CN104877061B - Synthetic polymer emulsion, water-based heavy-duty anticorrosive paint and preparation method thereof - Google Patents
Synthetic polymer emulsion, water-based heavy-duty anticorrosive paint and preparation method thereof Download PDFInfo
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- CN104877061B CN104877061B CN201510320987.XA CN201510320987A CN104877061B CN 104877061 B CN104877061 B CN 104877061B CN 201510320987 A CN201510320987 A CN 201510320987A CN 104877061 B CN104877061 B CN 104877061B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 80
- 229920001059 synthetic polymer Polymers 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003973 paint Substances 0.000 title claims description 42
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 238000005260 corrosion Methods 0.000 claims abstract description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- -1 hydroxyalkyl acrylates Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 235000010215 titanium dioxide Nutrition 0.000 claims description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 14
- 239000007921 spray Substances 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000003607 modifier Substances 0.000 abstract 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000002518 antifoaming agent Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 230000003260 anti-sepsis Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical group CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of anticorrosive coatings, and discloses a synthetic polymer emulsion, a water-based heavy anticorrosive coating and a preparation method thereof, wherein the synthetic polymer emulsion is obtained by emulsion polymerization of monomer raw materials comprising styrene, an acrylate monomer, an organic fluorine monomer and a functional monomer, the functional monomer comprises acrylic acid and a polymerizable modifier, the organic fluorine monomer accounts for 5-12% of the total mass of the monomer raw materials, and the polymerizable modifier accounts for 8-20% of the total mass of the monomer raw materials; the polymerizable modifier is prepared from raw materials including phosphorus pentoxide, hydroxyalkyl (meth) acrylate, alkyl cyclosiloxane, water and a polymerization inhibitor. The synthetic polymer emulsion has the advantages of environmental protection, strong adhesive force after film forming, and excellent antirust and salt spray corrosion resistance, and the water-based heavy-duty anticorrosive coating containing the synthetic polymer emulsion can form a heavy-duty anticorrosive coating independently, and has outstanding corrosion resistance.
Description
Technical field
The present invention relates to technical field of coatings, and in particular to a kind of synthetic polymer emulsion, aqueous heavy anti-corrosion paint and its
Preparation method.
Background technique
According to statistics, the metal equipment and material scrapped due to corrosion are equivalent to the 1/3 of metal annual output, and can not receive
It returns, causes the great wasting of resources.Forming erosion shield in metal surface by anticorrosive paint is current main anticorrosion
Technology.Existing anticorrosive paint not only causes environment dirt based on solvent based coating, but since it discharges pollution organic gas
Dye, while bringing inflammable, explosive security risk.And water-based anticorrosive paint meets environmental requirement, it has also become the weight of coating technology
Want developing direction and research hotspot.
Wherein, anticorrosive paint (Heavy-duty Coating) refers to relatively conventional anticorrosive paint, can be relatively harsh
It is used in corrosive environment, and a kind of anticorrosive paint with the protection period longer than conventional anticorrosive paint, heavy antisepsis can be reached and wanted
The coating asked usually has the characteristics that film forming thickness is big, multi-layer paint films are compound and paint film corrosion resistance is exsertile, mostly by film forming agent,
Solvent, filler, pigment composition, including aqueous epoxide resin paint, aqueous polyurethane coating and aqueous inorganic zinc silicate coating etc.,
And priming paint, middle layer and finishing coat are generally comprised, but there are construction cost height, coating performance are unstable for compound anticorrosive paint
Defect.
Summary of the invention
In order to solve the above-mentioned problems of the prior art, the present invention provides a kind of synthetic polymer emulsion, lotion tool
Have the advantages that after environmental protection, film forming that adhesive force strong, antirust and salt spray corrosion resistance are excellent, it is further provided poly- comprising the synthesis
The aqueous heavy anti-corrosion paint and preparation method thereof of object lotion is closed, which may be separately formed anticorrosion coat, and corrosion resistance reaches
To heavy antisepsis requirement.
The technical solution adopted by the present invention is that:
A kind of synthetic polymer emulsion, by including styrene, acrylate monomer, organic fluorine monomer and the list of function monomer
Body raw material is obtained through emulsion polymerization, and the function monomer includes acrylic acid and polymerizable modifying agent, and organic fluorine monomer accounts for list
The 5~12% of body total mass of raw material, the polymerizable modifying agent account for the 8~20% of raw material monomer gross mass；
The polymerizable modifying agent by include phosphorus pentoxide, (methyl) hydroxyalkyl acrylates, alkyl-cyclosiloxanes,
The raw material of water and polymerization inhibitor is prepared.
