open stirring, esterification is carried out at 200-210 DEG C, is made on epoxy resin graft to carboxylic acid molecules, makes
Obtain epoxy-ester intermediate；
Wherein, epoxy resin is the middle high molecular expoxy resin of 1500-5000, the epoxy molecule of middle high molecular weight
Chain length, obtained by modified acroleic acid resin aqueous dispersion side chain hydrophobic grouping it is more, response type crosslinked group is also more, crosslinking
Higher is spent, the water-tolerant for being formed by paint film is macroscopically shown as, paint film is finer and close, and antiseptic property is reinforced.
The linolenic acid with double bond selected is drying oil oleic acid, it can be with propylene with enough conjugation carbon-carbon double bonds
Acid and acrylate monomer carry out free radicals copolymerization reaction.
Esterification catalyst is zinc oxide, and dosage is the 0.04% of epoxy resin and linolenic acid gross mass.
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), to mixed
It closes and peroxide type initiators TBPB is added in object, at a temperature of 120 DEG C -130 DEG C, progress is free-radical polymerized, obtains epoxy
It is acrylic resin modified；
Wherein, epoxy-ester intermediate and acrylic acid and the mass ratio of acrylate monomer blend are 3:1-4:1, mixing
Acrylic acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass in object；The dosage of peroxide type initiators accounts for propylene
The 3-4% of acid and acryllic acid ester monomer gross mass.
Acrylic acid is added it is in later stage and neutralizer and form aqueous group so that resin has water solubility, addition
Acrylate monomer assigns resin side chain some groups, plays water-fast, the effects that increasing gloss of film, while its type and rear step
The acrylate monomer of rapid lotion is identical, and segment integral polarity difference is little, similar compatibility, provides preferably miscible with lotion
Property so that lotion is filled in film forming procedure automatically since lotion macromolecular squeezes the hole that is not close and being formed that forms a film, and is made
Lotion forms the film of complete densification, improves the defect that lotion molecule squeezes film forming, to make acrylic acid anti-corrosion lotion have more
Good anti-corrosion stability, greatly improves the antiseptic property of this product, especially salt spray resistance and has obtained larger promotion.
It is optimal through testing the gained resin property under the consumption proportion.
(3) neutralizer stirring is added in the epoxy modified acrylic resin obtained to step (2), reaches required pH value, adds
Enter deionized water and forms epoxy-modified acrylic acid resin aqueous dispersion.
Wherein, neutralizer is organic amine or ammonium hydroxide, adjusts pH to 7-9, and stable epoxy is formed deionized water is added
Modified acroleic acid resin aqueous dispersion, wherein epoxy-modified acrylic acid resin solid content is 40%.
Resin be added neutralizer in and after obtain aqueous group, viscosity can be substantially increased, and be not easy to later step
It uses, using water as solvent, it is in order to reduce system viscosity, to facilitate subsequent use to form aqueous dispersion.
2, the preparation of acrylic acid anti-corrosion lotion
(1) it is added deionized water into reaction kettle and mass fraction accounts for the vinyl sulfonic acid of the total dosage of emulsifier 30%
Salts reaction type emulsifier；
(2) deionized water, acrylic acid, acrylate monomer and function monomer and remaining 70% are added into emulsifying kettle
The step of (1) described in emulsifier, open stirring, rotating speed is more than 120rpm, carries out pre-emulsification, pre-emulsification object is obtained after 2 hours；
Wherein, function monomer is phosphoric acid ester function monomer, and dosage accounts for acrylic acid and the total matter of acryllic acid ester monomer
The 1.0%-1.5% of amount, acrylic acid account for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for third
The 1.2%-1.5% of olefin(e) acid and acryllic acid ester monomer gross mass.
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The persulfuric acid salt initiator of gross mass 0.1%-0.15% and 0.3%-0.45% open reaction kettle stirring, are warming up to 80 ± 5
℃；
(4) after temperature of reaction kettle reaches, the pre-emulsification object in emulsifying kettle is at the uniform velocity added dropwise into reaction kettle, at 80 ± 5 DEG C
At a temperature of carry out Raolical polymerizable, ammonium hydroxide is added after the completion of reaction and is neutralized to pH=7-9, acrylic acid anti-corrosion lotion is made.
