CN108250347A - A kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance - Google Patents

A kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance Download PDF

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CN108250347A
CN108250347A CN201711377667.3A CN201711377667A CN108250347A CN 108250347 A CN108250347 A CN 108250347A CN 201711377667 A CN201711377667 A CN 201711377667A CN 108250347 A CN108250347 A CN 108250347A
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acrylate
phosphate
emulsion
salt spray
parts
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CN108250347B (en
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许钧强
王茵键
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Jili New Material Science And Technology (zhuhai) Co Ltd
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Jili New Material Science And Technology (zhuhai) Co Ltd
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • 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 relates to a kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance, contain chain alkyl acrylate phosphate diester functional group on shell；Its ingredient has the soft or hard monomer of acrylate, acrylic acid, chain alkyl acrylate phosphate diester, neutralizer, initiator, emulsifier and water；The chain alkyl acrylate phosphate is by hydroxy-acrylate monomer, R6‑10OH and phosphorus pentoxide are made by reacting；The present invention also provides a kind of preparation methods of the phosphate modified Acrylate Core-shell Emulsion of salt spray resistance.The phosphate modified Acrylate Core-shell Emulsion, glass transition temperature is 30~45 DEG C, grain size is 60~150nm；The phosphate modified Acrylate Core-shell Emulsion of salt spray resistance produced by the present invention, with excellent adhesive force, water resistance, resistance to acid and alkali, salt fog resistance, anti-flash rusting and corrosion resistance, it is widely used in aqueous rust-proof coatings, aqueous steel structure coating, aqueous engineering coating, aqueous concrete anti-corrosive paint etc..

Description

A kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance
Technical field
The present invention relates to a kind of modified acrylic acid emulsion more particularly to a kind of phosphate modified acrylic acid cores of salt spray resistance Shell lotion belongs to water-base resin synthesis technical field.
Background technology
In recent years, as the pay attention to day by day of mankind's environmental pollution and the withered of Global Oil resource lack, solvent type The use scope of coating is restricted significantly, and coating such as water paint, high solid coating, the powder wood of low VOC and hypotoxicity apply Material, the research and development of radiation curable coating and production are grown rapidly.Wherein water paint, due to being situated between using water as dispersion Matter, pollution-free, no fire hazard, production cost is low, meets green production, has very vast potential for future development.
Corrosion of metal brings hundreds billion of dollars of economic losses to countries in the world every year, and all the time, people are using a variety of Metal is protected in technology, prevents the generation of corrosion.Wherein, anticorrosion with coat is that anticorrosive metal is most effective, most common side One of method.At present, as the development of modern industrial technology and people are to the raising of environmental requirement and sternly going out for environmental regulation Platform, the Water-borne modification of anticorrosive coating have become inevitable.
Water-based acrylic resin is usually prepared by free radical polymerisation process, and it is many to manufacture the available monomer of this resinoid, Arrcostab, hydroxy alkyl ester and vinyl monomer including acrylic acid, such as styrene.The final performance of acrylic resin can lead to It crosses and appropriate monomeric species is selected to be controlled, resin hardness, impact resistance can be controlled by adjusting the ratio of soft or hard monomer With flexible mutual balance.Waterborne acrylic paint has good flexibility, fabulous resistance to ag(e)ing and solvent resistance, Since its shrinking percentage is low, therefore there is preferable adhesive force to various base materials, be widely used as building coating, aqueous industrial painting In material.
Since general acrylic acid ester emulsion is polymerized in the presence of emulsifier, emulsifier since its molecular weight is small, Film coated surface easily is migrated to, so as to influence the Corrosion Protections such as the adhesive force after emulsion film forming, water resistance, salt fog resistance.
Phosphate is a kind of common adhesion promoter, special suitable for the various grounds such as copper, iron, aluminium, timber, plastics It is not that effect is obviously promoted to being attached with for the metal bases such as copper, iron, aluminium, this is because in the highly polar and base material of phosphate group Iron ion produce strong passivation, one layer of fine and close passivating film can be formed, so as to reach antirust, anti-corrosive function.
