CN115322607A - Chlorinated polyester alloy heat-resistant anticorrosive paint and preparation process thereof - Google Patents

Chlorinated polyester alloy heat-resistant anticorrosive paint and preparation process thereof Download PDF

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CN115322607A
CN115322607A CN202211081204.3A CN202211081204A CN115322607A CN 115322607 A CN115322607 A CN 115322607A CN 202211081204 A CN202211081204 A CN 202211081204A CN 115322607 A CN115322607 A CN 115322607A
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chlorinated polyester
styrene
chlorinated
alloy heat
parts
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CN115322607B (en
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王保军
拾振洪
王家振
金传亮
李海洋
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Anhui Xindalu Special Paint Co ltd
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Anhui Xindalu Special Paint Co ltd
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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
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses a chlorinated polyester alloy heat-resistant anticorrosive coating and a preparation process thereof, belonging to the technical field of anticorrosive coatings. The two phases in the blend still maintain respective characteristics, the interface of the two phases is combined, styrene phases in styrene, polystyrene latex and SIS emulsion in chlorinated polyester form a similar curing system characteristic, SIS has an elastic chain segment, the toughness can be improved, the impact resistance of the coating is improved, the coating has excellent oxidation resistance to oxidizing medium environments such as acid and wet chlorine, chlorine-containing chemical media such as hydrochloric acid and chlorine can be resisted, the coating can be applied to production devices such as wet chlorine and chlorine water, chlorine dioxide bleaching devices, storage tanks for storing chemicals, pipelines and the like, and the coating is also suitable for steel structures in various environments such as ocean atmosphere, high temperature and the like, and long-acting corrosion prevention of ships, ocean platforms, oil pipelines and the like is realized.

Description

Chlorinated polyester alloy heat-resistant anticorrosive paint and preparation process thereof
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a chlorinated polyester alloy heat-resistant anticorrosive coating and a preparation process thereof.
Background
The water-based paint is a paint using water as a solvent or as a dispersion medium. It features no poison, no odour and rich resources, and can greatly reduce the pollution of volatile organic solvent in paint to atmosphere. And water is used as a solvent, so that the safety of the coating in the processes of storage, transportation and construction can be greatly improved. At present, the water-based anticorrosive paint is successfully applied to the fields of architectural decoration, automobile manufacturing, ship and container manufacturing and the like. The water paint is used to replace solvent paint for chemical industry anticorrosive coating. The corrosion resistance of the coating is relatively corrosion resistant under certain conditions, but may not be corrosion resistant under other conditions. The chlorine dried at normal temperature slightly corrodes common metals, and the wet chlorine has strong oxidation effect and can corrode a plurality of metal or nonmetal materials; stray currents from the electrolysis system tend to exacerbate chemical corrosion of the material; the strong corrosive substances such as wet chlorine gas and the like need to be made of special corrosion-resistant metal or nonmetal materials. For example H in chlorine-containing humid gases 2 S, chlorine, hydrogen chloride high-temperature water vapor and other media are corroded to prevent condensed waterPoint corrosion, stress corrosion, chemical corrosion and potential corrosion, complex components and special working conditions, and the coating has the advantages of good heat resistance, corrosion resistance and wear resistance adhesive force, severe corrosion of the used wall and strict requirement on the performance of the anticorrosive coating. There are many types of corrosion commonly seen in the chemical industry, and they can be classified into homogeneous corrosion and localized corrosion according to the corrosion morphology, wherein localized corrosion is more harmful. The main forms of local corrosion include pitting corrosion, crevice corrosion, galvanic corrosion, intergranular corrosion, stress corrosion cracking, corrosion fatigue, filiform corrosion, and the like. Chemical metals come into contact with many corrosive media, and the common corrosive media are: high-temperature sodium chloride solution, high-temperature wet chlorine, alkali liquor, high-temperature saturated chlorine and water vapor, aqua regia, sulfuric acid, nitric acid and the like. For example, high temperature wet chlorine gas hydrolyzes to form highly corrosive hydrochloric acid and highly oxidizing hypochlorous acid. Hypochlorous acid can be decomposed to release new oxygen. The chemical properties of these materials are very reactive and most metallic and non-metallic materials will suffer severe corrosion in such environments. However, the existing waterborne polyester, waterborne polyurethane, waterborne acrylate and waterborne epoxy paint are difficult to meet the high-performance anticorrosion requirement. For example, CN105694655A discloses an environment-friendly epoxy resin acid-resistant anticorrosive coating and a preparation method thereof, and the existing chlorinated polyether and fluorocarbon coatings with better corrosion resistance are influenced by the synthesis technology, performance, higher cost and other factors, and the application in the chemical industry coating field is very limited. For example, common fluorocarbon coatings generally contain a large amount of volatile organic solvents, and the volatile organic solvents can volatilize into the atmosphere after the coating is constructed, so that the coating defects are caused, the corrosion prevention requirements are difficult to meet, and the environment is polluted. A chlorinated polyester alloy heat-resistant anticorrosive paint and a preparation process thereof are provided by the technical personnel in the field to meet the existing performance requirements and application requirements.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for preparing a rust-free anticorrosive primer with high penetration conversion.