Preferably, the glass transition temperature of the synthetic polymer emulsion is 40-55 DEG C.
Preferably, the styrene accounts for the 45~70% of raw material monomer gross mass, and it is total that acrylate monomer accounts for raw material monomer
The 10~25% of quality.
The function monomer can further comprise glycidyl methacrylate, N hydroxymethyl acrylamide, methyl-prop
One or more of olefin(e) acid.
Preferably, the acrylate monomer is selected from butyl acrylate, Isooctyl acrylate monomer, ethyl acrylate, acrylic acid
One or more of methyl esters.It is highly preferred that the acrylate monomer is Isooctyl acrylate monomer.
Preferably, organic fluorine monomer is that Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, perfluor are pungent
One or more of base ethyl acrylate.
Preferably, the acrylic acid accounts for the 1-2% of raw material monomer gross mass.
Preferably, in the raw material of the polymerizable modifying agent, the structural formula of alkyl-cyclosiloxanes are as follows:Wherein, m=4-6, R are identical or different selected from C1-C3Alkyl.
Preferably, in the raw material of the polymerizable modifying agent, the mass percent of alkyl-cyclosiloxanes is 40-60%.I.e.
In the raw material of polymerizable modifying agent, the quality of alkyl-cyclosiloxanes accounts for 40-60%.
Preferably, in the raw material of the polymerizable modifying agent, the molar ratio of phosphorus pentoxide and alkyl-cyclosiloxanes is
(0.2-0.6): 1.
In the raw material of the polymerizable modifying agent, (methyl) hydroxyalkyl acrylates be hydroxyalkyl acrylates and/
Or haloalkylacrylates, the alkyl are the alkyl of C1-C3, it is preferable that the alkyl is methyl.
Preferably, the polymerizable modifying agent is prepared by method comprising the following steps:
(1) (methyl) hydroxyalkyl acrylates are mixed with polymerization inhibitor, stirring is warming up to 60~65 DEG C, and five are added by several times
Two phosphorus are aoxidized, temperature is controlled at 65-85 DEG C, obtains mixed liquor；
(2) mixed liquor is warming up to 90~110 DEG C of reaction 1-2h, while alkyl-cyclosiloxanes and (methyl) acrylic acid is added dropwise
Water is added after being added dropwise to complete in hydroxyalkyl acrylate, cooling in 90~110 DEG C of reaction 1-3h, obtains polymerizable modifying agent.
Preferably, in the step (1), the molar ratio of (methyl) hydroxyalkyl acrylates and phosphorus pentoxide is (2-
4):1。
Preferably, in step (1), the phosphorus pentoxide is classified as several equal portions before use, is placed in 25-50 DEG C dry
In dry device.The gradation is that portion is added every time by several times, to reduce the water absorption rate of phosphorus pentoxide, and is conducive to control reaction temperature
Degree.
Preferably, in step (1), the addition phosphorus pentoxide is added in 1~2h.
Preferably, in step (1), the polymerization inhibitor is in p methoxy phenol, tert-butyl catechol, hydroquinone
It is one or two kinds of.
Preferably, with phosphorus pentoxide, (methyl) hydroxyalkyl acrylates, alkyl-cyclosiloxanes, water and polymerization inhibitor
Gross mass is 100 parts of meters, and the dosage of the polymerization inhibitor is 0.1~0.3 part.
Preferably, in step (2), the time of the dropwise addition is 1.5~3h.
Preferably, the quality of (methyl) hydroxyalkyl acrylates being added dropwise in step (2) is alkyl-cyclosiloxanes quality
7%~12%.
Preferably, in step (2), the water is deionized water or distilled water.
Preferably, the quality that water is added in the step (2) is (methyl) hydroxyalkyl acrylates and five in step (1)
Aoxidize the 3~5% of two phosphorus quality sums.
Cooling is to be cooled to room temperature in the step (2).
