CN105602388B - A kind of alkyd resin modified acroleic acid anticorrosive paint of core shell structure and preparation method thereof - Google Patents

A kind of alkyd resin modified acroleic acid anticorrosive paint of core shell structure and preparation method thereof Download PDF

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CN105602388B
CN105602388B CN201610037893.6A CN201610037893A CN105602388B CN 105602388 B CN105602388 B CN 105602388B CN 201610037893 A CN201610037893 A CN 201610037893A CN 105602388 B CN105602388 B CN 105602388B
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anticorrosive paint
shell structure
core shell
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CN105602388A (en
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涂伟萍
张翔
崔航
卢明
方增滨
张明徽
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate

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Abstract

The invention belongs to chemical anticorrosion paint field, discloses alkyd resin modified acroleic acid anticorrosive paint of a kind of core shell structure and preparation method thereof.The anticorrosive paint is prepared by following component by weight：Aqueous alkide resin 40~50, reaction monomers 45~63, pigment 15~20, deionized water 64~131, defoamer 1~2, initiator 0.12~0.38.The barrier propterty of anticorrosive paint prepared by the present invention has the characteristics that the weatherability that strong adhesive force, mechanical strength are good, corrosion resistant performance is excellent, splendid better than acrylic acid and the anticorrosive paint of alkyd.

Description

A kind of alkyd resin modified acroleic acid anticorrosive paint of core shell structure and preparation method thereof
Technical field
The invention belongs to chemical anticorrosion paint field, and in particular to a kind of alkyd resin modified propylene for possessing core shell structure Sour anticorrosive paint and preparation method thereof.
Background technology
Anticorrosive paint is a kind of organic liquid material using resin as main component additional functional additive, by additive institute group Into inorganic powder using rational proportion compounding form.In antirusting paint component, what is played a crucial role to anti-corrosion function is face Material and film forming matter.
Although traditional alkyd anticorrosive paint paint film is plentiful, strong adhesive force, mechanical strength are good, film is soft, acid and alkali-resistance Property is poor；And although Acrylic Anticorrosive Coatings have excellent corrosion resistance, but wetability is poor, and film forming speed is too fast, influences to apply Layer quality.
The Chinese patent application of Publication No. CN 103555158A discloses a kind of system of High-efficiency alkyd resin anticorrosion paint Preparation Method, on the basis of basic alkyd, by add phosphate, barium sulfate and talcum powder make product granularity uniformly, gloss holds Long and there is good corrosion resistance, but since the poor and slower drying property of weatherability caused by the characteristic of alkyd in itself remains unchanged It is not resolved, the compatibility between the acetate fiber and polyurethane that add in addition is still asking up for solution Topic.The Chinese patent application of Publication No. CN 104513575A discloses a kind of preparation method of acrylic acid series anticorrosive paint, leads to Cross and acrylic resin is modified, and by being modified to filler, improve the corrosion resistance and adhesive force of coating, but Mechanical performance, gloss and the richness of coating are all up for improving.
The problem of anticorrosive paint is most essential is fine and close coating, completely cuts off the contact of air and water with base material.Alkyd paint with Acrylic coating respectively has advantage and disadvantage on antiseptic property, but simply two kinds of coating of compounding are inherently fail between change coating The stability of consistency problem and coating.Preparing a kind of alkyd and the coating of the excellent antiseptic property of acrylic acid of having concurrently can widen The application range and condition of anticorrosive paint.
The content of the invention
The shortcomings that in order to overcome the prior art and deficiency, primary and foremost purpose of the invention are to provide a kind of alcohol of core shell structure Acid resin modified acroleic acid anticorrosive paint.The anticorrosive paint has had alkyd painting concurrently using alkyd resin as polymerisable emulsifier Material and the excellent antiseptic property of acrylic coating.The present invention is lacked from aqueous alkide resin and the excellent of two kinds of systems of polyacrylate dispersion Point considers, the means synthesized with lotion, has prepared a kind of barrier propterty better than acrylic acid and the anticorrosive paint of alkyd. The present invention, which solves the defects of existing product existing defects, mechanical property and water resistance, cannot meet growing anti-corrosion industry The problem of technical requirements, prepared anticorrosive paint have the advantages that strong adhesive force, mechanical strength are good, corrosion resistant performance is excellent.
