CN109251661A - A kind of very-high performance epoxy primer and preparation method thereof - Google Patents
A kind of very-high performance epoxy primer and preparation method thereof Download PDFInfo
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- 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
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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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C09D7/63—Additives non-macromolecular organic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- 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
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- C08K2201/011—Nanostructured additives
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- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention belongs to technical field of coatings, and in particular to a kind of very-high performance epoxy primer and preparation method thereof.Very-high performance epoxy primer provided by the invention, including component A and B component, wherein, the component A is made of Modified Epoxy Resin by Elastomers, dimethylbenzene, butanol, dispersing agent, activation siloxy group coupling agent, zinc molybdate modified pigment, the silicone-modified nano mica powder of activation, organic matter modification micaceous iron oxide, superfine talcum powder, ultra-fine barium sulfate, titanium dioxide, organoclay and carbon black；The B component is made of modified fatty amine, Epoxy curing accelerators K54, dimethylbenzene and isopropanol；The weight proportion of the component A and B component is 5:1.Very-high performance epoxy primer of the present invention has excellent anti-rust and corrosionproperties, water-fast, salt spray resistance and ageing-resistant performance；It is dry quick, there is good workability；Film even compact；Good mechanical stability, adhesive force are strong.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of very-high performance epoxy primer and preparation method thereof.
Background technique
Coating is main Anticorrosion measure, and obtains the key means of product good appearance, and coating is coating
Important source material.Coating is divided to have priming paint, (middle painting), finishing coat by coating.The adhesive force and corrosion resistance of paint film rely primarily on priming paint
Layer.Epoxy primer is a common industrial antisepsis coating, and antiseptic property is excellent.According to national standard HG/T4566-2013 ring
It is provided in oxygen resin primer, salt-fog resistant time is 120 hours.By epoxy bottom in HG/T4566-2013 epoxy resin primer standard
Paint is divided into two class of metal base product and concrete substrate product.It is divided into universal primer and closing in metal base product
Two class of priming paint, only universal primer have salt fog resistance requirement.Be specified that in HG/T4566-2013: epoxy primer is resistance to
Phenomena such as salt fog 120h, unidirectional corrosion≤2.0mm at index request scribing line, uncrossed area is without blistering, getting rusty, crack, peel off.
So epoxy primer salt-fog resistant time is at least 120h.Salt spray test imitates the marine atmosphere containing a large amount of salt to metal material
And its protective layer has strong corrosive situation, the resistance to corrosion of test paint film in the presence of a harsh environment, first 1939
Year begin to use, hereafter by improving, constantly improve it, to being commonly used at present as examining paint film corrosion resistance
Method.
Chinese patent application 201310517893.2A discloses a kind of modified epoxy priming paint, in parts by weight, including
Following each component: epoxy resin: 25~65 parts, nano silicon oxide: 1~10 part, thixotropic agent: 2~5 parts, dispersing agent: 1~3 part,
Anticorrosive packing: 10~20 parts, 10~20 parts of pigments and fillers, defoaming agent: 0.1~1 part；Polyamide-based curing agent: 20~40 parts；It is described
The epoxide equivalent of epoxy resin is 250~400EE.Although the modified epoxy priming paint that the invention provides can be applied directly to aluminium
Material surface, preferable with the adhesive force of aluminium material surface, still, salt spray resistance, water resistance are still undesirable.
Currently, the existing epoxy primer in market there are salt spray resistances undesirable, poor adhesive force, water resistance is undesirable etc. is asked
Topic.Therefore it needs to develop a kind of epoxy primer haveing excellent performance.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of very-high performance epoxy primer and its preparation sides
Method.Very-high performance epoxy primer provided by the invention has excellent anti-rust and corrosionproperties, water-fast, salt spray resistance；Fast drying
Speed has good workability；Film even compact；Good mechanical stability, adhesive force are strong.In addition, the superelevation that the present invention supplies
Performance epoxy primer has excellent ageing-resistant performance.
A kind of very-high performance epoxy primer, including component A and B component, wherein the component A is by following component and its again
Number is measured to form: 15-30 parts of Modified Epoxy Resin by Elastomers, 5-10 parts of dimethylbenzene, 5-10 parts of butanol, 0.1-0.6 parts of dispersing agent,
1-3 parts of siloxy group coupling agent of activation, activates silicone-modified nano mica powder 3-12 by 5-15 parts of zinc molybdate modified pigment
Part, micaceous iron oxide 5-15 parts of organic matter modification, 5-15 parts of superfine talcum powder, 3-12 parts of ultra-fine barium sulfate, 5-15 parts of titanium dioxide,
0.2-0.8 parts of organoclay, 0.2-0.5 parts of carbon black；
The B component is made of following component and its parts by weight: 30-60 parts of modified fatty amine, Epoxy curing accelerators
1-3 parts of K54,15-30 parts of dimethylbenzene, 10-20 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
Further, the very-high performance epoxy primer, including component A and B component, the component A is by following component
And its parts by weight composition: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, activity
1.5 parts of SiClx oxyalkyl coupling agent, activates 11 parts of silicone-modified nano mica powder by 12 parts of zinc molybdate modified pigment, organic
10 parts of micaceous iron oxide of object modification, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, carbon black
0.2 part；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54
1.2 parts, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
Further, the Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to and are leaked equipped with blender, condenser pipe, thermometer and dropping liquid
In the four-necked bottle of bucket, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C,
Even dropwise addition dibutyl tin dilaurate, time for adding 30min, the reaction was continued 1.5h after being added dropwise to complete obtain modifier, above-mentioned ring
Oxygen resin, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:
1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, above-mentioned elastomer is added
Weight be 15% of modifier weight obtained by step (1), the additional amount of above-mentioned tetrabutylammonium chloride is modified obtained by step (1)
The 1% of object weight is heated to 110 DEG C after tetrabutylammonium chloride melts completely, react 2h to get.