A kind of aqueous heavy anti-corrosion paint, including synthetic polymer emulsion, pigments and fillers, auxiliary agent, thickener and water, the synthesis
The mass percent of polymer emulsion is 45-60%, i.e., the quality of synthetic polymer emulsion accounts for 45- in aqueous heavy anti-corrosion paint
60%；
The synthetic polymer emulsion, by including styrene, acrylate monomer, organic fluorine monomer and the list of function monomer
Body raw material is obtained through emulsion polymerization, and the function monomer includes acrylic acid and polymerizable modifying agent, and organic fluorine monomer accounts for list
The 5~12% of body total mass of raw material, the polymerizable modifying agent account for the 8~20% of raw material monomer gross mass；
The polymerizable modifying agent by include phosphorus pentoxide, (methyl) hydroxyalkyl acrylates, alkyl-cyclosiloxanes,
The raw material of water and polymerization inhibitor is prepared.
Preferably, the styrene accounts for the 45~70% of raw material monomer gross mass, and it is total that acrylate monomer accounts for raw material monomer
The 10~25% of quality.
The polymerizable modifying agent is polymerizable modifying agent as described above.
Preferably, the pigments and fillers include following component according to parts by weight:
10-15 parts of trbasic zinc phosphate
40-60 parts of rutile type titanium white
20-30 parts of blanc fixe.
Preferably, the mass percent of the pigments and fillers is 20-30%.
The auxiliary agent includes film forming accelerating, coalescing agent and pH adjusting agent.Preferably, the film forming accelerating includes point
Powder, wetting agent, defoaming agent and levelling agent.
Preferably, the coalescing agent is alcohol ester 12, mass percent 3-6%.
Preferably, the thickener is hydroxyethyl cellulose.
The preparation method of the aqueous heavy anti-corrosion paint, comprising the following steps:
The preparation of pre-emulsion: cream is carried out after styrene, acrylate monomer, organic fluorine monomer and function monomer are mixed
Change, obtains pre-emulsion；
The preparation of seed emulsion: seed emulsion is prepared by part pre-emulsion；
The preparation of synthetic polymer emulsion: remaining pre-emulsion is added dropwise to seed emulsion and carries out emulsion polymerization, is synthesized
Polymer emulsion；
The preparation of aqueous heavy anti-corrosion paint: pigments and fillers, auxiliary agent, thickener, water and synthetic polymer emulsion are mixed, obtained
Aqueous heavy anti-corrosion paint.
Preferably, the reaction temperature in the preparation step of the seed emulsion is 80~85 DEG C.
Preferably, in the preparation step of synthetic polymer emulsion, the emulsion polymerization is in 85~88 DEG C of reaction 1-3h.
Preferably, in the preparation step of the aqueous heavy anti-corrosion paint, first thickener, water are mixed with part of auxiliary and is stirred
It mixes, adds pigments and fillers, synthetic polymer emulsion and remaining auxiliary agent, obtain aqueous heavy anti-corrosion paint, wherein the part of auxiliary
Including defoaming agent and pH adjusting agent, the residue auxiliary agent includes coalescing agent, defoaming agent and levelling agent.
Emulsifier is used in the preparation of pre-emulsion and the preparation step of seed emulsion, it is preferable that emulsifier is dodecane
Base sodium sulphate, sodium p styrene sulfonate, octyl phenol polyoxyethylene ether (OP-10), two in nonylphenol polyoxyethylene ether (NP-10)
Kind is two or more, and dosage is not particularly limited.Initiator is used in the preparation of pre-emulsion and the preparation step of seed emulsion,
Initiator is peroxide initiator, including potassium peroxide, ammonium persulfate etc., and dosage is not particularly limited.
Preferably, the quality of part pre-emulsion accounts for the 8- of pre-emulsion gross mass in the preparation step of the seed emulsion
15%.
The beneficial technical effect of the present invention: synthetic polymer emulsion of the invention is to contain the polymerizable of organophosphorus ester
Modifying agent is generation phenomena such as preparing one of raw material, avoid high silicon content synthetic polymer emulsion " floating oil ", gel, and with have
Machine fluorine monomer combined polymerization, make synthetic polymer emulsion have excellent antirust, adhesive force, water-fast, corrosion resistance, make by its into
Aqueous heavy anti-corrosion paint weather resistance made from one step is prominent, can be used alone in practical applications, the coating layer thickness of formation
When being 80~120 μm, it can be tested by 3000h neutral salt spray NSS and 400h copper ion accelerates acidity salt fog CASS test,
Reach heavy antisepsis performance requirement, and raw material is easy to get, preparation process is simple, and at low cost, VOC free discharge, safety and environmental protection is convenient for industry
Change.