3, the modification of acrylic acid anti-corrosion lotion
The epoxy-modified acrylic acid resin that the 5-10% of quality of the emulsion is added into obtained acrylic acid anti-corrosion lotion is water-dispersed
Body stirs, and 1 hour is kept the temperature at 80 DEG C, the cooling anti-corrosion lotion that the present invention is made.
Since epoxy-modified acrylic acid resin aqueous dispersion viscosity is larger, does not heat to be directly added into lotion and is not easy to disperse,
It can form caking, phenomena such as reunion, uniform mixture can not be formed.Present invention hot melting temperature at 80 DEG C is high, and resin glues
Degree declines, it is easier to epoxy-modified acrylic acid resin aqueous dispersion is dispersed in lotion by churned mechanically effect.
Advantageous effect：The present invention by being heated into epoxy modified acrylic resin aqueous dispersion in common anti-corrosion lotion,
Since macromolecular chain segment different polarities are small, better compatibility is had according to similar compatibility principle dispersion and lotion molecule so that
Lotion is filled in film forming procedure automatically since lotion macromolecular squeezes the hole that is not close and being formed that forms a film, and lotion is made to be formed
Complete fine and close film improves the defect that lotion molecule squeezes film forming, to make acrylic acid anti-corrosion lotion have better anti-corrosion
Stability greatly improves the antiseptic property of this product, especially salt spray resistance and has obtained larger promotion.
In addition, esterification catalyst dosage of the present invention is less, it is added in lotion and can be ignored.Remaining initiator and anti-
The type emulsifier of answering is involved in reaction during the reaction, will not be free in resin system, will not be impacted to film forming.
Specific implementation mode
Below by embodiment, the present invention will be described in detail.
Embodiment 1
1, epoxy modified aqueous acrylic acid dispersion is prepared
(1) according to 1:1.2 mass ratio is by the middle high molecular expoxy resin that molecular weight is 1500-5000 and with double bond
Linolenic acid heats in a kettle, and the zinc oxide of epoxy resin and linolenic acid gross mass 0.04% is added, is urged as esterification
Agent opens stirring, esterification is carried out at 200 DEG C, is made on epoxy resin graft to carboxylic acid molecules, is made among epoxy-ester
Body；
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), it is intermediate
Body is 3 with acrylic acid and the mass ratio of acrylate monomer blend:1, acrylic acid accounts for acrylic acid and acrylic acid acid esters list
The 30% of body gross mass, the tertiary fourth fat (TBPB) of benzoyl peroxide is added into mixture, and dosage accounts for acrylic acid and acrylic acid
The 3% of acid ester monomer gross mass, at a temperature of 120 DEG C, progress is free-radical polymerized, obtains epoxy modified acrylic resin；
(3) in the epoxy modified acrylic resin obtained to step (2) be added dimethylethanolamine stirring, dosage be until
Until system pH reaches 8, adds deionized water and form epoxy-modified acrylic acid resin aqueous dispersion.
2, the preparation of acrylic acid anti-corrosion lotion
(1) it is added deionized water into reaction kettle and mass fraction accounts for the vinyl sulfonic acid of the total dosage of emulsifier 30%
Sodium emulsifier；
(2) ionized water, acrylic acid, acrylate monomer and PAM-100 function monomers and residue are added into emulsifying kettle
Emulsifier in 70% the step of (1), function monomer dosage account for the 1.5% of acrylic acid and acryllic acid ester monomer gross mass, and third
Olefin(e) acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for acrylic acid and acrylic acid acid esters
The 1.3% of monomer gross mass opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, 2 as a child obtain pre-emulsification object afterwards；
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The ammonium persulfate initiator of gross mass 0.1% and 0.3% opens reaction kettle stirring, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches, 3h is at the uniform velocity added dropwise into reaction kettle for the pre-emulsification object in emulsifying kettle, keeps the temperature 2h,
Raolical polymerizable process is carried out at a temperature of 80 ± 5 DEG C, ammonium hydroxide, which is added, after the completion of reaction is neutralized to pH=7-9, is made
Acrylic acid anti-corrosion lotion.