Further, the step (2) elastomer is made by following components and its parts by weight:
10-13 parts of methyl methacrylate, 3-5 parts of butyl acrylate, 0.5-1 parts of acrylic acid, azodiisobutyronitrile 0.2-
0.5 part, 0.8-1.5 parts of thioacetic acid, 40-45 parts of n-butanol.
Further, the step (2) elastomer is made by following components and its parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azodiisobutyronitrile, sulfydryl second
1.2 parts, 42 parts of n-butanol of acid.
Further, the method for producing elastomers are as follows:
(a) methyl methacrylate, butyl acrylate, acrylic acid and azodiisobutyronitrile are uniformly mixed, obtain mixture；
(b) n-butanol is added into the four-necked bottle equipped with blender, condenser pipe, thermometer and dropping funel, sulfydryl is added
Mixture obtained by the step of acetic acid and 1/2 amount (a), is warming up to reflux temperature, after 30min, is continuously added dropwise and is remained with dropping funel
Mixture obtained by the step of surplus (a), time for adding 2h, after being added dropwise, 120 DEG C of insulation reaction 1.5h obtain mixed system；
(c) by the vacuum distillation of mixed system obtained by step (b) with remove solvent and unreacted monomer to get.
Further, the organic matter modification micaceous iron oxide is made by following components and its parts by weight:
12-15 parts of micaceous iron oxide, 0.5-1 parts of nano zine oxide, 1.8-3.5 parts of oleic acid, oleic acid diethyl amide 0.5-1
Part, 0.4-0.6 parts of dimethyl silicone polymer, 0.4-0.7 parts of neopelex, 40-50 parts of dehydrated alcohol.
Further, the organic matter modification micaceous iron oxide is made by following components and its parts by weight:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethyl amide, poly dimethyl
0.5 part of siloxanes, 0.6 part of neopelex, 46 parts of dehydrated alcohol.
Further, organic matter modification micaceous iron oxide the preparation method comprises the following steps:
(I) nano zine oxide is taken, oleic acid, oleic acid diethyl amide and dehydrated alcohol, the additional amount of dehydrated alcohol, which is added, is
8 times of above-mentioned nano zine oxide weight are 60 DEG C, ultrasonic power 100W in temperature, and supersonic frequency is ultrasonic reaction under 60Hz
25min obtains slurry；
(II) neopelex is taken, dehydrated alcohol is added, makes neopelex in dehydrated alcohol
Mass concentration is 6%, obtains alcoholic solution；
(III) micaceous iron oxide is taken, the dehydrated alcohol of slurry obtained by step (I) and surplus, ultrasound, ultrasonic function is added
Rate is 100W, supersonic frequency 50Hz, ultrasonic time 6min, and 20min is then stirred in 55 DEG C of waters bath with thermostatic control, is added poly- two
Methylsiloxane stirs evenly, and alcoholic solution obtained by step (II) is added, and constant temperature is stirred to react 1.5h, is filtered by vacuum, obtained solid
Be placed in a vacuum drying oven in 60 DEG C of dry 12h, crush to get.
Further, the silicone-modified nano mica powder of the activation the preparation method comprises the following steps:
1. nano mica powder is added in dehydrated alcohol, make mass concentration of the nano mica powder in dehydrated alcohol
20%, ultrasonic disperse is uniform, ultrasonic power 100W, supersonic frequency 60Hz, and ultrasonic time is that 15min obtains slurry；
2. taking activation siloxy group coupling agent, the amount of above-mentioned activation siloxy group coupling agent is the step 1. nanometer
The ethanol water that volume fraction is 95% is added in the 12% of mica powder weight, makes to activate siloxy group coupling agent in solution
Mass fraction be 20%, be 5 with the pH of second acid-conditioning solution, stir 40min, obtain hydrolyzate；
3. by step, 1. gained slurry is heated to 80 DEG C, and step 2. gained hydrolyzate, reaction time 1.5h, reaction is added
Product through suction filtration, washing, drying, grinding to get.
Further, the dispersing agent is by high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-
3050 form by weight 6-8:1-3.
Further, the dispersing agent is by high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-
3050 form by weight 7:2.
Further, the organoclay is organobentonite.
In addition, the present invention also provides the preparation methods of the very-high performance epoxy primer, comprising the following steps:
After S1 successively puts into the Modified Epoxy Resin by Elastomers of formula ratio, dimethylbenzene, butanol, dispersing agent, with 300-600r/
The speed of min stirs 5-10min, obtains mixture A, and the activation siloxy group coupling of formula ratio is added into said mixture A
Agent stirs 5-10min with the speed of 300-600r/min, obtains mixture B, sequentially add formula ratio into said mixture B
Zinc molybdate modified pigment, organic matter modification micaceous iron oxide, superfine talcum powder, surpasses the silicone-modified nano mica powder of activation
Thin barium sulfate, titanium dioxide, organoclay, carbon black, under the revolving speed of 900-1200r/min, being sanded to fineness is 35 μm hereinafter, temperature
60 DEG C hereinafter, flow 10-15L/min, obtains component A；
S2 mixes the dimethylbenzene of formula ratio and isopropanol, and under the revolving speed of 300-600r/min, changing for formula ratio is added
Property fatty amine, Epoxy curing accelerators K54, later under the revolving speed of 600-900r/min, stir 20min, obtain B component；
S3 by B component obtained by component A obtained by step S1 and step S2 be uniformly mixed to get.
The present invention uses polymethyl hydrogen siloxane to be modified epoxy resin first, so that living in polymethyl hydrogen siloxane
Bold and vigorous active group is reacted with the hydroxyl in epoxy resin under the effect of the catalyst, and modifier is made, then again with elasticity
Body is twice-modified to modifier progress, so that the carboxyl in elastomer carries out reacting elasticity obtained with the epoxy group in modifier
Modifies epoxy resin while greatly improving the crosslink density of system, can also hinder absorption of the paint film to cation, can not only
Enough enhance the corrosion resistance of paint film, additionally it is possible to improve the water resistance of paint film obtained, and the salt tolerant of paint film can be further enhanced
Mist.At the same time, additionally it is possible to enhance the stability, toughness and shock resistance of paint film.