The chlorinated polyester is unsaturated polyester resin prepared by polycondensation of chlorendic anhydride serving as a main raw material, and the introduced chlorine endows the resin with excellent flame retardant property and outstanding oxidation resistance medium property, so that the chlorinated polyester has good heat resistance.
A chlorinated polyester alloy heat-resistant anticorrosive paint is obtained by uniformly mixing and thermally curing independently packaged paint slurry and independently packaged curing liquid in a weight ratio of 7: 3 to 5, and a production process of the chlorinated polyester alloy heat-resistant anticorrosive paint comprises the following steps: 1. preparing a chlorinated polyester microemulsion: adding chlorinated polyester into a stirring kettle, then adding triethanolamine accounting for 0.9 to 1.0 mass percent of the chlorinated polyester, stirring at a stirring speed of 2500 to 3000rpm, and slowly dripping water into the stirring kettle to form uniform chlorinated polyester microemulsion with the solid content of 40 to 45 percent;
the molecular chain of the unsaturated polyester resin contains lipophilic groups such as alkyl, aromatic rings and unsaturated double bonds, and also contains hydrophilic groups such as carboxyl hydroxyl ester groups and aldehyde-oxygen bonds, so that the unsaturated polyester resin has certain emulsifying capacity, when the unsaturated polyester resin is added into the unsaturated polyester resin, neutralization reaction is carried out to generate salt, the salt has good lipophilicity, and the other end of the unsaturated polyester resin is a strong hydrophilic group, so that the unsaturated polyester resin can play a good emulsifying role and can be well dispersed in water;
2. preparing a curing liquid: heating styrene-isoprene-styrene block copolymer latex to 65-70 ℃, slowly adding aminated graphene oxide, wherein the ratio of aminated graphene oxide to styrene-isoprene-styrene block copolymer latex is 23-25: 3, stirring for 2-3 min at the stirring speed of 15000-16000rpm, and obtaining styrene-isoprene-styrene block copolymer emulsion; 3. grinding and stirring: 45-50 parts of styrene-isoprene-styrene block copolymer emulsion, 1-2 parts of accelerator, 14-16 parts of filler and 5-7 parts of curing agent by weight, transferring the mixture into a three-roll grinding machine, heating to 75-85 ℃, and grinding for 5-10min to obtain a curing glue solution; 4. uniformly mixing the chlorinated polyester microemulsion with a dispersing agent, an antifoaming agent, a thickening agent and a film forming aid to obtain paint paste, wherein the chlorinated polyester microemulsion accounts for 60 to 65 wt%, the polystyrene latex accounts for 15 to 20 wt%, the thickening agent accounts for 3 to 5 wt%, the dispersing agent accounts for 5 to 7 wt%, and the balance is the film forming aid, and the total weight is 100%. Further wherein said thickener is SN636 or TT-935, HASE thickener such as SN636 from Nopco, TT-935 from Rohm & Haas.
The dispersant is BYK-1640 or H188A, and the film-forming aid is one of dipropylene glycol methyl ether, tripropylene glycol methyl ether or 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate.