Chinese patent CN102408513A discloses a kind of preparation method of phosphate modified acrylic acid ester emulsion, institute It is trichloroethyl phosphate, trichlorine propyl phosphate or the positive ethyl ester of phosphoric acid with phosphate ester monomer, the phosphate modified acrylic acid of gained The molecular weight of polymer is 2000~3000 in ester lotion, and grain size is 0.2~0.6 μm, and initiator used is ammonium persulfate, is closed Into emulsion particle diameter it is larger, influence filming performance, and phosphate ester monomer alkyl carbon number used is less, water resistance, salt fog resistance It is poor.
Chinese patent CN101412781A discloses a kind of preparation method of phosphate modified acrylic acid ester emulsion, used Phosphate ester monomer is the PMA-100 (hydroxyethyl methacrylate phosphate monoester) of Rhodia or PMA-200 (hydroxyethyl methacrylate second Ester phosphate diester), the acrylic resin of preparation is configured to aqueous double-component coating, has excellent water resistance and salt fog resistance, But prepared acrylic resin is not nucleocapsid, is aqueous dispersion, it is necessary to two-component system, increase application cost.
Zhang Dongyang (synthesis of phosphate modified acrylic acid ester emulsion and performance study, Chinese coating, 2014,29 (10)； 38-43) report has synthesized phosphorus using methyl methacrylate, styrene, butyl acrylate, acrylic acid, phosphate function monomer Acid esters modified acrylate emulsion, phosphate ester monomer used are the PMA-100 or PMA-200 of Rhodia, and initiator is persulfuric acid Ammonium, emulsifier are single anionic emulsifier, and a kind of technology actually phosphate modified styrene-acrylate core/shell emulsion is ageing-resistant Property, salt fog resistance are also less desirable.
Water-based anticorrosive paint is short there are anticorrosion time limit at present, and erosion, emulsion intercalation method, water resistance and antirust are easily dodged after application The problems such as property.A kind of phosphate modified acrylic resin of salt fog resistance is developed, the antiseptic property for improving water paint is particularly important.
Invention content
In order to solve the technical issues of described, the present invention is introduced on acrylic resin molecular structure with alkyl acrylic Ester phosphate diester function monomer, the chain alkyl in bound phosphate groups have the function of the heat-resistant stable that self-emulsifying improves lotion Property, the hydrophobic performance of chain alkyl improves the water resistance of film；And bound phosphate groups can be produced with the iron in base material it is strong Passivation can form one layer of fine and close passivating film；It is attached between fortified resin and base material due to the double action of the phosphate Put forth effort and compactness, enter between resin and base material so as to be effectively isolated hydrone, chlorion, sodium ion etc., in hygrometric state ring Adhesive force and anti-flash rusting performance are improved under border, so as to improve its water resistance, salt fog resistance and antirust, anti-corrosive performance.
It is an object of the invention to provide a kind of phosphate modified Acrylate Core-shell Emulsions of salt spray resistance.
The present invention is that alkyl acrylate phosphate diester function monomer is introduced into acrylic copolymer shell molecular structure On side chain end group, ensure in resin film forming procedure, bound phosphate groups are easier to be enriched in substrate surface, and it is unique blunt to play its Change anti-flash rusting function.
The phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance of the present invention, is made of stratum nucleare and shell, contains on shell Chain alkyl-acrylate phosphate diester functional group, molecular structural formula are as follows：
Wherein, the R in molecular structural formula is C6-10Chain alkyl；N is 1~3；R2、R3For H ,-CH3And other alkyls take For group；R4For butyl ester base, different monooctyl ester base, laruyl alcohol ester group, bay ester group, octadecyl ester base；M is 18~26；The salt spray resistance Phosphate modified Acrylate Core-shell Emulsion, glass transition temperature Tg is 30~45 DEG C, grain size is 60~150nm.
The phosphate modified acrylate core-shell latex of salt spray resistance of the present invention, by weight, ingredient is：Propylene 30.0~50.0 parts of the soft or hard monomer of acid esters, 1.5~4.0 parts of acrylic acid, chain alkyl-acrylate phosphate diester 2.0~5.0 Part, 1.0~3.0 parts of neutralizer, 0.5~2.0 part of initiator, 1.5~3.0 parts of emulsifier, 40.0~60.0 parts of deionized water.
