CN103980407B - The phosphorous silicone-contained acrylic resin solution of aqueous and the directly coating of application on rusty scale - Google Patents
The phosphorous silicone-contained acrylic resin solution of aqueous and the directly coating of application on rusty scale Download PDFInfo
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Abstract
The present invention relates to the phosphorous silicone-contained acrylic resin solution of a kind of aqueous and the direct coating of application on rusty scale, belong to technical field of coatings.Coating composition, includes following component by weight percentage: the phosphorous silicone-contained acrylic resin solution 10%～25% of aqueous, aqueous alkide resin 10～20%, 2-aminooxyethanol 10～20%, corrosion inhibitor 5～15%, imidazoline 1～5%, function additive 1～5%, rust resisting pigment 10～15%, filler 10～15%.It is an advantage of the current invention that: 1, environmental protection；2, can directly application on rusty scale, it is not necessary to surface is carried out antirust treatment；3, corrosion-resistant high with adhesive force.
Description
Technical field
The present invention relates to the phosphorous silicone-contained acrylic resin solution of a kind of aqueous, its preparation method and a kind of can the direct coating composition of application on rusty scale, belong to technical field of coatings.
Background technology
Rusty scale coating is done many research.Such as, coating is divided into permeability, surely rust type, transformant by people.Although being made that many effort above-mentioned coating people, but remain without at technological layer and solve the problem that the adhesion of coating and rusty scale uses for a long time.Such as: current solution is organic molecule, such as coupling agent, but the adhesive force of improved coating, still it is difficult to meet the actual requirement of industry, even if disclosure satisfy that instructions for use at the coating initial stage, can being as the prolongation of the time used, organic molecule, gradually by the surface of diffusion coating, makes adhesive force deteriorate.Meanwhile, the coating used, because containing organic solvent, causing and pollute environment, environmental protection, the adhesive force and the antiseptic property that improve coating and rusty scale are the problems needing to solve.
Summary of the invention
For solving adhesive force and the environmental issue of coating and the rusty scale of coating, the present invention be the phosphorous silicone-contained acrylic resin solution of a kind of aqueous and include this resin can the direct coating composition of application on rusty scale.Technical scheme is as follows:
The phosphorous silicone-contained acrylic resin solution of aqueous, has the repeat unit structure as shown in formula (1):
In formula, R be for alkyl or cycloalkyl or aryl；It is preferred that, the carbon number of described alkyl is between 1～15；The carbon number of described cycloalkyl is between 3～15；It it is most preferably butyl；
In formula, R1 is carbon number is the alkyl between 4～8；
In formula, n1 is the integer between 1～4；N2 is the integer between 1～4；N3 is the integer between 1～4；N4 is the integer between 1～4.
The molecular weight of the phosphorous silicone-contained acrylic resin solution of above-mentioned aqueous is preferably between 20000～40000.
The preparation method that it is a further object to provide a kind of phosphorous silicone-contained acrylic resin solution of above-mentioned aqueous, comprises the steps:
Phosphatization hydroxyethyl acrylate monomers, methacrylic acid monomer, acrylate and siliceous hexenoic acid monomer are carried out copolymerization prepare.
In above-mentioned steps, shown in the structure such as formula (2) of described phosphatization 2-(Acryloyloxy)ethanol:
In formula (2), R be for alkyl or cycloalkyl or aryl；It is preferred that, described atomic number of alkyl carbon is between 1～15；The carbon number of described cycloalkyl is between 3～15；It it is most preferably butyl；Experiment finds that methyl, ethyl, propyl group hardness, dissolubility in water are better, and butyl adhesive force is best.
Shown in the structure such as formula (3) of above-mentioned siliceous hexenoic acid monomer:
CH2=CH-CH2-CH2Si (OCH3) 3
(3)。
In above-mentioned steps, shown in the structure of described acrylate such as formula (4):
CH2=CH-COOR1 (4)
In formula (4), R1 is carbon number is the alkyl between 4～8.