The oleic acid diethyl amide being added in organic matter modification micaceous iron oxide preparation of the present invention can not only improve nanometer
The dispersion performance of zinc oxide keeps nano zine oxide evenly dispersed, more fully participates in reaction, enhances it in coating system
Stability, additionally it is possible to enhance the Adhesion property of product, improve adhesive force, ageing-resistant performance and corrosion resistance.
The elasticity that will be prepared by methyl methacrylate, butyl acrylate, acrylic acid, thioacetic acid etc. in the present invention
Body is used to prepare Modified Epoxy Resin by Elastomers, can enhance adhesive force, the flexibility of paint film, keep film-formation result more preferable, simultaneously
With performances such as good water resistance, oil resistivity and solvent resistances.
Very-high performance epoxy primer provided by the invention is by Modified Epoxy Resin by Elastomers, zinc molybdate modified pigment, activity
The siloxane modified nano mica powder of SiClx, organic matter modification micaceous iron oxide etc. are prepared.Very-high performance ring provided by the invention
Oxygen priming paint has excellent anti-rust and corrosionproperties, water-fast, salt spray resistance；It is dry quick, there is good workability；Film
Even compact；Good mechanical stability；Also there is excellent adhesive force and ageing-resistant performance.
Compared with prior art, present invention has the advantage that
(1) very-high performance epoxy primer provided by the invention has superelevation patience, and salt spray resistance is (dry up to 1000 hours or more
40-50 μm of film), and drawing lattice to survey adhesive force is 0-1 grades；And the existing epoxy primer salt spray resistance in market was in 700 hours (dry film 40-
50 μm), it draws lattice and surveys adhesive force >=2 grade.
(2) very-high performance epoxy primer provided by the invention can polish after spraying at room temperature 12 hours, and not scab is beaten
Poly-putty base can be scraped after mill, without generating lifting phenomenon.
(3) very-high performance epoxy primer provided by the invention has excellent water resistance, water-fast 30 days or more, draws lattice and surveys
Adhesive force is 0-1 grades.
(4) present invention makees curing agent using modified fatty amine, and modified fatty amine has excellent adhesive force and corrosion resistance
Energy；Epoxy resin used spells flexible resin, is modified, is greatly improved adhesive force.
Specific embodiment
The following describes the present invention further through the description of specific embodiments, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention can make various modifications or improvements, but without departing from this
The basic thought of invention, is all within the scope of the present invention.
In the present invention, superfine talcum powder is purchased from Guang Yuan Ultramicro-powder Co., Ltd of Jiangyin City, 5000 mesh of specification；Ultra-fine sulfuric acid
Barium is purchased from Yuan Lei powder Co., Ltd of Foshan City, 1000 mesh of specification；Carbon black is purchased from the limited public affairs of the green sharp industry development of sea cowry
Department, brand: Cabot, model: M800；Epoxy resin is purchased from Guangzhou Kui Bang Chemical Co., Ltd., the trade mark: E-128, goods
Number: 0002516；Titanium dioxide is purchased from Dongguan City Wo Hai trade Co., Ltd, model: R-996；High molecular weight polyurethane dispersing agent
EFKA-4010 is purchased from the color Chemical Co., Ltd. in Kunshan thousand, model: EFKA-4010；Moist type dispersing agent C T-3050 is purchased from
Jinan Changtai Chemical Co., Ltd., model: CT-3050；Zinc molybdate modified pigment is purchased from Zhengzhou China and steps the limited public affairs of chemical products
Department, article No.: 20180226；Polymethyl hydrogen siloxane is purchased from Wuhan far at creating Science and Technology Ltd., article No.: 46305；Nanometer
Zinc oxide is purchased from Guangzhou Wei Xi Chemical Co., Ltd., model: aktiv, brand: LANXESS；Nano mica powder is purchased from Lingshou
De Zhou mineral products processing factory of county, article No.: 081425；Organobentonite is purchased from Lingshou County Li Hua mineral products processing factory, specification 200
Mesh；Activation siloxy group coupling agent is purchased from Guangzhou dawn coupling agent Co., Ltd, model: SI-69；Modified fatty amine is commercially available
From Jining Bai Chuan Chemical Co., Ltd., the trade mark: NP-3100, article No.: 101；Epoxy curing accelerators K54 is purchased from Shanghai and is full of admittedly
Chemical Co., Ltd., model: K54.
Embodiment 1, a kind of very-high performance epoxy primer
The very-high performance epoxy primer is made of component A and B component, wherein the component A is by following component and its again
Number is measured to form: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, active SiClx oxygen
1.5 parts of alkyl coupling agent, 12 parts of zinc molybdate modified pigment, activate 11 parts of silicone-modified nano mica powder, organic matter modification
10 parts of micaceous iron oxide, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, 0.2 part of carbon black；
The dispersing agent is by high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 7:2 group
At；The organoclay is organobentonite；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54
1.2 parts, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to and are leaked equipped with blender, condenser pipe, thermometer and dropping liquid
In the four-necked bottle of bucket, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C,
Even dropwise addition dibutyl tin dilaurate, time for adding 30min, the reaction was continued 1.5h after being added dropwise to complete obtain modifier, above-mentioned ring
Oxygen resin, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:
1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, above-mentioned elastomer is added
Weight be 15% of modifier weight obtained by step (1), the additional amount of above-mentioned tetrabutylammonium chloride is modified obtained by step (1)
The 1% of object weight is heated to 110 DEG C after tetrabutylammonium chloride melts completely, react 2h to get.