The mixed etherified glycoluril resin is suitable for water system. The adhesive has good crosslinking activity for interlayer adhesion of different paint films, and improves the adhesive force of the paint films;
improve the waterproof performance and the scrubbing resistance. Further, the accelerator is YPS-2005 etherified glycoluril resin or diethylaniline, and the filler is barite powder or cast stone powder.
Further, the curing agent is a mixture of benzyltriethylammonium chloride, a vulcanizing agent FSH, cumene hydroperoxide and benzoyl peroxide in a weight ratio of 0.5: 1: 2.
EB series photo-curable acrylate resins such as UV7314, which are a photo-curable acrylate and not a chlorinated unsaturated polyester, are obtained by chlorination modification of polyester acrylate for paints and inks for metals and plastics.
Further, the chlorinated polyester is chlorinated unsaturated polyester with the chlorine content of 55-60%.
Further, the aminated graphene oxide is prepared by adding 1.8-2 parts of graphene oxide and 180-200 parts of distilled water into a reaction kettle, carrying out ultrasonic oscillation reaction for 0.5-1h, adding 1.5-2 parts of polyethyleneimine, continuing the ultrasonic oscillation reaction for 1h to obtain a uniformly dispersed system, and carrying out high-speed centrifugation to separate the aminated graphene oxide.
Further, the particle size of the polystyrene latex is 25 to 45nm.
The beneficial effects of the invention are:
the invention discloses a chlorinated polyester alloy heat-resistant anticorrosive coating, which is prepared by mixing SIS styrene-isoprene-styrene emulsion and chlorinated polyester together by an emulsion alloy method, so that the obtained blended material has the dual characteristics of an elastomer and thermosetting unsaturated polyester. The two phases in the blend still maintain respective characteristics, and the interfaces of the two phases form combination, so that the performances of the two phases are complementary to each other, and the polymer alloy is prepared. The styrene phase in the crosslinking monomer styrene, polystyrene latex and SIS emulsion in the chlorinated polyester form similar curing system characteristics, the oxidation resistance and heat resistance are improved after halogen is introduced into the chlorinated polyester molecules, and ester bonds with strong polarity are more stable than ether bonds and are protected by steric hindrance. The curing reaction can be completed at room temperature, and the unsaturated double bond in the molecule can be completely cross-linked after being initiated by the curing agent to fully react. The aminated graphene oxide contains amino, has good water dispersibility and has a promoting effect on the curing of the resin, the unsaturated polyester resin can form a microemulsion with water under the action of alkaline triethanolamine, and the microemulsion can form the water-containing unsaturated polyester resin after crosslinking. The SIS has an elastic chain segment, can improve the toughness of the chlorinated polyester, improves the impact resistance of the coating, partially forms a micro-phase structure in the unsaturated polyester resin, and simultaneously reacts a partial structure in a molecule when the unsaturated polyester is cured, so that the curing speed of the resin is delayed. The open bond reaction of the double bonds of the chlorinated polyester and the exothermic effect further initiate the cross-linking of the SIS component and the polystyrene latex. The independently subpackaged lacquer pulp and the independently subpackaged curing liquid are independently subpackaged, chlorinated polyester cannot contact curing agent components in the curing liquid and is stable due to independent subpackaging, the curing agent and SIS emulsion in the curing liquid can better disperse the curing agent and filler components on the premise of no heat release effect, the filler is inert and resistant to acid corrosion, the independently subpackaged lacquer pulp and the independently subpackaged curing liquid are used as a coating when being uniformly mixed, the operation is convenient, and the curing characteristic of the chlorinated polyester alloy heat-resistant anticorrosive coating is met.