Wherein, the acrylate hard monomer for methyl acrylate, methyl methacrylate, ethyl methacrylate, The combination of the middle one or more of ethyl acrylate；The acrylate soft monomer is butyl acrylate, methacrylic acid fourth Ester, tert-butyl acrylate, n-BMA, Isobutyl methacrylate, isooctyl methacrylate, methacrylic acid Bay alcohol ester, lauryl acrylate, octadecyl methacrylate, octadecyl acrylate middle one or more combination；It is described The molar ratio of acrylate soft monomer and acrylate hard monomer be 1:0.1~1.
The chain alkyl-acrylate phosphate diester, is made by following reaction equation：
Wherein, the R in molecular structural formula1For H ,-CH3And other alkyls substituent groups, R C6-10Chain alkyl；N is 1 ~3.
The chain alkyl-acrylate phosphate diester, by weight, ingredient is：Hydroxy acryl acid ester list 35.0~45.0 parts of body, R6-1030~40.0 parts of OH, 0.1~0.5 part of hydroquinone, 20~30.0 parts of phosphorus pentoxide.
The hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, methacrylate middle one or more combination.
The R6-10OH is containing C6-10Chain alkyl single methanol.
The chain alkyl-acrylate phosphate diester, preparation process are as follows：
In a kettle, quantitative hydroxy acryl acid ester monomer and quantitative hydroquinone are added in, is stirred evenly, is heated up To 50 DEG C, by quantitative phosphorus pentoxide and R6-10OH is added portionwise, and is added in 1.5h, and temperature then is raised to 82 DEG C, protects Temperature reaction 3h, measures acid value, cools down after qualified, discharge, obtain the chain alkyl-acrylate phosphate diester.
The initiator uses azodiisobutyronitrile, because azodiisobutyronitrile initiator than peroxide can obtain molecule Amount is uniform, and distribution is narrower, and lotion is made to reach nanoscale.
Combination of the emulsifier for one or more of COPS-I, CO-436, OP-10.
The neutralizer is at least one of triethylamine, ammonium hydroxide, dimethylethanolamine.
The present invention also provides a kind of preparation method of the phosphate modified Acrylate Core-shell Emulsion of salt spray resistance, preparation processes It is as follows：
A) the soft or hard monomer of acrylic acid, 50~60% emulsifiers and deionized water, are weighed by formulation weight part ratio, at 50 DEG C High speed dispersion 30min, prepares pre-emulsion；
B) pre-emulsion, quantitative chain alkyl-acrylate phosphate diester and part azo two for, taking 20% or so are different Butyronitrile mixes, and stirs evenly, obtains phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 10~20% pre-emulsions, part Azodiisobutyronitrile and remaining emulsifier are warming up to 80~84 DEG C of reactions and seed emulsion are made；
D), when blueing light occurs in reaction, the acrylic acid, remaining pre-emulsion and remaining azo of mixing is slowly added dropwise Bis-isobutyronitrile is added dropwise in 1.5h~2.0h；Then phosphate diester mixing pre-emulsion is added dropwise, is dripped in 1.0h~1.5h Finish, heat up 85~90 DEG C, insulation reaction 1h, be cooled to 45 DEG C hereinafter, with neutralizer adjusting pH value between 7~8, filter out Material obtains the phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance.
The phosphate modified Acrylate Core-shell Emulsion of salt spray resistance of the present invention, is prepared using solventless method, meets green Production requirement.The phosphate modified Acrylate Core-shell Emulsion of salt spray resistance produced by the present invention has excellent adhesive force, water-fast Property, resistance to acid and alkali, resistance to ag(e)ing, salt fog resistance, anti-flash rusting and corrosion resistance, are widely used in aqueous rust-proof coatings, aqueous steel Structural paint, aqueous engineering coating, aqueous concrete anti-corrosive paint etc..
Specific embodiment
The present invention with the following Examples does further the preparation of the phosphate modified Acrylate Core-shell Emulsion of salt spray resistance Description.