System another object of the present invention is to the alkyd resin modified acroleic acid anticorrosive paint for providing above-mentioned core shell structure Preparation Method.
The alkyd resin modified acroleic acid anticorrosive paint of a kind of core shell structure, by following component preparation by weight Into：
The reaction monomers are by styrene, methacrylate-based monomer, α-methacrylic acid and esters of acrylic acid list Body forms；The methacrylate-based monomer is one or more of methyl methacrylate or butyl methacrylate, excellent Elect the mixture of methyl methacrylate or methyl methacrylate and butyl methacrylate as；The acrylic ester monomer For one or more of butyl acrylate, hydroxy-ethyl acrylate or hydroxypropyl acrylate.
Styrene, methacrylate-based monomer, α-methacrylic acid and esters of acrylic acid list in the reaction monomers The weight ratio of body is (14~21)：(14~21)：(10~18)：(0~8).
The aqueous alkide resin is prepared by following methods：
(1) by 80~90 parts by weight linseed oil, 12~15 parts by weight pentaerythrites, 0.03~0.05 parts by weight base catalysis Agent is placed in container, in 220~240 DEG C of 40~60min of alcoholysis；Obtain alcoholysis liquid；
Step (1) described basic catalyst is LiOH, CaO or lithium ricinoleate；
(2) under conditions of stirring, by alcoholysis liquid in step (1) and 30~50 parts by weight phthalic anhydrides, 0.5~3 Parts by weight maleic anhydride, 5~10 parts by weight 2,2- dihydromethyl propionic acids and the mixing of 4~8 parts by weight diglycols, and add 0.03~0.04 esterification catalyst, is heated to 150~180 DEG C, insulation reaction 40-60min；Then raise temperature to 220~ 230 DEG C, to certain acid number, obtain crude product；
Step (2) described esterification catalyst is bc-98 (trade name) or p-methyl benzenesulfonic acid；The acid number is 40~50mg/g KOH；The rotating speed is 160~190rpm；
(3) crude product is cooled down, it is 7~8 to be neutralized to pH with neutralizer, obtains aqueous alkide resin, the alkyd resin For micro- yellow transparent resin.
Step (3) described cooling temperature is 30~45 DEG C.
Neutralizer described in step (3) is triethylamine or mass percent concentration is 45% ammonium hydroxide.
For the present invention using pentaerythrite as polyalcohol, the alkyd resin of preparation has high oil content (60%~65%), soft The advantages of good toughness.
The initiator is one or more of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
The defoamer is one or more of BYK-361, BYK-355, BYK-354 or BYK-390.
The pigment is one or more of trbasic zinc phosphate, aluminum phosphate, zinc molybdate, calcium molybdate or barium metaborate.
The preparation method of the alkyd resin modified acroleic acid anticorrosive paint of the core shell structure, specifically includes following steps：
(a) 40~50 parts by weight aqueous alkide resins, 0.1~0.3 parts by weight initiator and 45~63 parts by weight are reacted Monomer is mixed, and adds 30~70 parts by weight of deionized water, high speed shearing emulsification, obtains pre-emulsion；
(b) 25~30 parts by weight pre-emulsions in step (a) are mixed with 30~55 parts by weight of deionized water, be heated to 78~82 DEG C, 20~40min of insulation reaction；The pre-emulsion of remainder is added dropwise；0.02~0.08 parts by weight are then added to trigger Agent and 4.0~6.0 parts by weight of deionized water, are warming up to 84~88 DEG C, keep the temperature 1.5~3h, obtain alkyd acrylic acid composite emulsion；
(c) 1~2 parts by weight of defoamer are added into the alkyd acrylic acid composite emulsion of step (b), is uniformly mixed, obtains Complex emulsions；
(d) complex emulsions of step (c) and 15~20 parts by weight pigment are dispersed with stirring to the alcohol for uniformly, obtaining core shell structure Acid resin modified acroleic acid anticorrosive paint.