Compared with the prior art, the invention has the following advantages:
in the past, media used in the production process of the chemical industry comprise strong acid, strong base, salt and the like, which have strong corrosivity on equipment and building materials, cause corrosion, serious even abandonment, influence the normal operation of safe production, and cause certain economic loss. For example, in a high-temperature chlorine-containing atmosphere, in addition to direct vapor phase corrosion, these metal chloride low-melting-point ash deposited salts undergo redox reaction with an oxide film on the metal surface layer to corrode the metal substrate, and general anticorrosive coatings have a short service life and are difficult to prevent corrosion. According to the chlorinated polyester alloy heat-resistant anticorrosive coating and the preparation process thereof disclosed by the invention, both the film-forming resin and the functional pigment and filler are inert materials, the coating has chemical corrosion resistance and self-leveling property, the coating is smooth and has smaller surface tension during film forming, knots can be effectively reduced, the construction process is simple and convenient, and the long-acting property of coating protection is determined by the anticorrosive property and good adhesive force of the coating. The paint has excellent oxidation resistance to oxidizing acid, wet chlorine and other oxidizing medium environments, especially chlorine-containing chemical medium, such as hydrochloric acid, hydrochloric acid vapor and the like, high temperature resistance, gas or vapor phase reaching 150 ℃, and good flame retardant property, is suitable for coating wet chlorine, chlorine water and other production devices in chemical industry, chlorine dioxide bleaching devices in pulp factories, pipelines for storing chemicals, chimneys, washing towers and other devices, and is also suitable for long-acting corrosion prevention of steel structures in various environments such as ocean atmosphere, high temperature and the like, such as ocean platforms, ships, containers, large steel components, oil pipelines and various chemical storage tank linings.
Detailed Description
The present invention is illustrated below by way of specific examples, which are not intended to be limiting.
Example 1
A chlorinated polyester alloy heat-resistant anticorrosive paint comprises the following steps: the first step, preparing chlorinated polyester microemulsion: adding Hetron197 chlorinated polyester into a stirring kettle, then adding triethanolamine accounting for 1.0 mass percent of the chlorinated polyester, stirring at a stirring speed of 3000rpm, and slowly dripping water into the stirring kettle to form uniform chlorinated polyester micro-emulsion with the solid content of 45%; step two, preparing a curing liquid: adding 100 parts by weight of cyclohexane solution of 30% by mass of Baling SIS1105 styrene-isoprene-styrene block copolymer into a reaction kettle, dropwise adding 18 parts by weight of mixed monomer of styrene, N-methylolacrylamide, methacrylic acid = 8: 3: 1 and 18 parts by weight of azodiisobutyramidine hydrochloride aqueous solution of 0.04wt%, carrying out SIS graft copolymerization reaction, controlling the temperature at 80 ℃ for 4 hours, adding 0.5 part by weight of hydroquinone, continuously stirring for 10 minutes, reducing the temperature to 60 ℃, adding 1 part by weight of compound emulsifier of OP-10 and hexadecyl trimethyl ammonium bromide = 8: 2, slowly dropwise adding deionized water under high-speed stirring to form emulsion, continuously stirring for 60 minutes at normal temperature, and filtering by a 400-mesh screen to obtain SIS styrene-isoprene-styrene block copolymer latex with the solid content of 42%. Heating styrene-isoprene-styrene block copolymer latex to 70 ℃, slowly adding aminated graphene oxide, wherein the weight ratio of the aminated graphene oxide to the styrene-isoprene-styrene block copolymer latex is 25: 3, the stirring time is 3min, the stirring speed is 16000rpm, obtaining styrene-isoprene-styrene block copolymer emulsion, adding 2 parts of graphene oxide and 200 parts of distilled water into a reaction kettle, carrying out ultrasonic oscillation reaction for 1h, adding 2 parts of polyethyleneimine, continuing the ultrasonic oscillation reaction for 1h, obtaining a uniformly dispersed system, and separating the aminated graphene oxide, the Baoqinlong graphene oxide GO-P001 and the polyethyleneimine Bairong chemical BRC-36 through high-speed centrifugation; step three, grinding and stirring: 50 parts of styrene-isoprene-styrene segmented copolymer emulsion, 2 parts of accelerator, 16 parts of filler and 7 parts of curing agent by weight, transferring the mixture into a three-roll grinder, heating to 85 ℃, grinding for 10min to obtain a cured glue solution, wherein the filler is Zhengzhou Zhongxing 800-mesh cast stone powder, and the curing agent is a mixture of benzyltriethylammonium chloride, a vulcanizing agent FSH, isopropylbenzene hydrogen peroxide and benzoyl peroxide in a weight ratio of 0.5: 1: 2; 4. uniformly mixing the chlorinated polyester microemulsion with a dispersing agent, a defoaming agent, a thickening agent and a film-forming aid to obtain the paint paste, wherein the chlorinated polyester microemulsion accounts for 65 wt%, the polystyrene latex accounts for 20 wt%, the thickening agent accounts for 5 wt%, the dispersing agent accounts for 7 wt%, and the rest is the film-forming aid and accounts for 100 wt%. The paint is prepared by uniformly mixing and thermally curing independently-packaged lacquer pulp and independently-packaged curing liquid in a weight ratio of 7: 5. When spraying, the spray gun is a gravity type coating spray gun, the caliber of the spray nozzle is preferably 5mm, the air pressure is preferably controlled to be 0.6Mpa, the distance between the spray nozzle and a spraying surface is 25cm, the spray nozzle is basically vertical to a base plane, and the moving direction of the spray gun is parallel to the surface of the base material.