Embodiment 1
A kind of octyl group-hydroxy-ethyl acrylate phosphate diester A, preparation process are as follows：
In a kettle, 0.2 part of 35.0 parts of hydroxy-ethyl acrylate and hydroquinone are added in, stirs evenly, is warming up to 50 DEG C, 28.0 parts of phosphorus pentoxide with octanol is added portionwise for 36.8 parts, is added in 1.5h, temperature is then raised to 82 DEG C, heat preservation is anti- 3h is answered, acid value is measured, cools down after qualified, discharge, obtain the octyl group-hydroxy-ethyl acrylate phosphate diester A.
Embodiment 2
It is a kind of that base-hydroxyethyl methacrylate phosphate diester B, preparation process are as follows：
In a kettle, 0.2 part of 40.0 parts of hydroxyethyl methacrylate and hydroquinone are added in, stirs evenly, is warming up to 50 DEG C, phosphorus pentoxide with 33.8 parts of alcohol is added portionwise for 26.0 parts, is added in 1.5h, temperature is then raised to 82 DEG C, Insulation reaction 3h measures acid value, cools down after qualified, discharge, obtains the base-hydroxyethyl methacrylate phosphate diester B.
Embodiment 3
A kind of octyl group-hydroxypropyl acrylate phosphate diester C, preparation process are as follows：
In a kettle, 0.2 part of 38.0 parts of hydroxypropyl acrylate and hydroquinone are added in, stirs evenly, is warming up to 50 DEG C, 30.0 parts of phosphorus pentoxide with octanol is added portionwise for 31.8 parts, is added in 1.5h, temperature is then raised to 82 DEG C, heat preservation is anti- 3h is answered, acid value is measured, cools down after qualified, discharge, obtain the octyl group-hydroxypropyl acrylate phosphate diester C.
Embodiment 4
A kind of phosphate modified Acrylate Core-shell Emulsion A of salt spray resistance1, preparation process is as follows：
A) 12.0 parts of methyl acrylate, 15.0 parts of methyl methacrylate, methyl-prop, are weighed by formulation weight part ratio 20.0 parts of 6.0 parts of olefin(e) acid butyl ester, 8.0 parts of isooctyl methacrylate, 0.3 part of OP-10 and deionized water, at 50 DEG C at a high speed Disperse 30min, prepare pre-emulsion；
B) 0.2 part of 12 parts of pre-emulsions, A4.0 parts of phosphate diester and azodiisobutyronitrile mixing, are taken, stirs evenly, obtains phosphorus Acid diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 7.3 parts of pre-emulsions, deionizations 0.5 part of 30.0 parts of water, 0.2 part of azodiisobutyronitrile and emulsifier COPS-I are warming up to 80~84 DEG C of reactions and seed breast are made Liquid；
D), when blueing light occurs in reaction, two isobutyl of 2.0 parts of acrylic acid, 42.0 parts of pre-emulsion and azo is slowly added dropwise The mixed liquor that 0.4 part of nitrile, is added dropwise in 1.5h~2.0h；Then 16.2 parts of phosphate diester mixing pre-emulsion is added dropwise, 1.0h~1.5h is added dropwise, and heats up 85~90 DEG C, insulation reaction 1h, is cooled to 45 DEG C hereinafter, with 1.4 parts of adjusting pH of triethylamine Value is between 7~8, filtering and discharging, obtains the phosphate modified Acrylate Core-shell Emulsion A of the salt spray resistance1。
Embodiment 5
A kind of phosphate modified Acrylate Core-shell Emulsion B of salt spray resistance1, preparation process is as follows：
A) 18.0 parts of methyl acrylate, 15.0 parts of methyl methacrylate, methacrylic acid, are weighed by formulation weight part ratio 20.0 parts of 10.0 parts of butyl ester, 0.3 part of OP-10 and deionized water, high speed dispersion 30min, prepares pre-emulsion at 50 DEG C；
B) 0.2 part of 12.5 parts of pre-emulsions, 3.0 parts of phosphate diester B and azodiisobutyronitrile mixing, are taken, is stirred evenly, Obtain phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 7.5 parts of pre-emulsions, deionizations 0.5 part of 28.0 parts of water, 0.2 part of azodiisobutyronitrile and emulsifier COPS-I are warming up to 80~84 DEG C of reactions and seed breast are made Liquid；