Step (d) speed of agitator is 100~170r/min.
The rotating speed of step (a) high speed shear is 4000~6000r/min, time of high speed shearing emulsification for 15~ 20min。
The speed being added dropwise described in step (b) is 10~20 drops/min.
The pre-emulsion of step (b) remainder need to be dripped off in 3.5~4h.
Compared with prior art, the present invention has the following advantages and beneficial effect：
Advantage and disadvantage of the invention based on two kinds of systems of aqueous alkide resin and polyacrylate dispersion consider, with breast The means of liquid synthesis, have prepared a kind of barrier propterty better than acrylic acid and the anticorrosive paint of alkyd.The present invention solves existing Compatibility issue of the product between two kinds of systems, using polymerizable alkyd as emulsifying agent, eliminates emulsifying agent and was forming a film Side effect in journey, has the characteristics that the weatherability that strong adhesive force, mechanical strength are good, corrosion resistant performance is excellent, splendid.
Brief description of the drawings
Fig. 1 is the SEM figures of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure prepared by embodiment 8.
Embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is further illustrated, but the reality of the present invention Apply mode not limited to this.
Embodiment 1
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) 80 parts by weight linseed oil, 12 parts by weight pentaerythrites, 0.03 parts by weight LiOH are mixed, in 220 DEG C of alcoholysis 60min；Obtain alcoholysis liquid；
(2) by alcoholysis liquid in step (1) and 30 parts by weight phthalic anhydrides, 0.5 parts by weight maleic anhydride, 5 parts by weight 2,2- dihydromethyl propionic acids and the mixing of 4 parts by weight diglycols, and 0.03 part by weight of catalyst (commodity bc-98) is added, Dimethylbenzene is added as cosolvent and water entrainer；175 DEG C are heated under 160r/min rotating speeds, insulation reaction 40min；With After be warming up to 220 DEG C, be 45mg/g KOH to system acid number, obtain crude product；
(3) crude product is cooled to 40 DEG C, it is 7 to be neutralized to pH with triethylamine, obtains micro- transparent alkyd resin of Huang i.e. alkyd Resin；
(4) by 40 parts by weight alkyd resins, 0.1 parts by weight ammonium persulfate and 15 parts by weight of styrene, 15 parts by weight methyl Methyl acrylate, 10 parts by weight α-methacrylic acids and 5 weight parts of methacrylic acid butyl esters mix in a device, add 36 weight Part deionized water, 4000r/min high speed shearing emulsification 15min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 25 parts by weight pre-emulsions and 40 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 82 DEG C, insulation reaction 20min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 3.5h is dripped off；With After add 0.02 parts by weight initiator (ammonium persulfate) and 4.0 parts by weight of deionized water, be warming up to 84 DEG C, keep the temperature 1.5h, obtain Alkyd acrylic acid composite emulsion；
(6) 1 parts by weight defoamer BYK-361 is added into alkyd acrylic acid composite emulsion, is uniformly mixed, obtains Composite Milk Liquid；
(7) complex emulsions obtained in step (6) are placed in dispersion machine, 20 parts by weight of phosphoric acid zinc are added, with 150/min Rotating speed stirring treat without any solid impurity untill, obtain the alkyd resin modified acroleic acid anticorrosive paint of core shell structure.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 4h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 1mm, impact resistance 30cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 2
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 90 parts by weight linseed oil, 15 parts by weight pentaerythrites, 0.05 parts by weight lithium ricinoleate in 240 DEG C of alcoholysis 40min；Obtain alcoholysis liquid；
(2) by alcoholysis liquid in step (1) and 50 parts by weight phthalic anhydrides, 3 parts by weight maleic anhydride, 5 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 4 parts by weight diglycols, and 0.03 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；150 DEG C are heated under 190r/min rotating speeds, insulation reaction 60min；Then raise temperature to 230 DEG C, it is 40mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 35 DEG C, is 7 with ammonium hydroxide and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd resin；
