CN106497318A - A kind of steel construction water-base epoxy anti-corrosion primer with highly-acidproof energy and preparation method thereof - Google Patents

A kind of steel construction water-base epoxy anti-corrosion primer with highly-acidproof energy and preparation method thereof Download PDF

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Publication number
CN106497318A
CN106497318A CN201610901145.8A CN201610901145A CN106497318A CN 106497318 A CN106497318 A CN 106497318A CN 201610901145 A CN201610901145 A CN 201610901145A CN 106497318 A CN106497318 A CN 106497318A
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attapulgite
parts
anacardol
water
modified
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CN201610901145.8A
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Chinese (zh)
Inventor
章阳
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ANHUI KINGYOUNG STRUCTURAL METAL WORK Co Ltd
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ANHUI KINGYOUNG STRUCTURAL METAL WORK Co Ltd
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Priority to CN201610901145.8A priority Critical patent/CN106497318A/en
Publication of CN106497318A publication Critical patent/CN106497318A/en
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • 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
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The present invention discloses a kind of steel construction water-base epoxy anti-corrosion primer with highly-acidproof energy, is made up of the raw material of following weight portion：Epoxy resin 50 70, anacardol 17 23, formalin 15 24, isophorone diamine 20 25, KH550 24, attapulgite 48,1mol/L hydrochloric acid solutions are appropriate, benzyltriethylammoinium chloride 0.8 1.5,30% sodium hydroxide solution 15 22, appropriate deionized water, stearmide 12, epoxide diluent 25, wax powder 12, mica powder 0.5 1, polyester resin 13.There is etherificate cross-linking reaction using the silicone hydroxyl in attapulgite's surface and anacardol herein, modified cashew pnenolic aldehyde amine hardener is prepared by chemical reaction again, modified firming agent has the advantages that general anacardol amide hardener, have attapulgite advantage concurrently, the epoxy coating of preparation have yellowing resistance preferably, low-temperature curable, acid-resistant anti-corrosion performance the characteristics of.