D), when blueing light occurs in reaction, two isobutyl of 2.5 parts of acrylic acid, 43.3 parts of pre-emulsion and azo is slowly added dropwise The mixed liquor that 0.4 part of nitrile, is added dropwise in 1.5h~2.0h；Then 15.7 parts of phosphate diester mixing pre-emulsion is added dropwise, 1.0h~1.5h is added dropwise, and heats up 85~90 DEG C, insulation reaction 1h, is cooled to 45 DEG C hereinafter, with 1.9 parts of adjusting pH of triethylamine Value is between 7~8, filtering and discharging, obtains the phosphate modified Acrylate Core-shell Emulsion B of the salt spray resistance1。
Embodiment 6
A kind of phosphate modified Acrylate Core-shell Emulsion C of salt spray resistance1, preparation process is as follows：
A) 28.0 parts of methyl methacrylate, 10.0 parts of lauryl acrylate, metering system, are weighed by formulation weight part ratio 20.0 parts of 5.0 parts of acid butyl ester, 0.3 part of OP-10 and deionized water, high speed dispersion 30min, prepares pre-emulsion at 50 DEG C；
B) 0.2 part of 12.5 parts of pre-emulsions, 2.5 parts of phosphate diester C and azodiisobutyronitrile mixing, are taken, is stirred evenly, Obtain phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 7.0 parts of pre-emulsions, deionizations 0.5 part of 29.0 parts of water, 0.2 part of azodiisobutyronitrile and emulsifier COPS-I are warming up to 80~84 DEG C of reactions and seed breast are made Liquid；
D), when blueing light occurs in reaction, two isobutyl of 2.0 parts of acrylic acid, 43.8 parts of pre-emulsion and azo is slowly added dropwise The mixed liquor that 0.4 part of nitrile, is added dropwise in 1.5h~2.0h；Then 15.2 parts of phosphate diester mixing pre-emulsion is added dropwise, 1.0h~1.5h is added dropwise, and heats up 85~90 DEG C, insulation reaction 1h, is cooled to 45 DEG C hereinafter, with 1.9 parts of dimethylethanolamine Adjusting pH value is between 7~8, filtering and discharging, obtains the phosphate modified Acrylate Core-shell Emulsion C of the salt spray resistance1。
According to relevant criterion, to the embodiment of the present invention lotion and the phosphate modified acrylic emulsion D of comparative example PMA-200 It is compared, the performance of lotion is as shown in table 1.
Glass transition temperature：It is tested with differentia scanning calorimetry DSC.
Grain size and particle diameter distribution：The samples of latex of 100g or so is taken, is tested with particle diameter distribution instrument.
Water-resistance property of coating：The water resistance of film is characterized with the water absorption rate of film, water absorption rate is higher, and water resistance is poorer；It will Coalescents are added to stirred evenly in lotion after be coated on polyfluortetraethylene plate, drying at room temperature 7 days peels film and weighs weight For W1, then film is totally immersed in deionized water, it takes out afterwards for 24 hours, the water on surface is blotted with filter paper, weigh weight as W2, then The water absorption rate of film=(W2- W1)/W1× 100%.
Anti- flash rusting：By lotion applicator on the tinplate handled well, drying at room temperature, range estimation dried coating film whether there is in the process Flash rusting.
Table 1：The embodiment of the present invention and comparative example emulsion film performance comparison
As seen from Table 1, the embodiment of the present invention is better than comparative example in water resistance, heat-resisting quantity, this is because phosphate Chain alkyl on group has the heat-resistant stable that self-emulsifying function improves lotion, and the hydrophobic performance of chain alkyl improves film Water resistance.
By the embodiment of the present invention latex A1、B1、C1It is pressed with comparative example (the phosphate modified acrylic emulsion D of PMA-200) It states formula and water-based anticorrosive paint A is respectively prepared2、B2、C2With comparative example D1。
Water-based anticorrosive paint formula：Lotion 30~50%, filler (talcum powder, mica powder) 10~18%, iron oxide red 10~ 20%th, composite zinc phosphate 20~30%, dispersant 0.5~1.5%, coalescents 1.0~5.0%, other auxiliary agents 1.0~ 4.0%th, remaining is deionized water.