(4) by 50 parts by weight alkyd resins, 0.2 parts by weight potassium peroxydisulfate and 16 amount part styrene, 16 amount part metering systems The container of sour methyl esters, 16 parts by weight α-methacrylic acids, 4 butyl methacrylates and 4 parts by weight of acrylic acid hydroxyl ethyl esters in 250ml Middle mixing, adds 65 parts by weight of deionized water, 4500r/min high speed shearing emulsification 15min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 25 parts by weight pre-emulsions and 30 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 75 DEG C, insulation reaction 40min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 3.5h is dripped off；With After add 0.04 parts by weight initiator (potassium peroxydisulfate) and 5.0 parts by weight of deionized water, be warming up to 86 DEG C, keep the temperature 2h, obtain alcohol Acid acrylic acid complex emulsions；
(6) 1 parts by weight defoamer BYK-390 is added into alkyd acrylic acid composite emulsion, is uniformly mixed, obtains Composite Milk Liquid；
(7) complex emulsions obtained in (6) are placed in dispersion machine, 15 parts by weight of phosphoric acid aluminium are added, with 100r/min's Untill rotating speed stirring is treated without any solid impurity, the alkyd resin modified acroleic acid anticorrosive paint of core shell structure is obtained.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 3h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 1mm, impact resistance 35cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 3
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 85 parts by weight linseed oil, 13 parts by weight pentaerythrites, 0.04 parts by weight CaO in 235 DEG C of alcoholysis 50min； To alcoholysis liquid；
(2) by alcoholysis liquid in step (1) and 45 parts by weight phthalic anhydrides, 2 parts by weight maleic anhydride, 7 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 6 parts by weight diglycols, and 0.04 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；180 DEG C are heated under 160r/min rotating speeds, insulation reaction 40min；Then raise temperature to 225 DEG C, it is 45mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 30 DEG C, is 7.5 with ammonium hydroxide and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd tree Fat；
(4) by 45 parts by weight alkyd resins, 0.30 parts by weight potassium peroxydisulfate, 14 amount part styrene, 14 amount part metering systems Sour methyl esters, 14 parts by weight α-methacrylic acids and 7 parts by weight of acrylic acid hydroxyl ethyl esters mix in the container of 250ml, add 50 weights Part deionized water is measured, 5000r/min high speed shearing emulsification 20min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 30 parts by weight pre-emulsions and 40 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 78 DEG C, insulation reaction 30min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 4h is dripped off；Then 0.08 parts by weight initiator (potassium peroxydisulfate) and 6.0 parts by weight of deionized water are added, are warming up to 88 DEG C, 3h is kept the temperature, obtains alkyd Acrylic acid composite emulsion；
(6) 2 parts by weight defoamer BYK-354 are added into alkyd acrylic acid composite emulsion, is uniformly mixed, obtains Composite Milk Liquid；
(7) complex emulsions obtained in (6) are placed in dispersion machine, 15 parts by weight zinc molybdates are added, with 170r/min's Untill rotating speed stirring is treated without any solid impurity, the alkyd resin modified acroleic acid anticorrosive paint of core shell structure is obtained.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 3h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 2mm, impact resistance 32cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 4
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 85 parts by weight linseed oil, 13 parts by weight pentaerythrites, 0.04 parts by weight CaO in 235 DEG C of alcoholysis 50min； To alcoholysis liquid.
