CN106893446B - A kind of epoxy group wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter - Google Patents
A kind of epoxy group wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter Download PDFInfo
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- CN106893446B CN106893446B CN201510961333.5A CN201510961333A CN106893446B CN 106893446 B CN106893446 B CN 106893446B CN 201510961333 A CN201510961333 A CN 201510961333A CN 106893446 B CN106893446 B CN 106893446B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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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
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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
- C09D7/65—Additives macromolecular
Abstract
The invention belongs to technical field of coatings, and in particular to a kind of epoxy group wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter.The polyformaldehyde particle of addition surface grafting epoxy resin is as filler in the coating, compatibility is good between epoxy resin in the epoxy resin and coating of the grafting of polyformaldehyde microparticle surfaces, filler in coating is avoided to reunite, it is precipitated, the disadvantages such as precipitating, so that polyformaldehyde filler may be homogenously dispersed in coating and paint spraying solidify after coating in, the polyformaldehyde particle for being dispersed in coat inside assigns the consistent bulk density of coating material and balanced stress distribution, inhibit corrosion-inhibiting coating that embrittlement cracking occurs, phenomena such as underfilm corrosion, to significantly improve the mechanical obdurability of corrosion-inhibiting coating, wearability, impact resistance and anti-corrosion life.Coating of the present invention can be using brushing, spraying, impregnating various ways coating, and the corrosion-inhibiting coating after coated solidified can be used alone, and can also match with corresponding intermediate coat or finishing coat.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter
And preparation method.
Background technique
A large amount of antiseptic project and scientific experiment prove that epoxy resin-matrix coating has excellent antiseptic property both at home and abroad,
It is the principal item of anticorrosive paint, yield accounts for about more than half of anticorrosive paint, but obtains after epoxy coating coated solidified
The wear-resisting and impact resistance of coating is bad.With the development of science and technology with the progress of technology, many metal components need coating now
Wear-resisting, impact resistance and corrosion resistant coating are usually added in coating for the wear-resisting and shock resistance for improving epoxy coating
A large amount of inorganic filler improves the performances such as the wear-resisting and shock resistance of coating, however the density of inorganic filler is much higher than epoxy resin
Density causes the overall weight of coating to be significantly increased, and after the overall weight increase of coating, will lead to component or equipment heaviness, mentions
High power consumption increases the problems such as carbon emission.
Polyformaldehyde is the engineering plastics of high comprehensive performance, by the difference of chemical structure in its strand, can be divided into homopolymerization
Formaldehyde and two kinds of copolymerized methanal have high mechanical property, such as intensity, modulus, wearability, toughness, fatigue durability and creep resistant
Property, it is one of five big general engineering plastics, is known as " supersteel " or " match steel ".Polyformaldehyde has the hardness, strong of metalloid
Degree and rigidity all have good self-lubrication, good fatigue durability in a wide temperature and humidity range, and are imbued with bullet
Property, furthermore it there are also preferable chemical-resistants.Polyformaldehyde is being substituted with the cost lower than other many engineering plastics
The market traditionally captured by metal, have been widely used for electronics, machinery, machinery, instrument, daily light industry, automobile, building materials,
The fields such as agricultural.
Summary of the invention
The epoxy group wear resistant and impact resistant anticorrosive paint and preparation side that the purpose of the present invention is to provide a kind of without inorganic matter
Method, the coating obtained after the paint spraying have good wear-resisting, impact resistance and corrosion protection effect.
The technical scheme is that
A kind of epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, the coating are made of component A and B component, press
Mass parts meter, including following component and dosage:
(1) component A:
(2) B component:
Curing agent 0.1~100.
The epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, it is preferred that in parts by mass, including it is as follows
Component and dosage:
(1) component A:
(2) B component:
Curing agent 5~60.
The epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, with two or more on epoxy molecule
Epoxy-functional, epoxy molecule be aliphatic structure or aromatic structure.
The epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, auxiliary agent are defoaming agent, levelling agent, adhesive force
It is promotor, drier, toughener, thickener, pigment dispersing agent, anti-skinning agent, delustering agent, light stabilizer, mould inhibitor, antistatic
Any combination of one or more of agent.
The epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, dispersing agent are toluene, dimethylbenzene, positive fourth
Any combination of one or more of alcohol, ethyl alcohol, isopropanol, acetone, deionized water.
The epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, curing agent are divided into two classes: the first kind is amine
Class compound, and more than two N-H structures are had on the molecule of aminated compounds, solidification agent molecule is aliphatic structure or virtue
Fragrant race's structure；Second class is binary acid, polyacid or its acid anhydrides, and solidification agent molecule is aliphatic structure or aromatic structure.
The preparation method of the epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, will in clean container
Epoxy resin, polyformaldehyde filler, auxiliary agent, the dispersing agent of surface grafting epoxy resin are agitated after evenly mixing, then use coating
Milling apparatus is handled 10~30 minutes, and the component A of coating is obtained after the screen to filtrate, canning and storage is injected, by the A group of coating
Part, B component are homogenously mixed together the coating being deployed into coating.
The preparation method of the epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, surface grafting epoxy resin
Polyformaldehyde filler preparation process it is as follows:
Amino silane with double bond is reacted generation with polyformaldehyde particle under the action of radical initiator and connect by the first step
Branch silane polyformaldehyde particle, the first step reaction specific requirement include: 1. room temperature to 150 DEG C react 0.5~12 hour；②
Dispersing agent is not added in the reaction bonus point powder；3. the material ratio reacted is that the mass ratio of amino silane and polyformaldehyde particle is
0.01:1~10:1；
Second step reacts the polyformaldehyde particle of grafted silane with epoxy resin, and the specific requirement of second step reaction includes:
1. room temperature to 180 DEG C react 0.5~24 hour；2. dispersing agent is not added in the reaction bonus point powder；3. the material ratio reacted is
The mass ratio of polyformaldehyde particle and epoxy resin is 0.01:1~10:1；
Third step dispersing agent washs repeatedly and is centrifuged or is filtered to remove unreacted epoxy resin, obtains grafted epoxy
The polyformaldehyde filler of resin, filler drying are saved or are saved in dispersing agent.
The epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, the silane with double bond meet following two simultaneously
A requirement: more than one carbon-carbon double bond structure is 1. had on the molecule of amino silane；2. at least band on the molecule of amino silane
There is more than one alkoxide；Polyformaldehyde particle meets following two requirements: the 1. chemical composition of polyformaldehyde particle simultaneously
For acefal homopolymer or copolymerized methanal；2. the partial size of polyformaldehyde particle is in 20 nanometers~100 micron ranges；Radical initiator is
The compound that can be generated free radicals under conditions of room temperature or heating；Dispersing agent is toluene, dimethylbenzene, n-butanol, ethyl alcohol, different
Any combination of one or more of propyl alcohol, acetone.
The preparation method of the epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, the coating process packet of coating
It includes following steps: sandblasting or sand paper grinding process 1. being carried out to metal base, remove the rust and other sundries of metallic substrate surface,
Then degreasing is removed using dehydrated alcohol or acetone cleaning metallic matrix, clean metallic matrix is obtained after drying and is put into drier
Interior preservation directly uses；2. being controlled using brushing, spraying or dipping prepares coating, coating layer thickness by coating number, spray every time
It applies with a thickness of 10~150 μm；3. the coating after coating solidifies at room temperature, or solidifies in a heated condition.
The invention has the advantages and beneficial effects that:
1, the present invention is free of the epoxy group wear resistant and impact resistant anticorrosive paint of inorganic matter, is made of component A, B component, wherein A
Polyformaldehyde filler in component containing Graft Epoxy Resin, coating prepared by coating have the characteristics that light weight, good mechanical property；
B component is curing agent.Inorganic filler is replaced with low-density, high performance polyformaldehyde particle, so that applying after coating and coated solidified
Coating and coating of the density of layer much smaller than addition inorganic filler；The coating is free of heavy metal, the coating obtained after paint solidification
It is nontoxic, pollution-free.
2, epoxy resin has suitable coating mobility and excellent antiseptic property, but the performances such as its wear-resisting and shock resistance
It is bad；Polyformaldehyde be difficult to be prepared into can coating flow regime, but polyformaldehyde is a kind of tough and tensile flexible material, has hardness
Greatly, the advantages that modulus height, creep resistant, wear-resisting and impact property.The present invention uses polyformaldehyde microparticle surfaces Graft Epoxy Resin
Technology improves the interface compatibility between polyformaldehyde particle and epoxy resin, and then comprehensive epoxy resin and polyformaldehyde are respectively
Performance advantage, formed it is a kind of have concurrently anti-corrosion, wear-resisting and impact work can coating and preparation method thereof.
3, the present invention claims the production of coating, coating process and common epoxy coating it is essentially identical, coating storage is steady
Qualitative good, the wear-resisting of coating, shock resistance and Corrosion Protection are excellent after paint solidification.