Example 2
A chlorinated polyester alloy heat-resistant anticorrosive paint comprises the following steps: the first step, preparing chlorinated polyester microemulsion: adding Fochen 791H chlorinated polyester into a stirring kettle, then adding triethanolamine accounting for 0.95% of the mass fraction of the chlorinated polyester, stirring at the stirring speed of 2700rpm, and slowly dropwise adding water into the stirring kettle to form uniform chlorinated polyester microemulsion with the solid content of 47.5%; step two, preparing curing liquid: adding 100 parts by weight of cyclohexane solution of 27.5% by mass of Baling SIS1105 styrene-isoprene-styrene block copolymer into a reaction kettle, dropwise adding 15 parts by weight of mixed monomer of styrene, N-hydroxymethyl acrylamide, methacrylic acid = 7: 2: 1 and 15 parts by weight of azodiisobutyramidine hydrochloride aqueous solution of 0.04wt%, carrying out SIS graft copolymerization, controlling the temperature at 75-80 ℃ for 4 hours, adding 0.5 part by weight of hydroquinone, continuously stirring for 10 minutes, reducing the temperature to 60 ℃, adding 0.5 part by weight of compound emulsifier OP-10: hexadecyl trimethyl ammonium bromide = 8: 2, slowly dropwise adding deionized water under high-speed stirring to form emulsion, continuously stirring for 60 minutes at normal temperature, and filtering by using a 400-mesh screen to obtain SIS styrene-isoprene-styrene block copolymer latex with the solid content of 40%. Heating styrene-isoprene-styrene block copolymer latex to 67.5 ℃, slowly adding aminated graphene oxide, wherein the weight ratio of the aminated graphene oxide to the styrene-isoprene-styrene block copolymer latex is 2.5: 3, the stirring time is 2min, and the stirring speed is 15500rpm, so as to obtain styrene-isoprene-styrene block copolymer emulsion, wherein the aminated graphene oxide is prepared by adding 1.8 parts of graphene oxide and 190 parts of distilled water into a reaction kettle, carrying out ultrasonic oscillation reaction for 0.75h, then adding 1.5 parts of polyethyleneimine, continuing the ultrasonic oscillation reaction for 1h, so as to obtain a uniformly dispersed system, and separating the aminated graphene oxide, baoqinlong graphene oxide GO-P001 and polyethyleneimine Bairong chemical BRC-36 through high-speed centrifugation; step three, grinding and stirring: according to the weight parts, 47.5 parts of styrene-isoprene-styrene segmented copolymer emulsion, 1.5 parts of accelerator, 14.5 parts of filler and 6 parts of curing agent are transferred into a three-roll grinder, the temperature is raised to 80 ℃, and the curing agent is a mixture of benzyltriethylammonium chloride, vulcanizing agent FSH, cumene hydroperoxide and benzoyl peroxide with the weight ratio of 0.5: 1: 2 after grinding for 7.5min to obtain a curing glue solution; 4. uniformly mixing the chlorinated polyester microemulsion with a dispersing agent, a defoaming agent, a thickening agent and a film-forming aid to obtain the paint paste, wherein the chlorinated polyester microemulsion accounts for 60 wt%, the polystyrene latex accounts for 15 wt%, the thickening agent accounts for 3 wt%, the dispersing agent accounts for 6 wt%, and the rest is the film-forming aid and accounts for 100 wt%. The coating is prepared by uniformly mixing and thermally curing independently-packaged paint slurry and independently-packaged curing liquid in a weight ratio of 7: 3, wherein the thickener is Rohm & Haast-935, the dispersant is BYK-1640, the film-forming additive is 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, the accelerator is diethylaniline, and the filler is 800-mesh cast stone powder of a Henwei heat-preservation fire-resistant anticorrosive material factory, zhang 38473a, the preparation method refers to (Zhang Feng. Preparation of monodisperse polystyrene latex [ J ]. Fine chemical industry, 1989 (05): 38-39 ]) fifth step.