Description

A kind of steel construction water-base epoxy anti-corrosion primer and its preparation with highly-acidproof energy Method
Technical field
The invention belongs to paint field, more particularly to a kind of steel construction water-base epoxy anti-corrosion bottom with highly-acidproof energy Paint and preparation method thereof.
Background technology
Countries in the world coating industry steps up the research of the environment-friendly type coating to low VOC emission, water-based anticorrosive paint in recent years Greatly reduce and even completely eliminated VOC emission, and safe and convenient to use, to develop rapidly.Mono-component aqueous anticorrosive paint Using base material polymer emulsion mostly be the performances such as thermoplastics type, hardness of film, resistance to medium, anti-pollution and be difficult to reach solvent-borne type work Industry Coating levels.Thus people start the research for being devoted to bi-component waterborne anticorrosive paint in recent years.Bi-component aqueous epoxy is prevented Rotten coating can be strong with room temperature crosslinking curing, adhesive force, and high mechanical strength, chemical mediator-resitant property are good, and its performance can reach molten Formulation epoxy coating level, thus solvent type epoxy anticorrosive paint can be substituted, it is applied to anticorrosion of steel structure.
Polyamide-based curing agent can have good anti-corrosive properties with the ambient temperature curing film forming of epoxy resin, the paint film after solidification And pliability.But drying time is long, its maximum shortcoming is that low temperature curing properties are poor, and generally, temperature is less than 10 DEG C When cannot just carry out normal construction, and the winter temperature of China's most area is all below 5 DEG C, and large-scale steel structure exists substantially Outdoor construction, which limits its use in the winter time.
Zhao Keming, Wang Feidi, Qiu Qinghua et al. are at which《The synthesis of modified by cardanol amine epoxy terrace curing agent and performance Research》In one text, with natural products discarded object cashew nut shell extract anacardol as raw material, with formaldehyde and polyamine（Divinyl three Amine, triethylene tetramine, m-xylene diamine, IPD）Reaction, synthesizes amine system epoxide terrace curing agent, existing fatty amine Normal temperature rapid curing and excellent chemical-resistant, have the low toxicity of low molecular polyamides, good pliability again.But due to waist Phenolic hydroxyl group-OH in fruit phenol molecule is not involved in reacting, the phenolic hydroxyl group containing weak acid in modified curing agent so as to film easily quilt Aoxidize and alkali resistance is not good, easily absorb ultraviolet light, be copolymerized, the epoxy coating Yellowing especially severe of solidification.
Therefore, there is etherificate cross-linking reaction using the silicone hydroxyl in attapulgite's surface and anacardol herein, then by changing Learn reaction and prepare modified cashew pnenolic aldehyde amine hardener, modified firming agent had both had general anacardol amide hardener, and Have the advantage of attapulgite concurrently, form metastable curing system, hence it is evident that improve the color inhibition of epoxy resin cure film Performance.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of water-base epoxy anti-corrosion of steel construction with having highly-acidproof energy Priming paint and preparation method thereof, improves the anti-yellowing property of epoxy resin cure film.
A kind of steel construction water-base epoxy anti-corrosion primer with highly-acidproof energy, is made up of the raw material of following weight portion： Epoxy resin 50-70 parts, anacardol 17-23 parts, formalin 15-24 part, isophorone diamine 20-25 part, KH550 2-4 Part, attapulgite 4-8 parts, 1mol/L hydrochloric acid solutions are appropriate, and benzyltriethylammoinium chloride 0.8-1.5 parts, 30% NaOH are molten Liquid 15-22 parts, appropriate deionized water, stearmide 1-2 parts, epoxide diluent 2-5 parts, wax powder 1-2 part, mica powder 0.5-1 parts, Polyester resin 1-3 parts.
Comprise the following steps that：
（1）Attapulgite modified anacardol：
1., attapulgite is added in the aqueous solution of KH550, pH to 3-4 is adjusted with 1mol/L hydrochloric acid solutions, at stirring at normal temperature Reason 12-18 hours, are washed with deionized afterwards, and 1500-2500r/min is centrifuged, and vacuum drying is crushed, and crosses 100-200 mesh Sieve, standby；
2., the attapulgite after anacardol, benzyltriethylammoinium chloride and modification is added in reaction bulb, in 70-90 Under the conditions of DEG C, constant temperature stirring 3-5 hours, are cooled to 50-70 DEG C, add 30% sodium hydroxide solution, under conditions constant temperature stirring 2-4 hours, are cooled to room temperature, wash to neutrality, separate and concentrate, obtain attapulgite modified anacardol；
（2）The preparation of modified cashew pnenolic aldehyde amine hardener：