(2) by alcoholysis liquid in step (1) and 45 parts by weight phthalic anhydrides, 2 parts by weight maleic anhydride, 7 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 6 parts by weight diglycols, and 0.04 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；180 DEG C are heated under 170r/min rotating speeds, insulation reaction 40min；Then raise temperature to 225 DEG C, it is 45mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 35 DEG C, is 8 with ammonium hydroxide and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd resin；
(4) by 50 parts by weight alkyd resins, 0.2 parts by weight ammonium persulfate, 18 amount part styrene, 18 amount part methacrylic acids The container of methyl esters, 18 parts by weight α-methacrylic acids, 2 parts by weight propylene acid butyl esters and 4 parts by weight of acrylic acid hydroxypropyl acrylates in 250ml Middle mixing, adds 45 parts by weight of deionized water, 5000r/min high speed shearing emulsification 20min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 30 parts by weight pre-emulsions and 40 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 78 DEG C, insulation reaction 30min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 4h is dripped off；Then 0.05 parts by weight initiator (ammonium persulfate) and 5.0 parts by weight of deionized water are added, are warming up to 86 DEG C, 3h is kept the temperature, obtains alkyd Acrylic acid composite emulsion；
(6) 2 parts by weight defoamer BYK-355 are added into alkyd acrylic acid composite emulsion, is uniformly mixed, obtains Composite Milk Liquid；
(7) complex emulsions obtained in (6) are placed in dispersion machine, 17 parts by weight zinc molybdates are added, with 170r/min's Untill rotating speed stirring is treated without any solid impurity, the alkyd resin modified acroleic acid anticorrosive paint of core shell structure is obtained.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 4h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 2mm, impact resistance 35cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 5
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 85 parts by weight linseed oil, 13 parts by weight pentaerythrites, 0.04 parts by weight CaO in 235 DEG C of alcoholysis 50min； To alcoholysis liquid.
(2) by alcoholysis liquid in step (1) and 45 parts by weight phthalic anhydrides, 2 parts by weight maleic anhydride, 7 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 6 parts by weight diglycols, and 0.04 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；180 DEG C are heated under 180r/min rotating speeds, insulation reaction 40min；Then raise temperature to 230 DEG C, it is 40mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 40 DEG C, is 7 with triethylamine and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd tree Fat；
(4) by 50 parts by weight alkyd resins, 0.3 parts by weight ammonium persulfate, 21 parts by weight of styrene, 21 parts by weight methyl-props E pioic acid methyl ester, 14 parts by weight α-methacrylic acids, 2 parts by weight propylene acid butyl esters and 5 parts by weight of acrylic acid hydroxypropyl acrylates are 250ml's Mixed in container, add 35 parts by weight of deionized water, 5000r/min high speed shearing emulsification 20min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 30 parts by weight pre-emulsions and 40 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 82 DEG C, insulation reaction 20min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 3.75h is dripped off；With After add 0.03 parts by weight initiator (ammonium persulfate) and 6.0 parts by weight of deionized water, be warming up to 84 insulation 1.5h, obtain alkyd Acrylic acid composite emulsion；
(6) 1.5 parts by weight defoamer BYK-355 are added into alkyd acrylic acid composite emulsion, is uniformly mixed, obtains compound Lotion；
(7) complex emulsions obtained in (6) are placed in dispersion machine, 20 parts by weight calcium molybdates are added, with 140r/min's Untill rotating speed stirring is treated without any solid impurity, the alkyd resin modified acroleic acid anticorrosive paint of core shell structure is obtained.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 2h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 1mm, impact resistance 30cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 6
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 85 parts by weight linseed oil, 13 parts by weight pentaerythrites, 0.04 parts by weight CaO in 235 DEG C of alcoholysis 50min； To alcoholysis liquid；
(2) by alcoholysis liquid in step (1) and 45 parts by weight phthalic anhydrides, 2 parts by weight maleic anhydride, 7 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 6 parts by weight diglycols, and 0.04 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；160 DEG C are heated under 180r/min rotating speeds, insulation reaction 40min；Then raise temperature to 230 DEG C, it is 45mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 45 DEG C, is 8 with triethylamine and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd tree Fat；
(4) by 50 parts by weight alkyd resins, 0.25 parts by weight sodium peroxydisulfate, 16 parts by weight of styrene, 16 parts by weight methyl Methyl acrylate, 16 parts by weight α-methacrylic acids, 1 parts by weight of acrylic acid hydroxyl ethyl ester and 7 parts by weight of acrylic acid hydroxypropyl acrylates exist Mixed in the container of 250ml, add 35 parts by weight of deionized water, 5000r/min high speed shearing emulsification 20min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 30 parts by weight pre-emulsions and 45 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 82 DEG C, insulation reaction 20min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 3.75h is dripped off；With After add 0.06 parts by weight initiator (sodium peroxydisulfate) and 4.0 parts by weight of deionized water, be warming up to 88 DEG C, keep the temperature 1.5h, obtain Alkyd acrylic acid composite emulsion；
(6) 1 parts by weight defoamer BYK-355 and 0.5 parts by weight BYK-390 are added into alkyd acrylic acid composite emulsion, It is uniformly mixed, obtains complex emulsions；
(7) complex emulsions obtained in (6) are placed in dispersion machine, 17 parts by weight barium metaborates are added, with 140r/min Rotating speed stirring treat without any solid impurity untill, obtain the alkyd resin modified acroleic acid anticorrosive paint of core shell structure.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 2h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 1mm, impact resistance 36cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 7
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 85 parts by weight linseed oil, 13 parts by weight pentaerythrites, 0.04 parts by weight CaO in 235 DEG C of alcoholysis 50min； To alcoholysis liquid.