Elastomer described in the preparation method step (2) of the Modified Epoxy Resin by Elastomers is by following components and its weight
Number is made:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azodiisobutyronitrile, sulfydryl second
1.2 parts, 42 parts of n-butanol of acid.
The method for producing elastomers are as follows:
(a) methyl methacrylate, butyl acrylate, acrylic acid and azodiisobutyronitrile are uniformly mixed, obtain mixture；
(b) n-butanol is added into the four-necked bottle equipped with blender, condenser pipe, thermometer and dropping funel, sulfydryl is added
Mixture obtained by the step of acetic acid and 1/2 amount (a), is warming up to reflux temperature, after 30min, is continuously added dropwise and is remained with dropping funel
Mixture obtained by the step of surplus (a), time for adding 2h, after being added dropwise, 120 DEG C of insulation reaction 1.5h obtain mixed system；
(c) by the vacuum distillation of mixed system obtained by step (b) with remove solvent and unreacted monomer to get.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethyl amide, poly dimethyl
0.5 part of siloxanes, 0.6 part of neopelex, 46 parts of dehydrated alcohol.
Organic matter modification micaceous iron oxide the preparation method comprises the following steps:
(I) nano zine oxide is taken, oleic acid, oleic acid diethyl amide and dehydrated alcohol, the additional amount of dehydrated alcohol, which is added, is
8 times of above-mentioned nano zine oxide weight are 60 DEG C, ultrasonic power 100W in temperature, and supersonic frequency is ultrasonic reaction under 60Hz
25min obtains slurry；
(II) neopelex is taken, dehydrated alcohol is added, makes neopelex in dehydrated alcohol
Mass concentration is 6%, obtains alcoholic solution；
(III) micaceous iron oxide is taken, the dehydrated alcohol of slurry obtained by step (I) and surplus, ultrasound, ultrasonic function is added
Rate is 100W, supersonic frequency 50Hz, ultrasonic time 6min, and 20min is then stirred in 55 DEG C of waters bath with thermostatic control, is added poly- two
Methylsiloxane stirs evenly, and alcoholic solution obtained by step (II) is added, and constant temperature is stirred to react 1.5h, is filtered by vacuum, obtained solid
Be placed in a vacuum drying oven in 60 DEG C of dry 12h, crush to get.
The silicone-modified nano mica powder of the activation the preparation method comprises the following steps:
1. nano mica powder is added in dehydrated alcohol, make mass concentration of the nano mica powder in dehydrated alcohol
20%, ultrasonic disperse is uniform, ultrasonic power 100W, supersonic frequency 60Hz, and ultrasonic time is that 15min obtains slurry；
2. taking activation siloxy group coupling agent, the amount of above-mentioned activation siloxy group coupling agent is the step 1. nanometer
The ethanol water that volume fraction is 95% is added in the 12% of mica powder weight, makes to activate siloxy group coupling agent in solution
Mass fraction be 20%, be 5 with the pH of second acid-conditioning solution, stir 40min, obtain hydrolyzate；
3. by step, 1. gained slurry is heated to 80 DEG C, and step 2. gained hydrolyzate, reaction time 1.5h, reaction is added
Product through suction filtration, washing, drying, grinding to get.
The preparation method of the very-high performance epoxy primer, comprising the following steps:
After S1 successively puts into the Modified Epoxy Resin by Elastomers of formula ratio, dimethylbenzene, butanol, dispersing agent, with 500r/min
Speed stir 7min, obtain mixture A, into said mixture A be added formula ratio activation siloxy group coupling agent, with
The speed of 500r/min stirs 7min, obtains mixture B, the molybdic acid zinc modification face of formula ratio is sequentially added into said mixture B
Expect, activate silicone-modified nano mica powder, organic matter modification micaceous iron oxide, superfine talcum powder, ultra-fine barium sulfate, titanium white
Powder, organoclay, carbon black, under the revolving speed of 1100r/min, being sanded to fineness is 35 μm hereinafter, temperature 60 C is hereinafter, flow 13L/
Min obtains component A；
S2 mixes the dimethylbenzene of formula ratio and isopropanol, and under the revolving speed of 400r/min, the modification rouge of formula ratio is added
Fat amine, Epoxy curing accelerators K54 stir 20min, obtain B component later under the revolving speed of 400r/min；
S3 by B component obtained by component A obtained by step S1 and step S2 be uniformly mixed to get.
Embodiment 2, a kind of very-high performance epoxy primer
The very-high performance epoxy primer is made of component A and B component, wherein the component A is by following component and its again
It measures number composition: 15 parts of Modified Epoxy Resin by Elastomers, 5 parts of dimethylbenzene, 5 parts of butanol, 0.1 part of dispersing agent, activating siloxanes
1 part of base coupling agent, 5 parts of zinc molybdate modified pigment, 3 parts of silicone-modified nano mica powder is activated, organic matter modifies mica oxygen
Change 5 parts of iron, 5 parts of superfine talcum powder, 3 parts of ultra-fine barium sulfate, 5 parts of titanium dioxide, 0.2 part of organoclay, 0.2 part of carbon black；The dispersion
Agent is made of high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 6:3；It is described to have
Machine soil is organobentonite.
The B component is made of following component and its parts by weight: 30 parts of modified fatty amine, Epoxy curing accelerators K54
1 part, 15 parts of dimethylbenzene, 10 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to and are leaked equipped with blender, condenser pipe, thermometer and dropping liquid
In the four-necked bottle of bucket, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C,
Even dropwise addition dibutyl tin dilaurate, time for adding 30min, the reaction was continued 1.5h after being added dropwise to complete obtain modifier, above-mentioned ring
Oxygen resin, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:
1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, above-mentioned elastomer is added
Weight be 15% of modifier weight obtained by step (1), the additional amount of above-mentioned tetrabutylammonium chloride is modified obtained by step (1)
The 1% of object weight is heated to 110 DEG C after tetrabutylammonium chloride melts completely, react 2h to get.