Specific embodiment
Specific embodiment is given below the present invention is further detailed.
Embodiment 1
Aqueous heavy anti-corrosion paint is prepared by following steps:
Prepare polymerizable modifying agent:
(1) 112.6g phosphorus pentoxide is taken, five equal portions are divided into, is placed in 50 DEG C of drying ovens stand-by；It will
257.8g hydroxyethyl methacrylate is mixed with 2g p methoxy phenol in investment reaction kettle, and stirring is warming up to 65 DEG C, accelerates to stir
Speed is mixed, a phosphorus pentoxide is successively added every time, controls temperature at 75 DEG C, 1h is added, and obtains mixed liquor；
(2) mixed liquor is warming up to 110 DEG C of reaction 1h, while 555.6g octamethylcy-clotetrasiloxane and 55.6g first is added dropwise
Base hydroxy-ethyl acrylate, 3h are added dropwise to complete, and 11.2g deionized water is added, cooling in 110 DEG C of reaction 2h, obtain polymerizable modification
Agent.
Prepare synthetic polymer emulsion:
The preparation of pre-emulsion: taking 2.5g ammonium persulfate to be dissolved in 40g deionized water, obtains causing liquid；Take 2.5g dodecane
Base sodium sulphate, 2.0g nonylphenol polyoxyethylene ether (NP-10), 130g deionized water, which are added in flask, quickly stirs 20min, is added
Styrene 275g, Isooctyl acrylate monomer 105g, acrylic acid 7g, Hexafluorobutyl mathacrylate 50g, polymerizable modifying agent 45g and
30g causes liquid, continues quickly stirring 20min and is emulsified, obtains pre-emulsion；
The preparation of seed emulsion: 1.5g sodium p styrene sulfonate, 2.0g nonylphenol polyoxyethylene ether (NP-10), 2.0g are taken
Lauryl sodium sulfate, the mixing of 350g deionized water are added in flask, and quickly stirring is warming up to 85 DEG C, be added 10g cause liquid and
62g pre-emulsion keeps the temperature 10min after the general obvious blue light of lotion, obtains seed emulsion；
The preparation of synthetic polymer emulsion: remaining pre-emulsion is added dropwise to seed emulsion, is dripped off in 2.5h, is warming up to 88
DEG C, 1.5h is kept the temperature, is cooled to 45 DEG C, with ammonium hydroxide tune pH value to 7~8, filtering and discharging obtains synthetic polymer emulsion.
The vitrifying temperature of gained synthetic polymer emulsion is tested according to GB 19466-2 using differential scanning calorimetry (DSC)
Degree is 47 DEG C.
Prepare aqueous heavy anti-corrosion paint:
Take hydroxyethyl cellulose 2g, deionized water 168g, ammonium hydroxide 0.2g, defoaming agent (sea profit chemical industry CF1259) 0.4g mixed
It closes, carries out low speed dispersion, accelerate rate of dispersion after solution thickening, sequentially add rutile type titanium white 144g, sulfate precipitate
Barium 56g and trbasic zinc phosphate 28g, the high speed dispersion 0.5h under 2500r/min reduce rate of dispersion, are slowly added to synthetic polymer cream
Liquid 550g, 12 50g of alcohol ester, levelling agent (core chemistry F66) 10g and defoaming agent (sea profit chemical industry CF1439) 4g, in 800r/
Continue to disperse 15min under the revolving speed of min, filter, discharging obtains aqueous heavy anti-corrosion paint.
Embodiment 2
Aqueous heavy anti-corrosion paint is prepared by following steps:
Prepare polymerizable modifying agent:
(1) 140g phosphorus pentoxide is taken, five equal portions are divided into, is placed in 50 DEG C of drying ovens stand-by；It will
257.8g hydroxyethyl methacrylate is mixed with 2g p methoxy phenol in investment reaction kettle, and stirring is warming up to 65 DEG C, accelerates to stir
Speed is mixed, a phosphorus pentoxide is successively added every time, controls temperature at 80 DEG C, 1h is added, and obtains mixed liquor；
(2) mixed liquor is warming up to 100 DEG C of reaction 1.5h, while 510g octamethylcy-clotetrasiloxane and 50g methyl is added dropwise
Hydroxy-ethyl acrylate, 2h are added dropwise to complete, and 13g deionized water is added, cooling in 100 DEG C of reaction 2h, obtain polymerizable modifying agent.