(2) by alcoholysis liquid in step (1) and 45 parts by weight phthalic anhydrides, 2 parts by weight maleic anhydride, 7 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 6 parts by weight diglycols, and 0.04 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；160 DEG C are heated under 170r/min rotating speeds, insulation reaction 50min；Then raise temperature to 220 DEG C, it is 42mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 35 DEG C, is 7.5 with ammonium hydroxide and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd tree Fat；
(4) by 50 parts by weight alkyd resins, 0.27 parts by weight sodium peroxydisulfate, 20 parts by weight of styrene, 20 parts by weight methyl Methyl acrylate, 14 parts by weight α-methacrylic acids and 7 parts by weight of acrylic acid hydroxypropyl acrylates mix in the container of 250ml, add 35 parts by weight of deionized water, 5000r/min high speed shearing emulsification 20min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 30 parts by weight pre-emulsions and 55 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 82 DEG C, insulation reaction 20min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 3.75h is dripped off；With After add 0.08 parts by weight initiator (sodium peroxydisulfate) and 5.0 parts by weight of deionized water, be warming up to 86 DEG C, keep the temperature 1.5h, obtain Alkyd acrylic acid composite emulsion；
(6) 1 parts by weight defoamer BYK-361 and 0.5 parts by weight BYK-390 are added into alkyd acrylic acid composite emulsion, It is uniformly mixed, obtains complex emulsions；
(7) complex emulsions obtained in (6) are placed in dispersion machine, add 10 parts by weight calcium molybdates and 7 parts by weight of phosphoric acid Zinc, untill the rotating speed stirring of 140r/min is treated without any solid impurity, obtains the alkyd resin modified acroleic acid of core shell structure Anticorrosive paint.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 3h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 2mm, impact resistance 33cm, Bin stability is by the way that salt fog resistance passes through.
Embodiment 8
A kind of preparation method of the alkyd resin modified acroleic acid anticorrosive paint of core shell structure, specifically includes following steps：
(1) by 85 parts by weight linseed oil, 13 parts by weight pentaerythrites, 0.04 parts by weight CaO in 235 DEG C of alcoholysis 50min； To alcoholysis liquid；
(2) by alcoholysis liquid in step (1) and 45 parts by weight phthalic anhydrides, 2 parts by weight maleic anhydride, 7 parts by weight 2, 2- dihydromethyl propionic acids and the mixing of 6 parts by weight diglycols, and 0.04 weight p-methyl benzenesulfonic acid is added, add dimethylbenzene and make For cosolvent and water entrainer；160 DEG C are heated under 180r/min rotating speeds, insulation reaction 50min；Then raise temperature to 225 DEG C, it is 45mg/g KOH to system acid number, obtains crude product；
(3) crude product is cooled to 30 DEG C, is 7.5 with triethylamine and to pH, obtains micro- transparent alkyd resin of Huang i.e. alkyd Resin；
(4) by 50 parts by weight alkyd resins, 0.15 parts by weight sodium peroxydisulfate, 17 parts by weight of styrene, 17 parts by weight methyl Methyl acrylate, 14 parts by weight α-methacrylic acids and 7 parts by weight of acrylic acid hydroxypropyl acrylates mix in the container of 250ml, add 35 parts by weight of deionized water, 5000r/min high speed shearing emulsification 20min, obtain pre-emulsion；
(5) under conditions of stirring (100r/min) 30 parts by weight pre-emulsions and 50 parts by weight deionizations in step (4), are taken Water mixes, and is heated to 82 DEG C, insulation reaction 20min；Then the pre-emulsion of remainder is at the uniform velocity added dropwise, 3.75h is dripped off；With After add 0.08 parts by weight initiator (sodium peroxydisulfate) and 4.0 parts by weight of deionized water, be warming up to 84 DEG C, keep the temperature 1.5h, obtain Alkyd acrylic acid composite emulsion；