4, the present invention mitigates corrosion-inhibiting coating system because the density of dab layer can be greatly reduced in coating without inorganic matter
Overall weight is conducive to be protected metal material lightweight, so that it is many to play spry and light, reduction power consumption, energy-saving and emission-reduction etc.
Beneficial effect.
Specific embodiment
In the specific implementation process, the present invention is added to without in the epoxy group wear resistant and impact resistant anticorrosive paint of inorganic matter
The ring in epoxy resin and coating that the polyformaldehyde particle of surface grafting epoxy resin is grafted as filler, polyformaldehyde microparticle surfaces
Compatibility is good between oxygen resin, caused by solving polyformaldehyde filler and epoxy resin because solubility parameters differs greatly to each other
The bad problem of interface compatibility avoids the disadvantages such as filler reunion, precipitation, precipitating in coating, so that polyformaldehyde filler
May be homogenously dispersed in coating and paint spraying solidify after coating in, be dispersed in the polyformaldehyde particle tax of coat inside
The consistent bulk density of precoat material and balanced stress distribution inhibit corrosion-inhibiting coating that brittle cracking, underfilm corrosion etc. occurs
Phenomenon, to significantly improve mechanical obdurability, wearability, impact resistance and the anti-corrosion life of corrosion-inhibiting coating.
Paint spraying and coating preparation:
The component A of coating, B component are homogenously mixed together to the coating being deployed into coating, the coating process packet of coating
It includes following steps: sandblasting or sand paper grinding process 1. being carried out to metal base, remove the rust and other sundries of metallic substrate surface,
Then degreasing is removed using dehydrated alcohol or acetone cleaning metallic matrix, clean metallic matrix is obtained after drying and is put into drier
Interior preservation directly uses.2. coating layer thickness is controlled by coating number, often using brushing, spraying, impregnating mode prepares coating
Secondary coating thickness is about 10~150 μm, can multiple coating.3. the coating after coating can solidify the also item in heating at room temperature
Solidify under part.Corrosion-inhibiting coating after coated solidified can be used alone, and can also match with corresponding intermediate coat or finishing coat.
In the following, the present invention is described in further detail in conjunction with the embodiments.
Embodiment 1
Install reflux condensing tube and water segregator additional on the clean closed heatproof container with agitating device, it should be tight between each component
Close connection guarantees the airtightness of device.Be added in container 10 gram particle diameters be 20 nanometers acefal homopolymer particle, 100 grams of toluene,
0.1 gram of vinyltriethoxysilane is stirred at room temperature uniformly, is warming up to refluxing toluene, the moisture in removing system, then
1 gram of cumyl peroxide is added in reaction system in three times under conditions of nitrogen protection, it is then small in 120 DEG C of reactions 3
When prepare the polyformaldehyde particle of surface grafting silane, toluene is evaporated under reduced pressure to spare in clean container after reaction.First
1000 grams of 160~180 (g.mol of epoxide equivalent are added into reaction system after steaming for benzene-1) bisphenol f type epoxy resin, heating
To 180 DEG C of reactions, reaction was completed within 0.5 hour, and product toluene washs repeatedly and is centrifuged or is filtered to remove unreacted asphalt mixtures modified by epoxy resin
Rouge, obtains the polyformaldehyde filler of Graft Epoxy Resin, which can dry preservation and also save in toluene.
By the polyformaldehyde filler of 5 grams of Graft Epoxy Resins, 100 grams of 185~208 (g.mol of epoxide equivalent-1) bisphenol A-type
Epoxy resin, 8 grams of toughener, 0.5 gram of defoaming agent, 0.5 gram of levelling agent, 0.3 gram of antistatic agent, 0.5 gram of pigment dispersing agent investment
It is handled 30 minutes to coating grinding equipment, the component A of coating is obtained after 300 mesh net filtrations, inject canning and storage.Then
Into coating component A be added 60 grams of cashew nut shell amine as curing agent, after mixing evenly with brush by paint spraying in metal testing plate
Surface solidifies two weeks at room temperature.It is added to the coating of same recipe with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities
Inside compare.The cure shrinkage of gained anticorrosive paint can reduce by 1.1 times, and the water absorption rate of coating can reduce by 55%, coating it is strong
Degree can be improved 12%, the wearability of coating improves 45%, and impact resistance can be improved 51%, and the salt-fog resistant time of coating can mention
It is high by 35%.