Example 3
A chlorinated polyester alloy heat-resistant anticorrosive paint comprises the following steps: the first step, preparing chlorinated polyester microemulsion: adding Huachang L into a stirring kettle 91 1, adding triethanolamine accounting for 0.9 percent of the mass fraction of the chlorinated polyester after the chlorinated polyester is chlorinated, stirring at the stirring speed of 2500rpm, and slowly dripping water into a stirring kettle to form uniform chlorinated polyester micro-emulsion with the solid content of 40 percent; step two, preparing a curing liquid: adding 100 parts by weight of cyclohexane solution of 25 percent by mass of Baling SIS1105 styrene-isoprene-styrene block copolymer into a reaction kettle, dropwise adding 15 parts by weight of mixed monomer of styrene, N-hydroxymethyl acrylamide and methacrylic acid = 7: 2: 1 and 15 parts by weight of azodiisobutyl amidine hydrochloride aqueous solution 0.04wt%, carrying out SIS graft copolymerization reaction, controlling the temperature at 75-80 ℃ for 4 hours, adding 0.5 part by weight of hydroquinone, continuously stirring for 10 minutes, reducing the temperature to 60 ℃, and then adding OP-10 to0.5 part of compound emulsifier with hexadecyl trimethyl ammonium bromide = 8: 2, slowly dripping deionized water to form emulsion under high-speed stirring, continuously stirring for 60min at normal temperature, and filtering by using a 400-mesh screen to obtain the SIS styrene-isoprene-styrene segmented copolymer latex with the solid content of 40%. Heating styrene-isoprene-styrene block copolymer latex to 65 ℃, slowly adding aminated graphene oxide, wherein the weight ratio of the aminated graphene oxide to the styrene-isoprene-styrene block copolymer latex is 23: 3, the stirring time is 2min, the stirring speed is 15000rpm, obtaining styrene-isoprene-styrene block copolymer emulsion, adding 1.8 parts of graphene oxide and 180 parts of distilled water into a reaction kettle, carrying out ultrasonic oscillation reaction for 0.5h, adding 1.5 parts of polyethyleneimine, continuing the ultrasonic oscillation reaction for 1h, obtaining a uniformly dispersed system, and separating the aminated graphene oxide, the Baoqinlong graphene oxide GO-P001 and the polyethyleneimine Bairong chemical BRC-36 through high-speed centrifugation; step three, grinding and stirring: the curing agent is a mixture of benzyltriethylammonium chloride, vulcanizing agent FSH, zibo win industrial grade cumene hydroperoxide and Qiangsheng BW50 benzoyl peroxide in the weight ratio of 0.5: 1: 2, and the filler is broad-source GY-1250 barite powder; 4. uniformly mixing the chlorinated polyester microemulsion with a dispersing agent, a defoaming agent, a thickening agent and a film-forming aid to obtain the paint paste, wherein the chlorinated polyester microemulsion accounts for 60 wt%, the polystyrene latex accounts for 15 wt%, the thickening agent accounts for 3 wt%, the dispersing agent accounts for 5 wt%, and the rest is the film-forming aid and accounts for 100 wt%. The preparation method comprises the steps of preparing a polystyrene latex, wherein the thickener is SN636, the dispersant is H188A, the film-forming aid is dipropylene glycol methyl ether, the accelerator is YPS-2005 etherified glycoluril resin, the particle size of the polystyrene latex is 25nm, and the preparation method refers to the preparation of (m-phoenix-monodisperse polystyrene latex [ J ] by means of]Fine chemical engineering, 1989 (05): 38-39.) the fifth step, the coating is obtained by mixing the independently-packaged coating paste and the independently-packaged curing liquid in a weight ratio of 7: 5 uniformly and then thermally curing.