In above-mentioned steps, the mass ratio of each monomer is preferably: phosphatization 2-(Acryloyloxy)ethanol: methyl acrylic monomer: acrylate: siliceous vinyl monomer=25:45:5:1.
In above-mentioned steps, the condition of copolyreaction is preferably: carrying out polymerisation in bulk under the initiator azo two fine initiation of isobutyl, polymerization temperature is 55～75 DEG C.
Present invention also offers include the phosphorous silicone-contained acrylic resin solution of above-mentioned aqueous can the direct coating composition of application on rusty scale, include following component by weight percentage: the phosphorous silicone-contained acrylic resin solution 10%～25% of aqueous, aqueous alkide resin 10～20%, 2-aminooxyethanol 10～20%, corrosion inhibitor 5～15%, imidazoline 1～5%, function additive 1～5%, rust resisting pigment 10～15%, filler 10～15%.
Preferably, rust resisting pigment is one or several the mixture in micaceous iron oxide, zinc phosphate, zinc powder；More preferably zinc phosphate；Most preferably, the particle diameter of zinc phosphate is 0.5～5 micron.
Preferably, filler is the mixture of one or more in iron oxide red, clay, Pulvis Talci, calcium carbonate, aluminium hydroxide, magnesium hydroxide, kieselguhr, wollastonite in powder, barium sulfate, antimony oxide；It it is more preferably Pulvis Talci；Most preferred, talcous particle diameter is 0.5～5 micron.
Preferably, described function additive refers to that cobalt naphthenate, cobalt octoate, tin laurate are the mixture of 1:2:1 according to weight ratio.
Preferably, corrosion inhibitor refers to the mixture of salicylic acid and P-hydroxybenzoic acid, and its mixing quality is than for 2:1.
The preparation method of above-mentioned coating is: first by phosphorous silicone-contained acrylic resin solution, aqueous alkide resin, 2-aminooxyethanol, corrosion inhibitor, imidazoline, function additive mix homogeneously, be subsequently adding zinc phosphate, Pulvis Talci stirs, then grind on grinder, finally pack.
Synergetical principle between component: described ethylene copolymer phosphorous, siliceous is the material for improving antiseptic property, and its molecular weight is between 20000-40000.The purpose being adopted such copolymerization mode is in that: phosphorous-containing monomers strengthens the molecular binding affinities of resin and rusty scale, methacrylic acid increases the water solublity of resin, acrylate increases toughness and the permeability and diffusivity in rusty scale of coating, increase-volume is forced on the spot simultaneously as solubilizing agent strengthening and alkyd resin, siliceous vinyl monomer increases the adhesive force at interface, increases interchain force, after being combined with rusty scale simultaneously, make coating be changed into by water solublity insoluble, improve the antiseptic power of coating.
Beneficial effect
It is an advantage of the current invention that: 1, environmental protection；2, can directly application on rusty scale, it is not necessary to surface is carried out antirust treatment；3, corrosion-resistant high with adhesive force.
Detailed description of the invention
Embodiment 1
1. the preparation of the phosphorous silicone-contained acrylic resin solution of aqueous
Phosphatization hydroxyethyl acrylate monomers, methacrylic acid monomer, acrylate and siliceous hexenoic acid monomer are carried out copolymerization prepare；The mass ratio of each monomer is: phosphatization 2-(Acryloyloxy)ethanol: methyl acrylic monomer: acrylate: siliceous vinyl monomer=25:45:5:1；The condition of copolymerization is: under the initiator azo two fine initiation of isobutyl, carrying out polymerisation in bulk, polymerization temperature is 65 DEG C, and polymerization reaction time is 5h.
The structure of acrylate is CH2=CH-COOR1, R1 is normal-butyl.
The structure of phosphatization 2-(Acryloyloxy)ethanol is:
Wherein, R is normal-butyl.