Elastomer described in the preparation method step (2) of the Modified Epoxy Resin by Elastomers is by following components and its weight
Number is made:
10 parts of methyl methacrylate, 3 parts of butyl acrylate, 0.5 part of acrylic acid, 0.2 part of azodiisobutyronitrile, sulfydryl second
0.8 part, 40 parts of n-butanol of acid.
The method for producing elastomers is similar to Example 1.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
12 parts of micaceous iron oxide, 0.5 part of nano zine oxide, 1.8 parts of oleic acid, 0.5 part of oleic acid diethyl amide, poly dimethyl
0.4 part of siloxanes, 0.4 part of neopelex, 40 parts of dehydrated alcohol.
The preparation method of the organic matter modification micaceous iron oxide is similar to Example 1.
The preparation method of the silicone-modified nano mica powder of activation is similar to Example 1.
The preparation method of the very-high performance epoxy primer, comprising the following steps:
After S1 successively puts into the Modified Epoxy Resin by Elastomers of formula ratio, dimethylbenzene, butanol, dispersing agent, with 300r/min
Speed stir 5min, obtain mixture A, into said mixture A be added formula ratio activation siloxy group coupling agent, with
The speed of 300r/min stirs 5min, obtains mixture B, the molybdic acid zinc modification face of formula ratio is sequentially added into said mixture B
Expect, activate silicone-modified nano mica powder, organic matter modification micaceous iron oxide, superfine talcum powder, ultra-fine barium sulfate, titanium white
Powder, organoclay, carbon black, under the revolving speed of 900r/min, being sanded to fineness is 35 μm hereinafter, temperature 60 C is hereinafter, flow 10L/
Min obtains component A；
S2 mixes the dimethylbenzene of formula ratio and isopropanol, and under the revolving speed of 300r/min, the modification rouge of formula ratio is added
Fat amine, Epoxy curing accelerators K54 stir 20min, obtain B component later under the revolving speed of 600r/min；
S3 by B component obtained by component A obtained by step S1 and step S2 be uniformly mixed to get.
Embodiment 3, a kind of very-high performance epoxy primer
The very-high performance epoxy primer is made of component A and B component, wherein the component A is by following component and its again
Number is measured to form: 30 parts of Modified Epoxy Resin by Elastomers, 10 parts of dimethylbenzene, 10 parts of butanol, 0.6 part of dispersing agent, active SiClx oxygen
3 parts of alkyl coupling agent, 15 parts of zinc molybdate modified pigment, 12 parts of silicone-modified nano mica powder is activated, organic matter modifies cloud
15 parts of female iron oxide, 15 parts of superfine talcum powder, 12 parts of ultra-fine barium sulfate, 15 parts of titanium dioxide, 0.8 part of organoclay, 0.5 part of carbon black；
The dispersing agent is by high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 8:1 group
At；The organoclay is organobentonite.
The B component is made of following component and its parts by weight: 60 parts of modified fatty amine, Epoxy curing accelerators K54
3 parts, 30 parts of dimethylbenzene, 20 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to and are leaked equipped with blender, condenser pipe, thermometer and dropping liquid
In the four-necked bottle of bucket, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C,
Even dropwise addition dibutyl tin dilaurate, time for adding 30min, the reaction was continued 1.5h after being added dropwise to complete obtain modifier, above-mentioned ring
Oxygen resin, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:
1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, above-mentioned elastomer is added
Weight be 15% of modifier weight obtained by step (1), the additional amount of above-mentioned tetrabutylammonium chloride is modified obtained by step (1)
The 1% of object weight is heated to 110 DEG C after tetrabutylammonium chloride melts completely, react 2h to get.
Elastomer described in the preparation method step (2) of the Modified Epoxy Resin by Elastomers is by following components and its weight
Number is made:
13 parts of methyl methacrylate, 5 parts of butyl acrylate, 1 part of acrylic acid, 0.5 part of azodiisobutyronitrile, thioacetic acid
1.5 parts, 45 parts of n-butanol.
The method for producing elastomers is similar to Example 1.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
15 parts of micaceous iron oxide, 1 part of nano zine oxide, 3.5 parts of oleic acid, 1 part of oleic acid diethyl amide, polydimethylsiloxanes
0.6 part of alkane, 0.7 part of neopelex, 50 parts of dehydrated alcohol.
The preparation method of the organic matter modification micaceous iron oxide is similar to Example 1.
The preparation method of the silicone-modified nano mica powder of activation is similar to Example 1.
The preparation method of the very-high performance epoxy primer, comprising the following steps:
After S1 successively puts into the Modified Epoxy Resin by Elastomers of formula ratio, dimethylbenzene, butanol, dispersing agent, with 600r/min
Speed stir 10min, obtain mixture A, into said mixture A be added formula ratio activation siloxy group coupling agent, with
The speed of 600r/min stirs 10min, obtains mixture B, the molybdic acid zinc modification face of formula ratio is sequentially added into said mixture B
Expect, activate silicone-modified nano mica powder, organic matter modification micaceous iron oxide, superfine talcum powder, ultra-fine barium sulfate, titanium white
Powder, organoclay, carbon black, under the revolving speed of 1200r/min, being sanded to fineness is 35 μm hereinafter, temperature 60 C is hereinafter, flow 15L/
Min obtains component A；
S2 mixes the dimethylbenzene of formula ratio and isopropanol, and under the revolving speed of 600r/min, the modification rouge of formula ratio is added
Fat amine, Epoxy curing accelerators K54 stir 20min, obtain B component later under the revolving speed of 900r/min；
S3 by B component obtained by component A obtained by step S1 and step S2 be uniformly mixed to get.