Embodiment 2
The copolymerized methanal particle, 100 that 200 gram particle diameters are 50 microns are added in the clean heatproof container with agitating device
Gram toluene, 2000 grams of vinyltrimethoxysilanes, 30 grams of methyl ethyl ketone peroxides are stirred at room temperature uniformly, are warming up to 125 DEG C
Reaction prepares the polyformaldehyde particle of surface grafting silane for 2 hours, is washed with toluene repeatedly remove unreacted silicon after reaction
20 grams of 165~185 (g.mol of epoxide equivalent are then added in alkane into reaction system-1) bisphenol f type epoxy resin, room temperature reaction
Reaction was completed within 24 hours, and product toluene washs repeatedly and be centrifuged or be filtered to remove unreacted epoxy resin, obtains grafting ring
The polyformaldehyde filler of oxygen resin, the filler can dry preservation and also save in toluene.
By the polyformaldehyde filler of 200 grams of Graft Epoxy Resins, 100 grams of 185~208 (g.mol of epoxide equivalent-1) bisphenol-A
Type epoxy resin, 19 grams of toughener, 0.3 gram of defoaming agent, 0.2 gram of adhesion promoter, 0.3 gram of thickener, 0.2 gram of mould inhibitor are thrown
Enter to coating grinding equipment and handle 30 minutes, the component A of coating is obtained after 120 mesh net filtrations, injects canning and storage.It connects
Into coating component A be added 5 grams of diethyl triolefins as curing agent, after mixing evenly with brush by paint spraying in metal testing plate
Surface solidifies one week at room temperature.It is added to the coating of same recipe with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities
Inside compare.The cure shrinkage of gained anticorrosive paint can reduce by 1.3 times, and the water absorption rate of coating can reduce by 5%, the intensity of coating
It can be improved 8%, the wearability of coating improves 40%, and impact resistance can be improved 35%, and the salt-fog resistant time of coating can be improved
5%.
Embodiment 3
Install reflux condensing tube and water segregator additional on the clean closed heatproof container with agitating device, it should be tight between each component
Close connection guarantees the airtightness of device.Be added in container 50 gram particle diameters be 1 micron acefal homopolymer particle, 100 grams of dimethylbenzene,
0.1 gram of vinyl methyl diethoxy silane is stirred at room temperature uniformly, is warming up to refluxing xylene, the water in removing system
Point, then 5 grams of cumyl peroxides are added in reaction system in three times under conditions of nitrogen protection, it is then anti-at 50 DEG C
The polyformaldehyde particle for preparing surface grafting silane in 12 hours is answered, dimethylbenzene is evaporated under reduced pressure to clean container after reaction
It is spare.100 grams of 200~220 (g.mol of epoxide equivalent are added into reaction system after steaming for dimethylbenzene-1) aliphatic epoxy tree
Rouge, reaction was completed within 24 hours for reaction at room temperature, and product dimethylbenzene washs repeatedly and is centrifuged or is filtered to remove unreacted ring
Oxygen resin, obtains the polyformaldehyde filler of Graft Epoxy Resin, which can dry preservation and also save in dimethylbenzene.
By the polyformaldehyde filler of 10 grams of Graft Epoxy Resins, 100 grams of 455~556 (g.mol of epoxide equivalent-1) bisphenol-f type
Epoxy resin, 0.5 gram of defoaming agent, 0.5 gram of levelling agent, 0.1 gram of anti-skinning agent, 0.3 gram of delustering agent, 0.2 gram 50 grams of light stabilizer
Dimethylbenzene, 10 grams of isopropanols put into coating grinding equipment and handle 30 minutes, and the A of coating is obtained after 200 mesh net filtrations
Component injects canning and storage.Then 15 grams of tetraethylenepentamine are added into coating component A as curing agent, use after mixing evenly
Infusion process in metal testing plate surface, solidifies paint spraying two weeks at room temperature.With the non-grafted epoxy resin of phase homogenous quantities
Polyformaldehyde, which is added in the coating of same recipe, to be compared.The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, coating
Water absorption rate can reduce by 35%, and the intensity of coating can be improved 32%, the wearability of coating improves 55%, and impact resistance can be improved
65%, the salt-fog resistant time of coating can be improved 30%.