The performances of the chlorinated polyester alloy heat-resistant anticorrosive coatings of examples 1 to 3 were measured, and the results are shown in Table 1
Results of testing the Properties of chlorinated polyester alloy Heat-resistant anticorrosive coatings of examples 1 to 3
Figure DEST_PATH_IMAGE002
Note: the base material and the base material processing test sample plate are processed according to the regulations of GB/T9271-2008, and the test sample plate is a tin plate except for other specified detection items such as workability, drying time, flexibility, adhesion (grid cutting method) and the like, and steel plates are used for other items. The adhesive force (pull-open method) and salt spray resistance substrate is a sand blasting steel plate, the derusting grade of the sand blasting steel plate reaches Sa21/2 grade specified in visual assessment of surface cleanliness of steel surface treatment before GB/T8923.1-2011 coating, and the surface roughness reaches middle grade RZ (40 to 70) mu m specified in the steel surface roughness characteristics after GB/T13288.1-2008 coating and spray cleaning of the steel surface treatment before GB/T13288.1-2008 coating. Coating method the paint films were prepared as specified in the general preparation of paint films of GB/T1727-1992, with a paint film thickness of 23 μm, in dry film. Detection of paint film properties adhesion (cross-hatch method), flexibility, hardness, impact, drying time were tested after actual drying. The thickness of the paint film is measured according to the GB/T13452.2-2008 regulation. The fineness is determined according to the paint fineness determination method of GB/T1724-1979 (1989). The drying time is determined according to the determination method of the drying time of paint films and putty films of GB/T1728-1979 (1989). The scoring tests were carried out as specified in GB/T9286-1998 scoring tests for paint and varnish films, (knife spacing 1 mm). The adhesion is carried out according to the adhesion test specification of GB/T5210-2006 paint and varnish by a pull-open method, and a test column with the diameter of 20mm is used. The flexibility is determined according to the GB/T1731-1993 paint flexibility determination method. The hardness is determined according to the specification of a pendulum damping test of a GB/T1730-1993 paint film hardness determination method. The impact resistance was determined according to the paint film impact test method of GB/T1732-1993. Two pieces of the constructability tinplate plates with the size of 700mm multiplied by 150mm multiplied by 0.3mm are not difficult to operate in the spraying process, and abnormal phenomena such as sagging, blistering and the like are observed after the surfaces are dried. Water resistance is carried out according to the GB/T1733-1993 paint film water resistance determination method. The panel was removed at the time specified by the standard and immediately rinsed with water and blotted dry with filter paper and left to stand for 2 hours before the paint film was inspected. And if 2 of the 3 test sample plates can not see the phenomena of foaming, falling off and rust, the water resistance is qualified. The salt water resistance is determined according to the 5 (soaking method) in the GB/T9274-1988 determination of the liquid-resistant medium of the colored paint and the varnish. The panel was removed at the time specified by the standard and immediately rinsed with water and blotted dry with filter paper and left to stand for 2 hours before the paint film was inspected. And if 2 of the 3 test sample plates can not see the phenomena of foaming, falling off and rust, the salt water resistance is qualified. The salt spray resistance is determined according to the specification of GB/T1771-2007 color paint and varnish for neutral salt spray resistance. According to the rating method of GB/T1766-2008 color paint and varnish coating aging. The panels were removed at the time specified by the standard and immediately rinsed with water and blotted dry with filter paper and allowed to stand for 2h before the paint film was inspected. If 2 of the 3 test samples can not see the phenomena of foaming and rust, the salt spray resistance is qualified. The alkali resistance and salt (sulfuric acid and nitric acid) resistance are determined according to the specification of 5 (soaking method) in the determination of GB/T9274-1988 colored paint and varnish liquid-resistant medium. The panel was removed at the time specified by the standard and immediately rinsed with water and blotted dry with filter paper and left to stand for 2 hours before the paint film was inspected. If 2 of the 3 test sample plates can not see the phenomena of foaming and shedding, the alkali resistance and the salt (sulfur and nitrate) resistance are qualified. In which the coating test panels of examples 1-3 were prepared as described in Table 2.