3, the modification of acrylic acid anti-corrosion lotion
5% step 1 gained resin of quality of the emulsion is added into lotion obtained in step 2, heat preservation 1 is small at 80 DEG C
When, the cooling anti-corrosion lotion that the present invention is made.
Embodiment 2
1, epoxy modified aqueous acrylic acid dispersion is prepared
(1) according to 1:1.3 mass ratio is by the middle high molecular expoxy resin that molecular weight is 1500-5000 and with double bond
Linolenic acid heats in a kettle, and the zinc oxide of epoxy resin and linolenic acid gross mass 0.04% is added, is urged as esterification
Agent opens stirring, esterification is carried out at 205 DEG C, is made on epoxy resin graft to carboxylic acid molecules, is made among epoxy-ester
Body；
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), it is intermediate
Body is 3.5 with acrylic acid and the mass ratio of acrylate monomer blend:1, acrylic acid accounts for acrylic acid and acrylic acid acid esters
The 30% of monomer gross mass, the tertiary fourth fat (TBPB) of benzoyl peroxide is added into mixture, and dosage accounts for acrylic acid and propylene
The 3% of sour acid ester monomer gross mass, at a temperature of 120 DEG C, progress is free-radical polymerized, obtains epoxy modified acrylic resin；
(3) in the epoxy modified acrylic resin obtained to step (2) be added dimethylethanolamine stirring, dosage be until
Until system pH reaches 8, adds deionized water and form epoxy-modified acrylic acid resin aqueous dispersion.
2, the preparation of acrylic acid anti-corrosion lotion
(1) it is added deionized water into reaction kettle and mass fraction accounts for the vinyl sulfonic acid of the total dosage of emulsifier 30%
Sodium emulsifier；
(2) ionized water, acrylic acid, acrylate monomer and PAM-100 function monomers and residue are added into emulsifying kettle
Emulsifier in 70% the step of (1), function monomer dosage account for the 1.0% of acrylic acid and acryllic acid ester monomer gross mass, and third
Olefin(e) acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for acrylic acid and acrylic acid acid esters
The 1.2% of monomer gross mass opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, 2 as a child obtain pre-emulsification object afterwards；
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The ammonium persulfate initiator of gross mass 0.1% and 0.3% opens reaction kettle stirring, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches, 3h is at the uniform velocity added dropwise into reaction kettle for the pre-emulsification object in emulsifying kettle, keeps the temperature 2h,
Raolical polymerizable process is carried out at a temperature of 80 ± 5 DEG C, ammonium hydroxide, which is added, after the completion of reaction is neutralized to pH=7-9, is made
Acrylic acid anti-corrosion lotion.
3, the modification of acrylic acid anti-corrosion lotion
The step 1 gained resin of the 5-10% of quality of the emulsion is added into lotion obtained in step 2, is kept the temperature at 80 DEG C
1 hour, the cooling anti-corrosion lotion that the present invention is made.
Embodiment 3
1, epoxy modified aqueous acrylic acid dispersion is prepared
(1) according to 1:1.5 mass ratio is by the middle high molecular expoxy resin that molecular weight is 1500-5000 and with double bond
Linolenic acid heats in a kettle, and the zinc oxide of epoxy resin and linolenic acid gross mass 0.04% is added, is urged as esterification
Agent opens stirring, esterification is carried out at 210 DEG C, is made on epoxy resin graft to carboxylic acid molecules, is made among epoxy-ester
Body；
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), it is intermediate
Body is 4 with acrylic acid and the mass ratio of acrylate monomer blend:1, acrylic acid accounts for acrylic acid and acrylic acid acid esters list
The 30% of body gross mass, into mixture be added peroxidized t-butyl perbenzoate (TBPB) initiator, dosage account for acrylic acid and
The 3.5% of acryllic acid ester monomer gross mass, at a temperature of 125 DEG C, progress is free-radical polymerized, obtains epoxy-modified acrylic acid
Resin；
(3) ammonium hydroxide stirring is added in the epoxy modified acrylic resin obtained to step (2), dosage is until system pH reaches
Until 7, adds deionized water and form epoxy-modified acrylic acid resin aqueous dispersion.