According to relevant criterion, performance contrasting detection, performance technologies index such as table 2 are carried out to above-mentioned water-based anticorrosive paint It is shown.
Table 2：Water-based anticorrosive paint technical performance index
As seen from Table 2, water-based anticorrosive paint made of lotion of the invention is in water resistance, salt fog resistance, hygrometric state attachment Power is better than comparative example, this is that (passivation is water-fast with height for the double action based on the ester modified acrylic resin of phosphide of the invention Property), strengthen the adhesive force and compactness between film and base material, be effectively isolated hydrone, chlorion, sodium ion etc. and enter tree Between fat and base material, adhesive force and anti-flash rusting performance are improved under wet condition, so as to improve its water resistance, salt fog resistance and prevent Become rusty antiseptic property.
Although the present invention has described it in detail and cited embodiments, it but for those of ordinary skill in the art, shows Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.

Claims (6)

1. a kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance, which is characterized in that the salt spray resistance it is phosphate modified Acrylate Core-shell Emulsion is made of stratum nucleare and shell, and chain alkyl-acrylate phosphate diester functional group is contained on shell, Its molecular structural formula is as follows：
Wherein, the R in molecular structural formula1、R2、R3For H ,-CH3Or other alkyls substituent groups；R4For butyl ester base, different monooctyl ester Base, laruyl alcohol ester group, bay ester group, octadecyl ester base；R is C6-10Chain alkyl；N=1~3；M=18~26；
The phosphate modified acrylate core-shell latex of the salt spray resistance, by weight, ingredient is：The soft or hard list of acrylate 30.0~50.0 parts of body, 1.5~4.0 parts of acrylic acid, chain alkyl -2.0~5.0 parts of acrylate phosphate diester, neutralizer 1.0 ~3.0 parts, 0.5~2.0 part of azodiisobutyronitrile, 1.5~3.0 parts of emulsifier, 40.0~60.0 parts of deionized water；
The chain alkyl-acrylate phosphate diester, is made by following reaction equation：
The phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance, glass transition temperature Tg is 30~45 DEG C, grain size be 60~ 150nm。
2. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that the propylene Acid esters hard monomer is methyl acrylate, methyl methacrylate, ethyl methacrylate, the middle one or more of ethyl acrylate Combination；The acrylate soft monomer is butyl acrylate, butyl methacrylate, tert-butyl acrylate, methacrylic acid N-butyl, Isobutyl methacrylate, isooctyl methacrylate, lauryl alcohol ester, lauryl acrylate, methyl Octadecyl acrylate, octadecyl acrylate middle one or more combination；The acrylate soft monomer and acrylate are hard The molar ratio of monomer is 1:0.1~1.
3. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that the long-chain Alkyl-acrylate phosphate diester, by weight, consisting of：35.0~45.0 parts of hydroxy acryl acid ester monomer, R6- 1030~40.0 parts of OH, 0.1~0.5 part of hydroquinone, 20~30.0 parts of phosphorus pentoxide；
Wherein, the hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, methacrylate middle one or more combination；The R6- 10OH is containing C6-10Chain alkyl single methanol；
The chain alkyl-acrylate phosphate diester, preparation process are as follows：In a kettle, quantitative hydroxyl is added in Acrylate monomer and quantitative hydroquinone, stir evenly, and are warming up to 50 DEG C, by quantitative phosphorus pentoxide and R6-10OH points It batch adds in, is added in 1.5h, be then warming up to 82 DEG C, insulation reaction 3h, measured acid value, cool down after qualified, discharge, obtained described Chain alkyl-acrylate phosphate diester.
4. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that the breast Combination of the agent for one or more of COPS-I, CO-436, OP-10.
5. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that in described With the combination that agent is one or more of triethylamine, ammonium hydroxide, dimethylethanolamine.