(6) 1.5 parts by weight defoamer BYK-390 are added into alkyd acrylic acid composite emulsion, is uniformly mixed, obtains compound Lotion；
(7) complex emulsions obtained in (6) are placed in dispersion machine, add 10 parts by weight calcium molybdates and 7 parts by weight of phosphoric acid Zinc, untill the rotating speed stirring of 140r/min is treated without any solid impurity, obtains the alkyd resin modified acroleic acid of core shell structure Anticorrosive paint, the SEM figures of the anticorrosive paint are as shown in Figure 1.
By gained anticorrosive paint according to《JG/T224-2007 People's Republic of China (PRC) building industry professional standard》In survey Examination requirement is tested for the property：Surface drying time 2h, water resistance is by, adhesion 1 grade, resistance to bend(ing) 1mm, impact resistance 36cm, Bin stability is by the way that salt fog resistance passes through.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description Other various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention All any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention Within the scope of.

Claims (7)

  1. A kind of 1. alkyd resin modified acroleic acid anticorrosive paint of core shell structure, it is characterised in that：By it is following by weight Component is prepared：
    The reaction monomers are by styrene, methacrylate-based monomer, α-methacrylic acid and acrylic ester monomer group Into；
    Styrene in the reaction monomers, methacrylate-based monomer, α-methacrylic acid and acrylic ester monomer Weight ratio is (14~21)：(14~21)：(10~18)：(0~8)；
    The aqueous alkide resin is prepared by following methods：
    (1) 80~90 parts by weight linseed oil, 12~15 parts by weight pentaerythrites, 0.03~0.05 parts by weight basic catalyst are put In container, in 220~240 DEG C of alcoholysis 40-60min；Obtain alcoholysis liquid；
    (2) under conditions of stirring, by alcoholysis liquid in step (1) and 30~50 parts by weight phthalic anhydrides, 0.5~3 weight Part maleic anhydride, 5~10 parts by weight 2,2- dihydromethyl propionic acids and the mixing of 4~8 parts by weight diglycols, and add 0.03 ~0.04 esterification catalyst, is heated to 150~180 DEG C, 40~60min of insulation reaction；Then raise temperature to 220~230 DEG C, to certain acid number, obtain crude product；
    (3) crude product is cooled down, it is 7~8 to be neutralized to pH with neutralizer, obtains aqueous alkide resin；
    The preparation method of the alkyd resin modified acroleic acid anticorrosive paint of the core shell structure, specifically includes following steps：
    (a) 40~50 parts by weight alkyd resins, 0.1~0.3 parts by weight initiator and 45~63 parts by weight reaction monomers are carried out Mixing, adds 30~70 parts by weight of deionized water, high speed shearing emulsification, obtains pre-emulsion；
    (b) 25~30 parts by weight pre-emulsions in step (a) are mixed with 30~55 parts by weight of deionized water, it is heated to 78~ 82 DEG C, 20~40min of insulation reaction；The pre-emulsion of remainder is added dropwise；Then add 0.02~0.08 parts by weight initiator and 4.0~6.0 parts by weight of deionized water, are warming up to 84~88 DEG C, keep the temperature 1.5~3h, obtain alkyd acrylic acid composite emulsion；
    (c) 1~2 parts by weight of defoamer are added into the alkyd acrylic acid composite emulsion of step (b), is uniformly mixed, obtains compound Lotion；
    (d) complex emulsions of step (c) and 15~20 parts by weight pigment are dispersed with stirring to the alkyd tree for uniformly, obtaining core shell structure Fat modified acroleic acid anticorrosive paint.