Prepare synthetic polymer emulsion:
The preparation of pre-emulsion: taking 2.5g ammonium persulfate to be dissolved in 40g deionized water, obtains causing liquid；Take 1.5g dodecane
Base sodium sulphate, 2.0g nonylphenol polyoxyethylene ether (NP-10), 130g deionized water, which are added in flask, quickly stirs 20min, is added
Styrene 310g, Isooctyl acrylate monomer 65g, acrylic acid 6g, Hexafluorobutyl mathacrylate 40g, polymerizable modifying agent 60g and
30g causes liquid, continues quickly stirring 20min and is emulsified, obtains pre-emulsion；
The preparation of seed emulsion: 1.5g sodium p styrene sulfonate, 2.0g nonylphenol polyoxyethylene ether (polyoxyethylene nonyl phenyl second are taken
Alkene ether (NP-10)), 2.0g lauryl sodium sulfate, 350g deionized water mixing be added flask in, quickly stirring be warming up to 85
DEG C, 10g is added and causes liquid and 62g pre-emulsion, keeps the temperature 10min after the general obvious blue light of lotion, obtains seed emulsion；
The preparation of synthetic polymer emulsion: remaining pre-emulsion is added dropwise to seed emulsion, is dripped off in 2.5h, is warming up to 88
DEG C, 1.5h is kept the temperature, is cooled to 45 DEG C, with ammonium hydroxide tune pH value to 7~8, filtering and discharging obtains synthetic polymer emulsion.
The vitrifying temperature of gained synthetic polymer emulsion is tested according to GB 19466-2 using differential scanning calorimetry (DSC)
Degree is 52 DEG C.
Prepare aqueous heavy anti-corrosion paint:
Take hydroxyethyl cellulose 2g, deionized water 168g, ammonium hydroxide 0.2g and defoaming agent (sea profit chemical industry CF1259): 0.4g is mixed
It closes, low speed dispersion accelerates rate of dispersion after solution thickening, sequentially adds rutile type titanium white 144g, blanc fixe
56g, trbasic zinc phosphate 28g, the high speed dispersion 0.5h under 2500r/min reduce rate of dispersion, are slowly added to synthetic polymer emulsion
550g, 12 50g of alcohol ester, levelling agent (core chemistry F66) 10g, defoaming agent (sea profit chemical industry CF1439) 4g, 800r/min's
Continue to disperse 15min under revolving speed, filter, discharging obtains aqueous heavy anti-corrosion paint.
Embodiment 3
Aqueous heavy anti-corrosion paint is prepared by following steps:
Prepare polymerizable modifying agent:
(1) 130g phosphorus pentoxide is taken, five equal portions are divided into, is placed in 50 DEG C of drying ovens stand-by；By 300g
Hydroxyethyl methacrylate is mixed with 2g p methoxy phenol in investment reaction kettle, and stirring is warming up to 65 DEG C, accelerates mixing speed,
A phosphorus pentoxide is successively added every time, controls temperature at 75 DEG C, 1h is added, and obtains mixed liquor；
(2) mixed liquor is warming up to 110 DEG C of reaction 2h, while 460g octamethylcy-clotetrasiloxane and 36g methyl-prop is added dropwise
Olefin(e) acid hydroxyl ethyl ester, 2h are added dropwise to complete, and 20g deionized water is added, cooling in 110 DEG C of reaction 1.5h, obtain polymerizable modifying agent.