Comparative example 1, a kind of epoxy primer
The epoxy primer is made of component A and B component, wherein the component A is by following component and its parts by weight array
At: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, activation siloxy group coupling
1.5 parts of agent, 12 parts of zinc molybdate modified pigment, 11 parts of silicone-modified nano mica powder is activated, organic matter modifies mica oxidation
10 parts of iron, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, 0.2 part of carbon black；The dispersion
Agent is made of high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 7:2；It is described to have
Machine soil is organobentonite；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54
1.2 parts, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
Epoxy resin is heated to 90 DEG C, elastomer and tetrabutylammonium chloride is added, the weight of above-mentioned elastomer is epoxy
The 15% of weight resin, the additional amount of above-mentioned tetrabutylammonium chloride is the 1% of weight epoxy, complete to tetrabutylammonium chloride
After thawing, be heated to 110 DEG C, react 2h to get.
The elastomer is made by following components and its parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azodiisobutyronitrile, sulfydryl second
1.2 parts, 42 parts of n-butanol of acid.
The method for producing elastomers is similar to Example 1.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethyl amide, poly dimethyl
0.5 part of siloxanes, 0.6 part of neopelex, 46 parts of dehydrated alcohol.
The preparation method of the organic matter modification micaceous iron oxide is similar to Example 1.
The preparation method of the silicone-modified nano mica powder of activation is similar to Example 1.
The preparation method of the very-high performance epoxy primer is similar to Example 1.
The difference from embodiment 1 is that epoxy resin is only modified primary.
Comparative example 2, a kind of epoxy primer
The epoxy primer is made of component A and B component, wherein the component A is by following component and its parts by weight array
At: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, activation siloxy group coupling
1.5 parts of agent, 12 parts of zinc molybdate modified pigment, 11 parts of silicone-modified nano mica powder is activated, organic matter modifies mica oxidation
10 parts of iron, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, 0.2 part of carbon black；The dispersion
Agent is made of high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 7:2；It is described to have
Machine soil is organobentonite；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54
1.2 parts, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The preparation method of the Modified Epoxy Resin by Elastomers is similar to Example 1.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.8 parts of oleic acid, 0.5 part of dimethyl silicone polymer, dodecyl
0.6 part of benzene sulfonic acid sodium salt, 46 parts of dehydrated alcohol.
The preparation method of the organic matter modification micaceous iron oxide is similar to Example 1.
The preparation method of the silicone-modified nano mica powder of activation is similar to Example 1.
The preparation method of the very-high performance epoxy primer is similar to Example 1.
The difference from embodiment 1 is that being not added with oleic acid diethyl amide in the organic matter modification micaceous iron oxide, increase
The parts by weight of oiling acid.
Comparative example 3, a kind of epoxy primer
The epoxy primer is made of component A and B component, wherein the component A is by following component and its parts by weight array
At: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, activation siloxy group coupling
1.5 parts of agent, 12 parts of zinc molybdate modified pigment, 11 parts of silicone-modified nano mica powder is activated, organic matter modifies mica oxidation
10 parts of iron, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, 0.2 part of carbon black；The dispersion
Agent is made of high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 7:2；It is described to have
Machine soil is organobentonite；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54
1.2 parts, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to and are leaked equipped with blender, condenser pipe, thermometer and dropping liquid
In the four-necked bottle of bucket, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C,
Even dropwise addition dibutyl tin dilaurate, time for adding 30min, the reaction was continued 1.5h after being added dropwise to complete obtain modifier, above-mentioned ring
Oxygen resin, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:
1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, above-mentioned elastomer is added
Weight be 15% of modifier weight obtained by step (1), the additional amount of above-mentioned tetrabutylammonium chloride is modified obtained by step (1)
The 1% of object weight is heated to 110 DEG C after tetrabutylammonium chloride melts completely, react 2h to get.
Elastomer described in the preparation method step (2) of the Modified Epoxy Resin by Elastomers is by following components and its weight
Number is made:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azodiisobutyronitrile, sulfydryl second
1.2 parts of alcohol, 42 parts of n-butanol.
The method for producing elastomers is similar to Example 1.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethyl amide, poly dimethyl
0.5 part of siloxanes, 0.6 part of neopelex, 46 parts of dehydrated alcohol.
The preparation method of the organic matter modification micaceous iron oxide is similar to Example 1.
The preparation method of the silicone-modified nano mica powder of activation is similar to Example 1.
The preparation method of the very-high performance epoxy primer is similar to Example 1.
The difference from embodiment 1 is that thioacetic acid is replaced with mercaptoethanol in the elastomer.
Comparative example 4, a kind of epoxy primer
The epoxy primer is made of component A and B component, wherein the component A is by following component and its parts by weight array
At: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, activation siloxy group coupling
1.5 parts of agent, 12 parts of zinc molybdate modified pigment, 11 parts of silicone-modified nano mica powder is activated, organic matter modifies mica oxidation
10 parts of iron, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, 0.2 part of carbon black；The dispersion
Agent is made of high molecular weight polyurethane dispersing agent EFKA-4010 and moist type dispersing agent C T-3050 by weight 7:2；It is described to have
Machine soil is organobentonite；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54
1.2 parts, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
The Modified Epoxy Resin by Elastomers the preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to and are leaked equipped with blender, condenser pipe, thermometer and dropping liquid
In the four-necked bottle of bucket, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C,
Even dropwise addition dibutyl tin dilaurate, time for adding 30min, the reaction was continued 1.5h after being added dropwise to complete obtain modifier, above-mentioned ring
Oxygen resin, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:
1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, above-mentioned elastomer is added
Weight be 15% of modifier weight obtained by step (1), the additional amount of above-mentioned tetrabutylammonium chloride is modified obtained by step (1)
The 1% of object weight is heated to 110 DEG C after tetrabutylammonium chloride melts completely, react 2h to get.