The structure of siliceous hexenoic acid monomer:
CH2=CH-CH2-CH2Si (OCH3) 3
2. the preparation of coating
Take the phosphorous silicone-contained acrylic resin solution of aqueous that the 1st step prepares, prepare coating according to following masses percentage ratio:
Corrosion inhibitor refers to that salicylic acid and P-hydroxybenzoic acid mixing quality are than the mixture for 2:1, and function additive refers to that cobalt naphthenate, cobalt octoate, tin laurate are the mixture of 1:2:1 according to weight ratio.
Preparation method is: first by phosphorous silicone-contained acrylic resin solution, aqueous alkide resin, 2-aminooxyethanol, corrosion inhibitor, imidazoline, function additive mix homogeneously, be subsequently adding zinc phosphate, Pulvis Talci stirs, then grind on grinder, it is ground to grain diameter and reaches 0.5-2.5 μm, carry out fill.
Reference examples 1
It is distinctive in that with embodiment 1: the 1st step does not add phosphatization hydroxyethyl acrylate monomers in the preparation process of co-polypropylene acid resin.The co-polypropylene acid resin prepared and other component are made coating according to proportioning and the method for same embodiment 1.
Reference examples 2
It is distinctive in that with embodiment 1: the 1st step does not add acrylate monomer in the preparation process of co-polypropylene acid resin.The co-polypropylene acid resin prepared and other component are made coating according to proportioning and the method for same embodiment 1.
Reference examples 3
It is distinctive in that with embodiment 1: the 1st step does not add siliceous vinyl monomer in the preparation process of co-polypropylene acid resin.The co-polypropylene acid resin prepared and other component are made coating according to proportioning and the method for same embodiment 1.
" mensuration of the resistance to neutral salt spray performance of the GB/T1771-1991 paint and varnish " standard of employing detects, and adhesive force assay method is according to GB/T1720-1979 " paint film adhesion algoscopy " test.Result is as follows:
The steel plate got rusty is carried out St2 level surface treatment, brushes this paint, build about 80 μm, the performance test results in each embodiment and reference examples is as follows:
| Embodiment 1 | Reference examples 1 | Reference examples 2 | Reference examples 3 | |
| Salt-fog resistant time h | 1100 | 800 | 700 | 800 |
| Adhesive force | 1 grade | 2 grades | 2 grades | 2 grades |
As can be seen from the table, co-polypropylene acid resin adds phosphatization hydroxyethyl acrylate monomers, acrylate monomer or siliceous vinyl monomer respectively, be conducive to the raising of coating and the adhesion of base material, and the performance of salt spray resistance can be improved.
Embodiment 2
1, the preparation of the phosphorous silicone-contained acrylic resin solution of aqueous
Phosphatization hydroxyethyl acrylate monomers, methacrylic acid monomer, acrylate and siliceous hexenoic acid monomer are carried out copolymerization prepare；The mass ratio of each monomer is: phosphatization 2-(Acryloyloxy)ethanol: methyl acrylic monomer: acrylate: siliceous vinyl monomer=25:45:5:1；The condition of copolymerization is: under the initiator azo two fine initiation of isobutyl, carrying out polymerisation in bulk, polymerization temperature is 65 DEG C, and polymerization reaction time is 5h.
The structure of acrylate is CH2=CH-COOR1, R1 is normal-butyl.
The structure of phosphatization 2-(Acryloyloxy)ethanol is:
Wherein, R is respectively adopted methyl, ethyl, propyl group, normal-butyl, cyclopropane base, phenyl.
The structure of siliceous hexenoic acid monomer:
CH2=CH-CH2-CH2Si (OCH3) 3
2. the preparation of coating
Take the phosphorous silicone-contained acrylic resin solution of aqueous that the 1st step prepares, prepare coating according to following masses percentage ratio:
Corrosion inhibitor refers to that salicylic acid and P-hydroxybenzoic acid mixing quality are than the mixture for 2:1, and function additive refers to that cobalt naphthenate, cobalt octoate, tin laurate are the mixture of 1:2:1 according to weight ratio.