6. a kind of preparation method of the phosphate modified acrylate core-shell latex of salt spray resistance as described in claim 1, feature It is, preparation process is as follows：
A) the soft or hard monomer of acrylic acid, 50~60% emulsifiers and deionized water, are weighed by formulation weight part ratio, at 50 DEG C at a high speed Disperse 30min, prepare pre-emulsion；
B) 20% or so pre-emulsion, quantitative chain alkyl-acrylate phosphate diester and part azodiisobutyronitrile, is taken Mixing, stirs evenly, obtains phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 10~20% pre-emulsions, part azo Bis-isobutyronitrile and remaining emulsifier are warming up to 80~84 DEG C of reactions and seed emulsion are made；
D), when blueing light occurs in reaction, the acrylic acid, remaining pre-emulsion and remaining azo two that mixing is slowly added dropwise are different Butyronitrile is added dropwise in 1.5h~2.0h；Then phosphate diester mixing pre-emulsion is added dropwise, is added dropwise in 1.0h~1.5h, Be warming up to 85~90 DEG C, insulation reaction 1h, be cooled to 45 DEG C hereinafter, with neutralizer adjust pH value between 7~8, filtering and discharging, Obtain the phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance.
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CN110117339A (en) * 2019-06-13 2019-08-13 深圳市志邦科技有限公司 A kind of ability cathode electrophoresis coating resins of high salt spray resistance and preparation method thereof
CN110452567A (en) * 2019-08-28 2019-11-15 林芬 A kind of selfreparing anticorrosive paint and preparation method for seawater hypersaline environment
CN110511318A (en) * 2019-09-24 2019-11-29 泰兴盛嘉树脂有限公司 A kind of method that methacrylic acid phosphoric acid ester is acrylic resin modified
CN110818828A (en) * 2019-12-07 2020-02-21 合众（佛山）化工有限公司 Self-retardant fuel alcohol polyether-2 phosphate modified waterborne acrylic acid anticorrosive resin and preparation method thereof
CN111471396A (en) * 2020-05-29 2020-07-31 国网河南省电力公司南召县供电公司 Anti-icing coating for transmission cable and preparation method thereof
CN113604146A (en) * 2021-09-10 2021-11-05 中建安装集团南京建设有限公司 Large-diameter corrosion-resistant steel pipe for pipe jacking construction and machining process thereof
CN114085588A (en) * 2021-12-15 2022-02-25 合众（佛山）化工有限公司 Allyl polyoxyethylene ether phosphate modified acrylic resin water-based paint
CN114133846A (en) * 2021-12-15 2022-03-04 合众（佛山）化工有限公司 Allyl polyoxyethylene ether phosphate modified alkyd resin water-based paint

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117339A (en) * 2019-06-13 2019-08-13 深圳市志邦科技有限公司 A kind of ability cathode electrophoresis coating resins of high salt spray resistance and preparation method thereof
CN110452567A (en) * 2019-08-28 2019-11-15 林芬 A kind of selfreparing anticorrosive paint and preparation method for seawater hypersaline environment
CN110511318A (en) * 2019-09-24 2019-11-29 泰兴盛嘉树脂有限公司 A kind of method that methacrylic acid phosphoric acid ester is acrylic resin modified
CN110511318B (en) * 2019-09-24 2021-03-30 泰兴盛嘉树脂有限公司 Method for modifying acrylic resin by methacrylic acid phosphate
CN110818828A (en) * 2019-12-07 2020-02-21 合众（佛山）化工有限公司 Self-retardant fuel alcohol polyether-2 phosphate modified waterborne acrylic acid anticorrosive resin and preparation method thereof
CN110818828B (en) * 2019-12-07 2022-05-03 合众（佛山）化工有限公司 Self-retardant fuel alcohol polyether-2 phosphate modified waterborne acrylic acid anticorrosive resin and preparation method thereof
CN111471396A (en) * 2020-05-29 2020-07-31 国网河南省电力公司南召县供电公司 Anti-icing coating for transmission cable and preparation method thereof
CN113604146A (en) * 2021-09-10 2021-11-05 中建安装集团南京建设有限公司 Large-diameter corrosion-resistant steel pipe for pipe jacking construction and machining process thereof
CN114085588A (en) * 2021-12-15 2022-02-25 合众（佛山）化工有限公司 Allyl polyoxyethylene ether phosphate modified acrylic resin water-based paint
CN114133846A (en) * 2021-12-15 2022-03-04 合众（佛山）化工有限公司 Allyl polyoxyethylene ether phosphate modified alkyd resin water-based paint

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