The step (2) elastomer is made by following components and its parts by weight:
5.6 parts of methyl methacrylate, 5.6 parts of butyl acrylate, 5.6 parts of acrylic acid, 0.4 part of azodiisobutyronitrile, mercapto
1.2 parts of guanidine-acetic acid, 42 parts of n-butanol.
The method for producing elastomers is similar to Example 1.
The organic matter modification micaceous iron oxide is made by following components and its parts by weight:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethyl amide, poly dimethyl
0.5 part of siloxanes, 0.6 part of neopelex, 46 parts of dehydrated alcohol.
The preparation method of the organic matter modification micaceous iron oxide is similar to Example 1.
The preparation method of the silicone-modified nano mica powder of activation is similar to Example 1.
The preparation method of the very-high performance epoxy primer is similar to Example 1.
The difference from embodiment 1 is that the mass fraction of methyl methacrylate is modified by 12 parts in the elastomer
It is 5.6 parts, the mass fraction of butyl acrylate is revised as 5.6 parts by 4 parts, the mass fraction of acrylic acid is modified by 0.8 part
It is 5.6 parts.
Test example one, performance test
1, test material: embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 are made
The epoxy primer obtained.
2, it test method: is tested referring to water resistance, salt fog resistance of the relevant criterion to epoxy primer.
3, test result: test result such as table 1 shows.
Table 1: the performance test results
By table 1, it can be concluded that, the salt spray corrosion resistance of epoxy primer produced by the present invention is excellent, and water resistance is strong, wherein
Made from embodiment 3 after epoxy primer resisting salt fog corrosion 1000 hours, adhesive force is to carry out water resistance test 30 at 0 grade, 40 DEG C
After it, measurement adhesive force is 0 grade, and the salt spray corrosion resistance and water resistance of embodiment 3 are best, is best implementation of the invention
Example；Compared with comparative example 1-4, the performance of epoxy primer produced by the present invention is more preferable.
Test example two, adhesive force test
1, test material: embodiment 1, embodiment 2, embodiment 3, comparative example 2, comparative example 3, epoxy made from comparative example 4
Priming paint.
2, test method: blade coating poly-putty base (2mm thickness) doubling assessment adhesive force (1 preferably, and 5 is worst) after 30 minutes is surveyed
Examination and poly-putty base adhesive force.Referring to GB/T 9286 to have priming paint zine plate, steel plate, aluminium sheet adhesive force (ground is not polished) into
Row test.
3, test result: test result is as shown in table 2, table 3.
Table 2: with poly-putty base adhesive force test result
By table 2, it can be concluded that, very-high performance epoxy primer and poly-putty base adhesive force produced by the present invention are excellent.With comparative example
2-4 is compared, and embodiment 3 and the adhesive force of poly-putty base are stronger.
Table 3: to the adhesive force test result of zine plate, steel plate, aluminium sheet
By table 3, it can be concluded that, very-high performance epoxy primer produced by the present invention all has zine plate, steel plate, aluminium sheet relatively strong
Adhesive force, wherein the adhesive force of embodiment 3 is most strong, be preferred embodiment；Compared with comparative example 2-4, the present invention is real
The adhesive force for applying example 3 is stronger.
Claims (10)
1. a kind of very-high performance epoxy primer, which is characterized in that including component A and B component, wherein the component A is by such as the following group
Divide and its parts by weight form: 15-30 parts of Modified Epoxy Resin by Elastomers, 5-10 parts of dimethylbenzene, 5-10 parts of butanol, dispersing agent
0.1-0.6 parts, 1-3 parts of siloxy group coupling agent are activated, 5-15 parts of zinc molybdate modified pigment, activates silicone-modified nanometer
3-12 parts of mica powder, micaceous iron oxide 5-15 parts of organic matter modification, 5-15 parts of superfine talcum powder, 3-12 parts of ultra-fine barium sulfate, titanium
5-15 parts of white powder, 0.2-0.8 parts of organoclay, 0.2-0.5 parts of carbon black；
The B component is made of following component and its parts by weight: 30-60 parts of modified fatty amine, Epoxy curing accelerators K54
1-3 parts, 15-30 parts of dimethylbenzene, 10-20 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
2. very-high performance epoxy primer as described in claim 1, which is characterized in that the component A is by following component and its again
Number is measured to form: 20 parts of Modified Epoxy Resin by Elastomers, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, active SiClx oxygen
1.5 parts of alkyl coupling agent, 12 parts of zinc molybdate modified pigment, activate 11 parts of silicone-modified nano mica powder, organic matter modification
10 parts of micaceous iron oxide, 9 parts of superfine talcum powder, 4 parts of ultra-fine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organoclay, 0.2 part of carbon black；
The B component is made of following component and its parts by weight: 54 parts of modified fatty amine, Epoxy curing accelerators K54 1.2
Part, 26.8 parts of dimethylbenzene, 18 parts of isopropanol；
The weight proportion of the component A and B component is 5:1.
3. very-high performance epoxy primer as claimed in claim 1 or 2, which is characterized in that the Modified Epoxy Resin by Elastomers
The preparation method comprises the following steps:
(1) epoxy resin, cyclohexanone and butyl acetate are added to equipped with blender, condenser pipe, thermometer and dropping funel
In four-necked bottle, 70 DEG C are heated to, polymethyl hydrogen siloxane is added after epoxy resin melts completely, is warming up to 160 DEG C, is uniformly dripped
Add dibutyl tin dilaurate, time for adding 30min, the reaction was continued after being added dropwise to complete 1.5h obtain modifier, above-mentioned asphalt mixtures modified by epoxy resin
Rouge, cyclohexanone, butyl acetate, polymethyl hydrogen siloxane and dibutyl tin dilaurate weight ratio be 50:10:15:6:1；
(2) modifier obtained by step (1) is cooled to 90 DEG C, elastomer and tetrabutylammonium chloride, the weight of above-mentioned elastomer is added
Amount is 15% of modifier weight obtained by step (1), and the additional amount of above-mentioned tetrabutylammonium chloride is modifier weight obtained by step (1)
The 1% of amount is heated to 110 DEG C after tetrabutylammonium chloride melts completely, reaction 2h to get.