Preparation method is: first by phosphorous silicone-contained acrylic resin solution, aqueous alkide resin, 2-aminooxyethanol, corrosion inhibitor, imidazoline, function additive mix homogeneously, be subsequently adding zinc phosphate, Pulvis Talci stirs, then grind on grinder, it is ground to grain diameter and reaches 0.5-2.5 μm, carry out fill.
According to the test method in embodiment 1, coating property being tested, performance test results is as follows:
| R | Methyl | Ethyl | Propyl group | Normal-butyl | N-pentyl | Cyclopropane base | Phenyl |
| Salt-fog resistant time h | 800 | 800 | 700 | 1100 | 800 | 700 | 600 |
| Adhesive force | 2 grades | 2 grades | 2 grades | 1 grade | 2 grades | 2 grades | 2 grades |
As can be seen from the table, when the R in phosphatization 2-(Acryloyloxy)ethanol is butyl, the coating obtained has good adhesive force and salt-fog resistant time.
Embodiment 3
Phosphorous silicone-contained acrylic resin solution identical in the same embodiment 1 adopted, prepares coating according to following percentage by weight formula:
Corrosion inhibitor refers to that salicylic acid and P-hydroxybenzoic acid mixing quality are than the mixture for 2:1, and function additive refers to that cobalt naphthenate, cobalt octoate, tin laurate are the mixture of 1:2:1 according to weight ratio.
In the present embodiment, adopting different rust resisting pigments, the coating prepared carries out the test in same embodiment 1, and result is following table such as:
| Rust resisting pigment | Micaceous iron oxide | Zinc phosphate | Zinc powder |
| Salt-fog resistant time h | 700 | 1200 | 700 |
| Adhesive force | 2 grades | 1 grade | 2 grades |
As can be seen from the table, when zinc phosphate is as rust resisting pigment, salt spray resistance and adhesive force that coating has are better than other two kinds of rust resisting pigments.
Embodiment 4
Phosphorous silicone-contained acrylic resin solution identical in the same embodiment 1 adopted, prepares coating according to following percentage by weight formula:
Corrosion inhibitor refers to that salicylic acid and P-hydroxybenzoic acid mixing quality are than the mixture for 2:1, and function additive refers to that cobalt naphthenate, cobalt octoate, tin laurate are the mixture of 1:2:1 according to weight ratio.
In the present embodiment, adopting different fillers, the coating prepared carries out the test in same embodiment 1, and result is following table such as:
| Filler | Iron oxide red | Pulvis Talci | Aluminium hydroxide | Kieselguhr |
| Salt-fog resistant time h | 800 | 1400 | 800 | 900 |
| Adhesive force | 2 grades | 1 grade | 2 grades | 2 grades |
As can be seen from the table, when adopting Pulvis Talci as filler, salt spray resistance and adhesive force that coating has are better than other two kinds of rust resisting pigments, are most highly preferred embodiment of the invention.
Claims (10)
1. the phosphorous silicone-contained acrylic resin solution of aqueous, has the repeat unit structure as shown in formula (1):
In formula, R is alkyl, cycloalkyl or aryl；
In formula, R1Be carbon number it is the alkyl between 4～8；
In formula, n1It it is the integer between 1～4；N2It it is the integer between 1～4；N3It it is the integer between 1～4；N4It it is the integer between 1～4.
2. the phosphorous silicone-contained acrylic resin solution of aqueous according to claim 1, it is characterised in that: the molecular weight of the phosphorous silicone-contained acrylic resin solution of described aqueous is between 20000～40000.