2, the preparation of acrylic acid anti-corrosion lotion
(1) deionized water is added into reaction kettle and mass fraction accounts for the sodium vinyl sulfonate emulsification of total dosage 30%
Agent；
(2) ionized water, acrylic acid, acrylate monomer and PAM-100 function monomers and residue are added into emulsifying kettle
Emulsifier in 70% the step of (1), function monomer dosage account for the 1.5% of acrylic acid and acryllic acid ester monomer gross mass, and third
Olefin(e) acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for acrylic acid and acrylic acid acid esters
The 1.5% of monomer gross mass opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, 2 as a child obtain pre-emulsification object afterwards；
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The ammonium persulfate initiator of gross mass 0.15% and 0.4% opens reaction kettle stirring, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches, 3h is at the uniform velocity added dropwise into reaction kettle for the pre-emulsification object in emulsifying kettle, keeps the temperature 2h,
Raolical polymerizable process is carried out at a temperature of 80 ± 5 DEG C, ammonium hydroxide, which is added, after the completion of reaction is neutralized to pH=7-9, is made
Acrylic acid anti-corrosion lotion.
3, the modification of acrylic acid anti-corrosion lotion
The step 1 gained resin of the 5-10% of quality of the emulsion is added into lotion obtained in step 2, is kept the temperature at 80 DEG C
1 hour, the cooling anti-corrosion lotion that the present invention is made.
Comparative example 1
1, epoxy modified aqueous acrylic acid dispersion is prepared
(1) according to 1:1.2 mass ratio is by the middle high molecular expoxy resin that molecular weight is 1500-5000 and with double bond
It is heated in behenic acid reaction kettle, the zinc oxide of epoxy resin and linolenic acid gross mass 0.04% is added, as esterification catalyst,
Stirring is opened, esterification is carried out at 200 DEG C, is made on epoxy resin graft to carboxylic acid molecules, epoxy-ester intermediate is made；
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), it is intermediate
Body is 3 with acrylic acid and the mass ratio of acrylate monomer blend:1, acrylic acid accounts for acrylic acid and acrylic acid acid esters list
The 30% of body gross mass, into mixture be added peroxidized t-butyl perbenzoate (TBPB) initiator, dosage account for acrylic acid and
The 3% of acryllic acid ester monomer gross mass, at a temperature of 120 DEG C, progress is free-radical polymerized, obtains epoxy-modified acrylic acid tree
Fat；
(3) in the epoxy modified acrylic resin obtained to step (2) be added dimethylethanolamine stirring, dosage be until
Until system pH reaches 8, adds deionized water and form epoxy-modified acrylic acid resin aqueous dispersion.
2, the preparation of acrylic acid anti-corrosion lotion
(1) deionized water is added into reaction kettle and mass fraction accounts for the sodium vinyl sulfonate emulsification of total dosage 30%
Agent；
(2) ionized water, acrylic acid, acrylate monomer and PAM-100 function monomers and residue are added into emulsifying kettle
Emulsifier in 70% the step of (1), function monomer dosage account for the 1.5% of acrylic acid and acryllic acid ester monomer gross mass, and third
Olefin(e) acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for acrylic acid and acrylic acid acid esters
The 1.3% of monomer gross mass opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, 2 as a child obtain pre-emulsification object afterwards；
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The ammonium persulfate initiator of gross mass 0.1% and 0.3% opens reaction kettle stirring, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches, 3h is at the uniform velocity added dropwise into reaction kettle for the pre-emulsification object in emulsifying kettle, keeps the temperature 2h,
Raolical polymerizable process is carried out at a temperature of 80 ± 5 DEG C, ammonium hydroxide, which is added, after the completion of reaction is neutralized to pH=7-9, is made
Acrylic acid anti-corrosion lotion.
3, the modification of acrylic acid anti-corrosion lotion
5% step 1 gained resin of quality of the emulsion is added into lotion obtained in step 2, heat preservation 1 is small at 80 DEG C
When, the cooling anti-corrosion lotion that the present invention is made.