4. very-high performance epoxy primer as claimed in claim 3, which is characterized in that the step (2) elastomer by with
Lower component and its parts by weight are made:
10-13 parts of methyl methacrylate, 3-5 parts of butyl acrylate, 0.5-1 parts of acrylic acid, azodiisobutyronitrile 0.2-0.5
Part, 0.8-1.5 parts of thioacetic acid, 40-45 parts of n-butanol.
5. very-high performance epoxy primer as claimed in claim 4, which is characterized in that the elastomer is by following components and its again
Number is measured to be made:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azodiisobutyronitrile, thioacetic acid
1.2 parts, 42 parts of n-butanol.
6. very-high performance epoxy primer as claimed in claim 4, which is characterized in that the method for producing elastomers are as follows:
(a) methyl methacrylate, butyl acrylate, acrylic acid and azodiisobutyronitrile are uniformly mixed, obtain mixture；
(b) n-butanol is added into the four-necked bottle equipped with blender, condenser pipe, thermometer and dropping funel, thioacetic acid is added
And mixture obtained by the step of 1/2 amount (a), it is warming up to reflux temperature, after 30min, surplus is added dropwise continuously with dropping funel
The step of (a) obtained by mixture, time for adding 2h, after being added dropwise, 120 DEG C of insulation reaction 1.5h obtain mixed system；
(c) by the vacuum distillation of mixed system obtained by step (b) with remove solvent and unreacted monomer to get.
7. very-high performance epoxy primer as claimed in claim 1 or 2, which is characterized in that the organic matter modification mica oxidation
Iron is made by following components and its parts by weight:
12-15 parts of micaceous iron oxide, 0.5-1 parts of nano zine oxide, 1.8-3.5 parts of oleic acid, 0.5-1 parts of oleic acid diethyl amide,
0.4-0.6 parts of dimethyl silicone polymer, 0.4-0.7 parts of neopelex, 40-50 parts of dehydrated alcohol.
8. very-high performance epoxy primer as claimed in claim 7, which is characterized in that organic matter modification micaceous iron oxide by
Following components and its parts by weight are made:
13 parts of micaceous iron oxide, 0.6 part of nano zine oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethyl amide, polydimethylsiloxanes
0.5 part of alkane, 0.6 part of neopelex, 46 parts of dehydrated alcohol.
9. very-high performance epoxy primer as claimed in claim 7, which is characterized in that the organic matter modification micaceous iron oxide
The preparation method comprises the following steps:
(I) nano zine oxide is taken, oleic acid, oleic acid diethyl amide and dehydrated alcohol is added, the additional amount of dehydrated alcohol is above-mentioned
8 times of nano zine oxide weight are 60 DEG C, ultrasonic power 100W in temperature, and supersonic frequency is ultrasonic reaction under 60Hz
25min obtains slurry；
(II) neopelex is taken, dehydrated alcohol is added, makes quality of the neopelex in dehydrated alcohol
Concentration is 6%, obtains alcoholic solution；
(III) micaceous iron oxide is taken, the dehydrated alcohol of slurry obtained by step (I) and surplus, ultrasound is added, ultrasonic power is
Then 100W, supersonic frequency 50Hz, ultrasonic time 6min stir 20min in 55 DEG C of waters bath with thermostatic control, poly dimethyl is added
Siloxanes stirs evenly, and alcoholic solution obtained by step (II) is added, and constant temperature is stirred to react 1.5h, is filtered by vacuum, and obtained solid is placed in
In 60 DEG C of dry 12h in vacuum oven, crush to get.
10. as the described in any item very-high performance epoxy primers of claim 1-9 preparation method, which is characterized in that including with
Lower step:
After S1 successively puts into the Modified Epoxy Resin by Elastomers of formula ratio, dimethylbenzene, butanol, dispersing agent, with 300-600r/min
Speed stir 5-10min, obtain mixture A, into said mixture A be added formula ratio activation siloxy group coupling agent,
5-10min is stirred with the speed of 300-600r/min, mixture B is obtained, the molybdic acid of formula ratio is sequentially added into said mixture B
Zinc modification pigment, the silicone-modified nano mica powder of activation, organic matter modify micaceous iron oxide, superfine talcum powder, ultra-fine sulphur
Sour barium, titanium dioxide, organoclay, carbon black, under the revolving speed of 900-1200r/min, being sanded to fineness is 35 μm hereinafter, temperature 60 C
Hereinafter, flow 10-15L/min, obtains component A；
S2 mixes the dimethylbenzene of formula ratio and isopropanol, and under the revolving speed of 300-600r/min, the modification rouge of formula ratio is added
Fat amine, Epoxy curing accelerators K54 stir 20min, obtain B component later under the revolving speed of 600-900r/min；
S3 by B component obtained by component A obtained by step S1 and step S2 be uniformly mixed to get.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256941A (en) * | 2019-07-18 | 2019-09-20 | 江苏华云涂料有限公司 | A kind of epoxy high-performance thick-slurry type priming paint |
| CN112251108A (en) * | 2020-10-26 | 2021-01-22 | 衡阳拓创聚合新材料有限公司 | Solvent-free silicon modified elastic epoxy elastic floor coating |
| CN112358799A (en) * | 2020-11-09 | 2021-02-12 | 雅图高新材料股份有限公司 | Primer-topcoat polyurethane protective coating |
| CN112552466A (en) * | 2019-09-26 | 2021-03-26 | 雅图高新材料有限公司 | Self-drying water-based silicon modified acrylic emulsion for primer-topcoat coating, coating and preparation method |
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| CN109251661B (en) | 2020-07-14 |
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