3. the preparation method of the phosphorous silicone-contained acrylic resin solution of aqueous described in claim 1, it is characterised in that: comprise the steps: phosphatization hydroxyethyl acrylate monomers, methacrylic acid monomer, acrylate and siliceous hexenoic acid monomer copolymerization product are carried out copolymerization and prepared.
4. the preparation method of the phosphorous silicone-contained acrylic resin solution of aqueous according to claim 3, it is characterised in that:
Shown in the structure such as formula (2) of described phosphatization 2-(Acryloyloxy)ethanol:
In formula (2), R is alkyl, cycloalkyl or aryl；
Shown in the structure such as formula (3) of above-mentioned siliceous hexenoic acid monomer:
CH2=CH-CH2-CH2Si (OCH3) 3 (3)
Shown in the structure of described acrylate such as formula (4): CH2=CH-COOR1(4)
In formula (4), R1Be carbon number it is the alkyl between 4～8.
5. the preparation method of the phosphorous silicone-contained acrylic resin solution of aqueous according to claim 3, it is characterised in that: the mass ratio of each described monomer is preferably: phosphatization 2-(Acryloyloxy)ethanol: methyl acrylic monomer: acrylate: siliceous vinyl monomer=25:45:5:1；The condition of copolymerization is: under initiator azodiisobutyronitrile causes, carrying out polymerisation in bulk, polymerization temperature is 55～75 DEG C.
6. what include the phosphorous silicone-contained acrylic resin solution of the aqueous described in claim 1 can the direct coating composition of application on rusty scale, it is characterised in that: include following component by weight percentage: the phosphorous silicone-contained acrylic resin solution 10%～25% of aqueous, aqueous alkide resin 10～20%, 2-aminooxyethanol 10～20%, corrosion inhibitor 5～15%, imidazoline 1～5%, function additive 1～5%, rust resisting pigment 10～15%, filler 10～15%.
7. according to claim 6 can the direct coating composition of application on rusty scale, it is characterised in that: rust resisting pigment is one or several the mixture in micaceous iron oxide, zinc phosphate, zinc powder.
8. according to claim 6 can the direct coating composition of application on rusty scale, it is characterised in that: filler is the mixture of one or more in iron oxide red, clay, Pulvis Talci, calcium carbonate, aluminium hydroxide, magnesium hydroxide, kieselguhr, wollastonite in powder, barium sulfate, antimony oxide.
9. according to claim 6 can the direct coating composition of application on rusty scale, it is characterised in that: described function additive refers to that cobalt naphthenate, cobalt octoate, tin laurate are the mixture of 1:2:1 according to weight.
10. according to claim 6 can the direct coating composition of application on rusty scale, it is characterised in that: corrosion inhibitor refers to the mixture of salicylic acid and P-hydroxybenzoic acid, and its mixing quality is than for 2:1.
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| CN109535312B (en) * | 2018-12-19 | 2022-02-15 | 广东衡光新材料科技有限公司 | Core-shell styrene-acrylic emulsion for primer coating and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101704914A (en) * | 2009-11-03 | 2010-05-12 | 深圳市海润德润滑油有限公司 | Waterborne rust conversion polymer emulsion, coating thereof and method for preparing same |
| CN102079933A (en) * | 2009-11-30 | 2011-06-01 | 程雷 | Aqueous acrylate emulsion antirust paint |
| CN103666151A (en) * | 2013-12-06 | 2014-03-26 | 江苏科技大学 | Acrylic resin paint directly applied to rust layer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101704914A (en) * | 2009-11-03 | 2010-05-12 | 深圳市海润德润滑油有限公司 | Waterborne rust conversion polymer emulsion, coating thereof and method for preparing same |
| CN102079933A (en) * | 2009-11-30 | 2011-06-01 | 程雷 | Aqueous acrylate emulsion antirust paint |
| CN103666151A (en) * | 2013-12-06 | 2014-03-26 | 江苏科技大学 | Acrylic resin paint directly applied to rust layer and preparation method thereof |
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