Comparative example 2
1, epoxy modified aqueous acrylic acid dispersion is prepared
(1) according to 1:1.2 mass ratio is by molecular weight for 500-1000 low-molecular-weight epoxy resins and with flax of double bond
Oleic acid heats in a kettle, and the zinc oxide of epoxy resin and linolenic acid gross mass 0.04% is added, as esterification catalyst,
Stirring is opened, esterification is carried out at 200 DEG C, is made on epoxy resin graft to carboxylic acid molecules, epoxy-ester intermediate is made；
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), it is intermediate
Body is 3 with acrylic acid and the mass ratio of acrylate monomer blend:1, the tertiary fourth of benzoyl peroxide is added into mixture
Fat (TBPB) initiator, at a temperature of 120 DEG C, progress is free-radical polymerized, obtains epoxy modified acrylic resin；
(3) in the epoxy modified acrylic resin obtained to step (2) be added dimethylethanolamine stirring, dosage be until
Until system pH reaches 8, adds deionized water and form epoxy-modified acrylic acid resin aqueous dispersion.
2, the preparation of acrylic acid anti-corrosion lotion
(1) deionized water is added into reaction kettle and mass fraction accounts for the sodium vinyl sulfonate emulsification of total dosage 30%
Agent；
(2) ionized water, acrylic acid, acrylate monomer and PAM-100 function monomers and residue are added into emulsifying kettle
Emulsifier in 70% the step of (1), function monomer dosage account for the 1.5% of acrylic acid and acryllic acid ester monomer gross mass, and third
Olefin(e) acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for acrylic acid and acrylic acid acid esters
The 1.3% of monomer gross mass opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, 2 as a child obtain pre-emulsification object afterwards；
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The ammonium persulfate initiator of gross mass 0.1% and 0.3% opens reaction kettle stirring, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches, 3h is at the uniform velocity added dropwise into reaction kettle for the pre-emulsification object in emulsifying kettle, keeps the temperature 2h,
Raolical polymerizable process is carried out at a temperature of 80 ± 5 DEG C, ammonium hydroxide, which is added, after the completion of reaction is neutralized to pH=7-9, is made
Acrylic acid anti-corrosion lotion.
3, the modification of acrylic acid anti-corrosion lotion
5% step 1 gained resin of quality of the emulsion is added into lotion obtained in step 2, heat preservation 1 is small at 80 DEG C
When, the cooling anti-corrosion lotion that the present invention is made.
Comparative example 3
The preparation of acrylic acid anti-corrosion lotion
(1) deionized water is added into reaction kettle and mass fraction accounts for the sodium vinyl sulfonate emulsification of total dosage 30%
Agent；
(2) ionized water, acrylic acid, acrylate monomer and PAM-100 function monomers and residue are added into emulsifying kettle
Emulsifier in 70% the step of (1), function monomer dosage account for the 1.5% of acrylic acid and acryllic acid ester monomer gross mass, and third
Olefin(e) acid accounts for the 30% of acrylic acid and acryllic acid ester monomer gross mass, and the total dosage of emulsifier accounts for acrylic acid and acrylic acid acid esters
The 1.3% of monomer gross mass opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, 2 as a child obtain pre-emulsification object afterwards；
(3) it after the completion of pre-emulsification, is separately added into emulsifying kettle and reaction kettle and accounts for acrylic acid and acryllic acid ester monomer
The ammonium persulfate initiator of gross mass 0.1% and 0.3% opens reaction kettle stirring, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches, 3h is at the uniform velocity added dropwise into reaction kettle for the pre-emulsification object in emulsifying kettle, keeps the temperature 2h,
Raolical polymerizable process is carried out at a temperature of 80 ± 5 DEG C, ammonium hydroxide, which is added, after the completion of reaction is neutralized to pH=7-9, is made
Acrylic acid anti-corrosion lotion.
Anti-corrosion emulsion property data produced by the present invention are shown in Table 1, the alcohol ester of its quality 5% will be added in lotion obtained,
It is brushed in rectangle tinplate with 50 μm of bars, room temperature forms a film for 7 days, tests paint film property such as table 2.