Prepare synthetic polymer emulsion:
The preparation of pre-emulsion: taking 2.5g ammonium persulfate to be dissolved in 40g deionized water, obtains causing liquid；Take 1.5g dodecane
Base sodium sulphate, 1.0g nonylphenol polyoxyethylene ether (NP-10), 130g deionized water, which are added in flask, quickly stirs 20min, is added
Styrene 265g, Isooctyl acrylate monomer 95g, acrylic acid 5g, Hexafluorobutyl mathacrylate 30g, polymerizable modifying agent 80g and
30g causes liquid, continues quickly stirring 20min and is emulsified, obtains pre-emulsion；
The preparation of seed emulsion: 1.5g sodium p styrene sulfonate, 2.0g nonylphenol polyoxyethylene ether (NP-10), 2.0g are taken
Lauryl sodium sulfate, the mixing of 350g deionized water are added in flask, and quickly stirring is warming up to 85 DEG C, be added 10g cause liquid and
62g pre-emulsion keeps the temperature 10min after the general obvious blue light of lotion, obtains seed emulsion；
The preparation of synthetic polymer emulsion: remaining pre-emulsion is added dropwise to seed emulsion, is dripped off in 2.5h, is warming up to 88
DEG C, 1.5h is kept the temperature, is cooled to 45 DEG C, with ammonium hydroxide tune pH value to 7~8, filtering and discharging obtains synthetic polymer emulsion.
The vitrifying temperature of gained synthetic polymer emulsion is tested according to GB 19466-2 using differential scanning calorimetry (DSC)
Degree is 46 DEG C.
Prepare aqueous heavy anti-corrosion paint:
Take hydroxyethyl cellulose 2g, deionized water 168g, ammonium hydroxide 0.2g and defoaming agent (sea profit chemical industry CF1259): 0.4g is mixed
It closes, low speed dispersion accelerates rate of dispersion after solution thickening, sequentially adds rutile type titanium white 144g, blanc fixe
56g, trbasic zinc phosphate 28g, the high speed dispersion 0.5h under 2500r/min reduce rate of dispersion, are slowly added to synthetic polymer emulsion
550g, 12 50g of alcohol ester, levelling agent (core chemistry F66) 10g, defoaming agent (sea profit chemical industry CF1439) 4g, 800r/min's
Continue to disperse 15min under revolving speed, filter, discharging obtains aqueous heavy anti-corrosion paint.
Testing example
Application performance test is carried out to the aqueous heavy anti-corrosion paint prepared in embodiment 1-3 respectively, the method is as follows:
1, the surface drying of paint film is measured according to GB 1728-79 paint film, putty membrane drying time measuring method and done solid work the time.
2, blasting treatment is carried out by 150mm × 50mm, with a thickness of the tinplate surface of 0.3mm, makes up to St2 grades,
Aqueous heavy anti-corrosion paint is sprayed into through on processed tinplate with seven apertures in the human head high atomization spray gun for paint under 0.5MPa air pressure, to surface drying
It sprays again afterwards 1 time, surface drying, obtains the sample with aqueous anticorrosion coat, testing coating is with a thickness of 80~120 μm；
Sample is put into 80 DEG C of oven dryings for 24 hours, draws "×" simultaneously on the aqueous anticorrosion coat of sample by ISO 17872
After depth and substrate, it is put into progress salt spray resistance experiment in salt spray test chamber, referring in GBT10125-2012 artificial atmosphere corrosion test
Property salt spray test (NSS) (3000h) and copper accelerated acetic acid salt spray test (CASS) (400h) respectively carry out coating salt spray resistance examination
It tests, investigates the corrosion degree and coating adhesion of sample after salt spray resistance experiment, if Corrosion Protection is bad, drawing will be sent out at "×"
It gets rusty erosion, causes coating expansion and blister, and spread under coating, cause to draw and generate greater area of corrosion at "×", simultaneously
It is also tested for the adhesive force by anticorrosion coat before and after salt spray test, adhesive force test is tested according to hundred lattice of GB9286-98 marks
Standard carries out, and test result is shown in Table 1.