TABLE 2 preparation of coating test panels for examples 1-3
Figure DEST_PATH_IMAGE004
。

Claims (7)

1. A chlorinated polyester alloy heat-resistant anticorrosive paint is obtained by uniformly mixing independently subpackaged paint slurry and independently subpackaged curing liquid in a weight ratio of 7: 3 to 5 and then thermally curing, and is characterized in that the production process of the chlorinated polyester alloy heat-resistant anticorrosive paint comprises the following steps: 1. preparing a chlorinated polyester microemulsion: adding chlorinated polyester into a stirring kettle, then adding triethanolamine accounting for 0.9 to 1.0 mass percent of the chlorinated polyester, stirring at a stirring speed of 2500 to 3000rpm, and slowly dripping water into the stirring kettle to form uniform chlorinated polyester microemulsion with the solid content of 40 to 45 percent; 2. preparing a curing liquid: heating styrene-isoprene-styrene block copolymer latex with the solid content of 42% to 65-70 ℃, slowly adding aminated graphene oxide, wherein the ratio of the aminated graphene oxide to the styrene-isoprene-styrene block copolymer latex is 23-25: 3, stirring for 2-3min at the stirring speed of 15000-16000rpm, and obtaining styrene-isoprene-styrene block copolymer emulsion; 3. grinding and stirring: 45 to 50 parts of styrene-isoprene-styrene segmented copolymer emulsion, 1 to 2 parts of accelerator, 14 to 16 parts of filler and 5 to 7 parts of curing agent by weight are transferred into a three-roll grinding machine, the temperature is raised to 75 to 85 ℃, and the mixture is ground for 5 to 10min to obtain a curing glue solution; 4. uniformly mixing the chlorinated polyester microemulsion with a dispersing agent, an antifoaming agent, a thickening agent and a film forming aid to obtain paint paste, wherein the chlorinated polyester microemulsion accounts for 60 to 65 wt%, the polystyrene latex accounts for 15 to 20 wt%, the thickening agent accounts for 3 to 5 wt%, the dispersing agent accounts for 5 to 7 wt%, and the balance is the film forming aid, and the total weight is 100%.
2. The chlorinated polyester alloy heat-resistant anticorrosive paint according to claim 1, wherein the thickener is SN636 or TT-935, the dispersant is BYK-1640 or H188A, and the film-forming aid is one of dipropylene glycol methyl ether or tripropylene glycol methyl ether or 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate.
3. The chlorinated polyester alloy heat-resistant anticorrosive paint according to claim 1, wherein the accelerator is YPS-2005 etherified glycoluril resin or diethylaniline, and the filler is barite powder or cast stone powder.
4. The chlorinated polyester alloy heat-resistant anticorrosive paint according to claim 1, wherein the curing agent is a mixture of benzyltriethylammonium chloride, a vulcanizing agent FSH, cumene hydroperoxide and benzoyl peroxide in a weight ratio of 0.5: 1: 2.
5. The chlorinated polyester alloy heat-resistant anticorrosive paint according to claim 1, wherein the chlorinated polyester contains chlorinated unsaturated polyester with a chlorine content of 55% to 60%.
6. The chlorinated polyester alloy heat-resistant anticorrosive paint as claimed in claim 1, wherein the aminated graphene oxide is prepared by adding 1.8-2 parts of graphene oxide and 180-200 parts of distilled water into a reaction kettle, carrying out ultrasonic oscillation reaction for 0.5-1h, adding 1.5-2 parts of polyethyleneimine, carrying out ultrasonic oscillation reaction for 1h to obtain a uniformly dispersed system, and carrying out high-speed centrifugation to separate the aminated graphene oxide.
7. The chlorinated polyester alloy heat-resistant anticorrosive paint according to claim 1, wherein the particle size of the polystyrene latex is 25 to 45nm.
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