1 emulsion property of table
2 paint film property of table
Claims (6)
1. a kind of preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function, it is characterised in that：The system
Preparation Method includes the following steps：
1, epoxy modified aqueous acrylic acid dispersion is prepared
(1) according to 1:1-1:1.5 mass ratio heats epoxy resin and the linolenic acid with double bond in a kettle, and ester is added
Change catalyst, open stirring, esterification is carried out at 200-210 DEG C, is made on epoxy resin graft to carboxylic acid molecules, ring is made
Oxygen ester intermediate；
(2) acrylic acid and acrylate monomer blend are added dropwise into epoxy-ester intermediate made from step (1), to mixture
Middle addition peroxide type initiators, at a temperature of 120 DEG C -130 DEG C, progress is free-radical polymerized, obtains epoxy-modified propylene
Acid resin；
(3) neutralizer stirring is added in the epoxy modified acrylic resin obtained to step (2), reaches required pH value, addition is gone
Ionized water forms epoxy-modified acrylic acid resin aqueous dispersion；
2, the preparation of acrylic acid anti-corrosion lotion
(1) it is added deionized water into reaction kettle and mass fraction accounts for the vinyl sulfonic acid salt of the total dosage of emulsifier 30%
Reactive emulsifier；
(2) be added deionized water into emulsifying kettle, acrylic acid, acrylate monomer and function monomer and remaining 70% second
Olefin sulfonic acid salt reactive emulsifier opens stirring, and rotating speed is more than 120rpm, carries out pre-emulsification, pre-emulsification is obtained after 2 hours
Object；
(3) after the completion of pre-emulsification, it is separately added into persulfuric acid salt initiator into emulsifying kettle and reaction kettle, opens reaction kettle and stirs
It mixes, is warming up to 80 ± 5 DEG C；
(4) after temperature of reaction kettle reaches 80 ± 5 DEG C, the pre-emulsification object in emulsifying kettle is at the uniform velocity added dropwise into reaction kettle, carries out freely
Base polymerisation is added ammonium hydroxide after the completion of reaction and neutralizes, acrylic acid anti-corrosion lotion is made；
3, the modification of acrylic acid anti-corrosion lotion
The epoxy-modified acrylic acid resin aqueous dispersion of quality of the emulsion 5-10% is added into acrylic acid anti-corrosion lotion obtained, stirs
It mixes, 1 hour is kept the temperature at 80 DEG C, the cooling anti-corrosion lotion that the present invention is made.
2. the preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function as described in claim 1, special
Sign is：During preparing epoxy modified aqueous acrylic acid dispersion, step (1) described epoxy resin is 1500-5000's
Middle high molecular expoxy resin, esterification catalyst are zinc oxide, and dosage is：Epoxy resin and linolenic acid gross mass
0.04%.
3. the preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function as described in claim 1, special
Sign is：During preparing epoxy modified aqueous acrylic acid dispersion, step (2) the epoxy-ester intermediate and acrylic acid with
And the mass ratio of acrylate monomer blend is 3:1-4:1, acrylic acid accounts for acrylic acid and acrylic acid acid esters list in mixture
The dosage of the 30% of body gross mass, peroxide type initiators accounts for acrylic acid and the 3-4% of acryllic acid ester monomer gross mass.
4. the preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function as described in claim 1, special
Sign is：During preparing epoxy modified aqueous acrylic acid dispersion, step (3) described neutralizer is organic amine or ammonia
Water adjusts pH to 7-9.
5. the preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function as described in claim 1, special
Sign is：In the preparation process of acrylic acid anti-corrosion lotion, step (2) described function monomer is phosphoric acid ester function monomer, is used
Amount accounts for acrylic acid and the 1.0%-1.5% of acryllic acid ester monomer gross mass, and acrylic acid accounts for acrylic acid and acrylic acid acid esters
The 30% of monomer gross mass, the total dosage of emulsifier account for acrylic acid and the 1.2%-1.5% of acryllic acid ester monomer gross mass.
6. the preparation method of the polyacrylate anti-corrosion lotion with excellent salt spray resistance function as described in claim 1, special
Sign is：In the preparation process of acrylic acid anti-corrosion lotion, step (3) initiator being added into emulsifying kettle and reaction kettle point
Acrylic acid and acryllic acid ester monomer gross mass 0.1%-0.15% and 0.3%-0.45% are not accounted for.
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