Will be equipped with electric mixer, the four-hole boiling flask of condenser pipe is placed in 30-50 DEG C of water bath with thermostatic control, add step（1）Prepare Attapulgite modified anacardol, is added dropwise IPD while stirring, adds formalin and stir, water-bath liter Warm 90-100 DEG C, isothermal reaction 2-4 hours are cooled to 60-75 DEG C, and control pressure carries out decompression steaming in 0.0085-0.0095MPa Evaporate, modification cashew pnenolic aldehyde amine hardener is obtained；
（3）Prepared by component A：
1., first by part steps（2）The modified cashew pnenolic aldehyde amine hardener that obtains is premixed with defoamer, water, add afterwards wax powder, Mica powder, is ground to fineness less than 20 μm through sand mill；
2., afterwards under stirring, remaining modified cashew pnenolic aldehyde amine hardener, stearmide, 15-30 point of stirring are added Clock, obtains final product component A；
（4）After epoxy resin, epoxide diluent and polyester resin are sufficiently mixed, stir and individually pack as component B.
Wherein, step（1）The concentration of aqueous solution of described KH550 is 5%.
Compared with prior art, the present invention has advantages below：
（1）The present invention processed using silane coupler after a large amount of silicone hydroxyl structures for containing of attapulgite, the phenol with anacardol There is etherificate cross-linking reaction in hydroxyl, substitute phenolic hydroxyl structure, so as to obtain the more preferable cashew nut phenol ether through reaction of anti-yellowing property, in modification On the basis of cashew pnenolic aldehyde amine hardener, develop a kind of novel epoxy coating, with yellowing resistance preferably, low-temperature curable and The characteristics of antiseptic property is excellent.
（2）In the present invention there is etherificate cross-linking reaction with the phenolic hydroxyl group of anacardol in modified attapulgite, contain simultaneously Hydrogen bond, then modification cashew pnenolic aldehyde amine hardener is obtained with isophorone diamine, formaldehyde reaction, both solid with general anacardol acid amides The advantage of agent, has the advantage of attapulgite again concurrently, hence it is evident that improve the crosslinking degree of modified firming agent, is formed metastable solid Change system, improves toughness, resistance to impact and the heat resistance of epoxy resin cure film.
（3）High acid-resistant oxygen anti-corrosion primer of the present invention, is a kind of two component epoxy priming paint, strong with object adhesive force, paint film Bright in color, acid-resistant anti-corrosion excellent performance can effectively improve the resistance to raindrop erosion of film for outdoor steel structure when building Performance, long service life is the priming paint of a class high comprehensive performance.
Specific embodiment
A kind of steel construction water-base epoxy anti-corrosion primer with highly-acidproof energy, by following weight portion（Kilogram）Raw material Composition：Epoxy resin 65, anacardol 19, formalin 21, isophorone diamine 23, KH550 3, attapulgite 7,1mol/L salt Appropriate acid solution, benzyltriethylammoinium chloride 1,30% sodium hydroxide solution 19, appropriate deionized water, stearmide 2, epoxy Diluent 3, wax powder 1.5, mica powder 0.8, polyester resin 2.
Comprise the following steps that：
（1）Attapulgite modified anacardol：
1., attapulgite is added in the aqueous solution of KH550, pH to 3.5 is adjusted with 1mol/L hydrochloric acid solutions, at stirring at normal temperature Reason 16 hours, is washed with deionized afterwards, and 2000r/min is centrifuged, and vacuum drying is crushed, and crosses 200 mesh sieves, standby；
2., the attapulgite after anacardol, benzyltriethylammoinium chloride and modification is added in reaction bulb, in 80 DEG C of bars Under part, constant temperature is stirred 4 hours, is cooled to 60 DEG C, adds 30% sodium hydroxide solution, and constant temperature is stirred 3 hours under conditions, cooling To room temperature, wash to neutrality, separate and concentrate, obtain attapulgite modified anacardol；
（2）The preparation of modified cashew pnenolic aldehyde amine hardener：
Will be equipped with electric mixer, the four-hole boiling flask of condenser pipe is placed in 40 DEG C of waters bath with thermostatic control, add step（1）Prepared is concavo-convex The modified anacardol of rod soil, is added dropwise IPD while stirring, adds formalin and stir, water-bath intensification 95 DEG C, isothermal reaction 3 hours is cooled to 70 DEG C, and control pressure carries out vacuum distillation in 0.0095MPa, and modification cashew pnenolic aldehyde is obtained Amine hardener；
（3）Prepared by component A：
1., first by part steps（2）The modified cashew pnenolic aldehyde amine hardener that obtains is premixed with defoamer, water, add afterwards wax powder, Mica powder, is ground to fineness less than 20 μm through sand mill；
2., afterwards under stirring, the remaining modified cashew pnenolic aldehyde amine hardener of addition, stearmide, stirring 25 minutes, i.e., Obtain component A；
（4）After epoxy resin, epoxide diluent and polyester resin are sufficiently mixed, stir and individually pack as component B.
Wherein, step（1）The concentration of aqueous solution of described KH550 is 5%.
The performance test results：
Adhesive force：1 grade；Pliability：2mm；Salt fog resistance/h：>500；Petrol-resistance：200h coatings are intact.