Table 1
Seen from table 1, it compared with existing product, is all had by the anticorrosion coat that anticorrosive paint of the invention obtains excellent
Different adhesive force, corrosion resistance and durability can reach heavy antisepsis performance requirement, and raw material by heavy antisepsis salt spray test
It is easy to get, preparation process is simple, and VOC free discharge, safety and environmental protection has a extensive future in heavy antisepsis field.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (9)
1. a kind of synthetic polymer emulsion, by including styrene, acrylate monomer, organic fluorine monomer and the monomer of function monomer
Raw material is obtained through emulsion polymerization, and the function monomer includes acrylic acid and polymerizable modifying agent, and organic fluorine monomer accounts for monomer
The 5~12% of total mass of raw material, the polymerizable modifying agent account for the 8~20% of raw material monomer gross mass；
The polymerizable modifying agent by include phosphorus pentoxide, (methyl) hydroxyalkyl acrylates, alkyl-cyclosiloxanes, water and
The raw material of polymerization inhibitor is prepared, and the polymerizable modifying agent is prepared by method comprising the following steps:
(1) (methyl) hydroxyalkyl acrylates are mixed with polymerization inhibitor, stirring is warming up to 60~65 DEG C, and five oxidations are added by several times
Two phosphorus control temperature at 65-85 DEG C, obtain mixed liquor；
(2) mixed liquor is warming up to 90~110 DEG C of reaction 1-2h, while alkyl-cyclosiloxanes and (methyl) dihydroxypropyl is added dropwise
Water is added after being added dropwise to complete in Arrcostab, cooling in 90~110 DEG C of reaction 1-3h, obtains polymerizable modifying agent；
In step (1), the molar ratio of (methyl) hydroxyalkyl acrylates and phosphorus pentoxide is (2-4): 1.
2. synthetic polymer emulsion as described in claim 1, which is characterized in that the styrene accounts for raw material monomer gross mass
45~70%, acrylate monomer accounts for the 10~25% of raw material monomer gross mass.
3. synthetic polymer emulsion as claimed in claim 1 or 2, which is characterized in that in the raw material of the polymerizable modifying agent,
The structural formula of alkyl-cyclosiloxanes are as follows:Wherein, m=4-6, R are identical or different selected from C1~C3's
Alkyl.
4. synthetic polymer emulsion as claimed in claim 3, which is characterized in that in the raw material of the polymerizable modifying agent, alkane
The mass percent of cyclosiloxane is 40-60%.
5. synthetic polymer emulsion as claimed in claim 1 or 2, which is characterized in that in the raw material of the polymerizable modifying agent,
The molar ratio of phosphorus pentoxide and alkyl-cyclosiloxanes is (0.2-0.6): 1.
6. synthetic polymer emulsion as described in claim 1, which is characterized in that (methyl) acrylic acid being added dropwise in step (2)
The quality of hydroxyalkyl acrylate is the 7%~12% of alkyl-cyclosiloxanes quality.
7. a kind of aqueous heavy anti-corrosion paint, including pigments and fillers, auxiliary agent, thickener, water and synthetic polymer emulsion, synthetic polymer
The mass percent of lotion is 45-60%；
The synthetic polymer emulsion, it is former by the monomer for including styrene, acrylate monomer, organic fluorine monomer and function monomer
Material is obtained through emulsion polymerization, and the function monomer includes acrylic acid and polymerizable modifying agent, and organic fluorine monomer accounts for monomer original
Expect the 5~12% of gross mass, the polymerizable modifying agent accounts for the 8~20% of raw material monomer gross mass；
The polymerizable modifying agent by include phosphorus pentoxide, (methyl) hydroxyalkyl acrylates, alkyl-cyclosiloxanes, water and
The raw material of polymerization inhibitor is prepared.
8. aqueous heavy anti-corrosion paint as claimed in claim 7, which is characterized in that the styrene accounts for raw material monomer gross mass
45~70%, acrylate monomer accounts for the 10~25% of raw material monomer gross mass.
9. aqueous heavy anti-corrosion paint as claimed in claim 7, which is characterized in that the pigments and fillers include it is following in parts by weight
The component of meter:
10-15 parts of trbasic zinc phosphate
40-60 parts of rutile type titanium white
20-30 parts of blanc fixe.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1557848A (en) * | 2004-01-15 | 2004-12-29 | 曹晓利 | Silicon-fluorin acrylic acid ternary polymerization latex and method for preparation thereof |
| CN102964514A (en) * | 2012-11-23 | 2013-03-13 | 陕西科技大学 | Preparation method of polyacrylate emulsion containing silicon, fluorine and phosphate group |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557848A (en) * | 2004-01-15 | 2004-12-29 | 曹晓利 | Silicon-fluorin acrylic acid ternary polymerization latex and method for preparation thereof |
| CN102964514A (en) * | 2012-11-23 | 2013-03-13 | 陕西科技大学 | Preparation method of polyacrylate emulsion containing silicon, fluorine and phosphate group |
Non-Patent Citations (1)
| Title |
|---|
| 磷酸酯功能单体对苯丙乳液及其水性涂料性能的影响;山丹丹等;《涂料工业》;20070901(第09期);14-16 * |
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