  2. 2. the alkyd resin modified acroleic acid anticorrosive paint of core shell structure according to claim 1, it is characterised in that：The first Base acrylic ester monomer is one or more of methyl methacrylate or butyl methacrylate；The esters of acrylic acid list Body is one or more of butyl acrylate, hydroxy-ethyl acrylate or hydroxypropyl acrylate.
  3. 3. the alkyd resin modified acroleic acid anticorrosive paint of core shell structure according to claim 2, it is characterised in that：The first Base acrylic ester monomer is methyl methacrylate or the mixture of methyl methacrylate and butyl methacrylate.
  4. 4. the alkyd resin modified acroleic acid anticorrosive paint of core shell structure according to claim 1, it is characterised in that：Step (1) basic catalyst is LiOH, CaO or lithium ricinoleate；
    Step (2) described esterification catalyst is bc-98 or p-methyl benzenesulfonic acid；Step (2) described acid number is 40~50mg/g KOH.
  5. 5. the alkyd resin modified acroleic acid anticorrosive paint of core shell structure according to claim 1, it is characterised in that：Step (2) speed of agitator is 160~190rpm；Step (3) described cooling temperature is 30~45 DEG C；
    Neutralizer described in step (3) is triethylamine or mass percent concentration is 45% ammonium hydroxide.
  6. 6. the alkyd resin modified acroleic acid anticorrosive paint of core shell structure according to claim 1, it is characterised in that：It is described to draw Hair agent is one or more of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate；
    The defoamer is one or more of BYK-361, BYK-355, BYK-354 or BYK-390；
    The pigment is one or more of trbasic zinc phosphate, aluminum phosphate, zinc molybdate, calcium molybdate or barium metaborate.
  7. 7. the alkyd resin modified acroleic acid anticorrosive paint of core shell structure according to claim 1, it is characterised in that：Step (d) speed of agitator is 100~170r/min；
    The rotating speed of step (a) high speed shear is 4000~6000r/min, and the time of high speed shearing emulsification is 15~20min； The speed being added dropwise described in step (b) is 10~20 drops/min；The pre-emulsion of step (b) remainder need to be in 3.5~4h Drip off.
CN201610037893.6A 2016-01-20 2016-01-20 A kind of alkyd resin modified acroleic acid anticorrosive paint of core shell structure and preparation method thereof Expired - Fee Related CN105602388B (en)

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WO2021138433A1 (en) * 2020-01-02 2021-07-08 Avery Dennison Corporation Hybrid alkyd-acrylic based pressure sensitive adhesives and methods of making and using thereof

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CN108059695A (en) * 2017-12-22 2018-05-22 帝斯曼先达合成树脂(佛山)有限公司 A kind of preparation method of new bio matrix soap-free nucleocapsid aqueous acrylic emulsion
CN110317302B (en) * 2019-06-10 2022-05-13 长兴化学工业(中国)有限公司 Acrylic acid modified alkyd resin and preparation method thereof

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CN101591500A (en) * 2009-06-23 2009-12-02 常州光辉化工有限公司 Waterborne normal-temperature self-crosslinking acrylic acid modified alkyd antirust paint
CN102358815A (en) * 2011-07-25 2012-02-22 上海电动工具研究所 One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method
CN102603991B (en) * 2012-01-18 2013-08-21 海洋化工研究院有限公司 Environmental-friendly waterborne protective and decorative paint for inner cabin of ship
CN102746762B (en) * 2012-05-29 2014-08-06 兰州理工大学 Alkyd acrylic hybrid latex paint and preparation method thereof

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WO2021138433A1 (en) * 2020-01-02 2021-07-08 Avery Dennison Corporation Hybrid alkyd-acrylic based pressure sensitive adhesives and methods of making and using thereof

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