Claims (3)

1. a kind of steel construction with have highly-acidproof can water-base epoxy anti-corrosion primer, it is characterised in that by following weight portion Raw material is constituted：Epoxy resin 50-70 parts, anacardol 17-23 parts, formalin 15-24 part, isophorone diamine 20-25 part, KH550 2-4 parts, attapulgite 4-8 parts, 1mol/L hydrochloric acid solutions are appropriate, benzyltriethylammoinium chloride 0.8-1.5 parts, 30% Sodium hydroxide solution 15-22 parts, appropriate deionized water, stearmide 1-2 parts, epoxide diluent 2-5 parts, wax powder 1-2 part, mica Powder 0.5-1 parts, polyester resin 1-3 parts.
2. preparation of a kind of steel construction according to claims 1 with the water-base epoxy anti-corrosion primer with highly-acidproof energy Method, it is characterised in that comprise the following steps that：
（1）Attapulgite modified anacardol：
1., attapulgite is added in the aqueous solution of KH550, pH to 3-4 is adjusted with 1mol/L hydrochloric acid solutions, at stirring at normal temperature Reason 12-18 hours, are washed with deionized afterwards, and 1500-2500r/min is centrifuged, and vacuum drying is crushed, and crosses 100-200 mesh Sieve, standby；
2., the attapulgite after anacardol, benzyltriethylammoinium chloride and modification is added in reaction bulb, in 70-90 Under the conditions of DEG C, constant temperature stirring 3-5 hours, are cooled to 50-70 DEG C, add 30% sodium hydroxide solution, under conditions constant temperature stirring 2-4 hours, are cooled to room temperature, wash to neutrality, separate and concentrate, obtain attapulgite modified anacardol；
（2）The preparation of modified cashew pnenolic aldehyde amine hardener：
Will be equipped with electric mixer, the four-hole boiling flask of condenser pipe is placed in 30-50 DEG C of water bath with thermostatic control, add step（1）Prepare Attapulgite modified anacardol, is added dropwise IPD while stirring, adds formalin and stir, water-bath liter Warm 90-100 DEG C, isothermal reaction 2-4 hours are cooled to 60-75 DEG C, and control pressure carries out decompression steaming in 0.0085-0.0095MPa Evaporate, modification cashew pnenolic aldehyde amine hardener is obtained；
（3）Prepared by component A：
1., first by part steps（2）The modified cashew pnenolic aldehyde amine hardener that obtains is premixed with defoamer, water, add afterwards wax powder, Mica powder, is ground to fineness less than 20 μm through sand mill；
2., afterwards under stirring, remaining modified cashew pnenolic aldehyde amine hardener, stearmide, 15-30 point of stirring are added Clock, obtains final product component A；
（4）After epoxy resin, epoxide diluent and polyester resin are sufficiently mixed, stir and individually pack as component B.
3. preparation of a kind of steel construction according to claims 2 with the water-base epoxy anti-corrosion primer with highly-acidproof energy Method, it is characterised in that step（1）The concentration of aqueous solution of described KH550 is 5%.
CN201610901145.8A 2016-10-14 2016-10-14 A kind of steel construction water-base epoxy anti-corrosion primer with highly-acidproof energy and preparation method thereof Pending CN106497318A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001780A2 (en) * 1998-07-03 2000-01-13 Shell Internationale Research Maatschappij B.V. Waterborne epoxy resin coating compositions
CN1597812A (en) * 2004-08-20 2005-03-23 广州秀珀化工有限公司 Water epoxy paint for ground floor and its mfg. process and construction technology
CN101613112A (en) * 2009-07-06 2009-12-30 江南大学 A kind of preparation of attapulgite modified by silane coupling agent
CN103936021A (en) * 2014-04-04 2014-07-23 浙江工业大学 Method for preparing organobentonite with low viscosity and high settling resistance

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001780A2 (en) * 1998-07-03 2000-01-13 Shell Internationale Research Maatschappij B.V. Waterborne epoxy resin coating compositions
CN1597812A (en) * 2004-08-20 2005-03-23 广州秀珀化工有限公司 Water epoxy paint for ground floor and its mfg. process and construction technology
CN101613112A (en) * 2009-07-06 2009-12-30 江南大学 A kind of preparation of attapulgite modified by silane coupling agent
CN103936021A (en) * 2014-04-04 2014-07-23 浙江工业大学 Method for preparing organobentonite with low viscosity and high settling resistance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黄坤: "植物油基环氧热固单体的合成、固化与性能", 《《中国博士学位论文全文数据库工程科技I辑》 *

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Application publication date: 20170315