Embodiment 4
The acefal homopolymer particle, 30 that 150 gram particle diameters are 50 microns are added in the clean heatproof container with agitating device
Gram ethyl alcohol, 30 grams of isopropanols, 10 grams of n-butanols, 40 grams of deionized waters, 20 grams of vinyl methyl dimethoxysilanes, 3 grams of over cures
Sour potassium is stirred at room temperature uniformly, and room temperature reaction prepares the polyformaldehyde particle of surface grafting silane for 4 hours, after reaction with third
Ketone washs repeatedly removes unreacted silane, and 80 grams of 185~195 (g.mol of epoxide equivalent are then added into reaction system-1)
Novolac epoxy resin, reaction was completed within 0.5 hour for 180 DEG C of reactions, and product acetone washs repeatedly and is centrifuged or is filtered to remove and is not anti-
The epoxy resin answered, obtains the polyformaldehyde filler of Graft Epoxy Resin, which can dry preservation and also save in acetone.
By the polyformaldehyde filler of 140 grams of Graft Epoxy Resins, 100 grams of 215~230 (g.mol of epoxide equivalent-1) phenolic aldehyde ring
Oxygen resin, 0.8 gram of defoaming agent, 0.5 gram of levelling agent, 0.2 gram of drier, 0.7 gram of pigment dispersing agent, 70 grams of dimethylbenzene are put into painting
Abrasive lapping equipment is handled 30 minutes, and the component A of coating is obtained after 100 mesh net filtrations, injects canning and storage.Then to painting
Expect component A in be added 50 grams of Mannich polyamines as curing agent, after mixing evenly with infusion process by paint spraying in metal testing plate
Surface solidifies two weeks at room temperature.It is added to the coating of same recipe with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities
Inside compare.The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, and the water absorption rate of coating can reduce by 25%, coating it is strong
Degree can be improved 9%, and the wearability of coating improves 70%, and impact resistance can be improved 85%, and the salt-fog resistant time of coating can be improved
15%.
Embodiment 5
The copolymerized methanal particle, 70 grams that 120 gram particle diameters are 2 microns are added in the clean heatproof container with agitating device
Acetone, 9 grams of vinyl triacetyl oxosilanes, 5 grams of azodiisobutyronitriles are stirred at room temperature uniformly, and 64 DEG C prepare for reaction 6 hours
The polyformaldehyde particle of surface grafting silane is washed with acetone remove unreacted silane after reaction, repeatedly then to reaction
90 grams of 210~244 (g.mol of epoxide equivalent are added in system-1) bisphenol A type epoxy resin, 140 DEG C terminate within reaction 2 hours it is anti-
It answers, product acetone washs repeatedly and be centrifuged or be filtered to remove unreacted epoxy resin, obtains the poly- first of Graft Epoxy Resin
Aldehyde filler, the filler can dry preservation and also save in acetone.
By the polyformaldehyde filler of 100 grams of Graft Epoxy Resins, 100 grams of 215~230 (g.mol of epoxide equivalent-1) phenolic aldehyde ring
Oxygen resin, 0.1 gram of anti-skinning agent, 0.1 gram of delustering agent, 0.1 gram of light stabilizer, 0.3 gram of mould inhibitor, 0.1 gram of antistatic agent, 30 grams
Dimethylbenzene, investment to coating grinding equipment are handled 30 minutes, and the component A of coating is obtained after 200 mesh net filtrations, inject tank
Dress storage.Then 35 grams of pyromellitic acid dianhydrides are added into coating component A as curing agent, after mixing evenly with spray gun by coating
It is coated on metal testing plate surface, is solidified 24 hours at 200 DEG C.With the nanometer titanium dioxide of the non-grafted epoxy resin of phase homogenous quantities
Silicon, which is added in the coating of same recipe, to be compared.The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, the water suction of coating
Rate can reduce by 10%, and the intensity of coating can be improved 18%, and the wearability of coating improves 75%, and impact resistance can be improved 80%,
The salt-fog resistant time of coating can be improved 2%.
Embodiment 6
Install reflux condensing tube and water segregator additional on the clean closed heatproof container with agitating device, it should be tight between each component
Close connection guarantees the airtightness of device.Be added in container 50 gram particle diameters be 70 nanometers copolymerized methanal particle, 100 grams of toluene,
0.1 gram of vinyltriisopropenyloxysilane is stirred at room temperature uniformly, is warming up to refluxing toluene, the moisture in removing system,
Then 5 grams of benzoyl peroxides are added in reaction system under conditions of nitrogen protection, then react 3 hours and makes at 105 DEG C
Toluene, is evaporated under reduced pressure to spare in clean container by the polyformaldehyde particle of standby surface grafting silane after reaction.Toluene steams
30 grams of 455~556 (g.mol of epoxide equivalent are added after out into reaction system-1) bisphenol A type epoxy resin, be warming up to 120 DEG C
Reaction was completed within 5 hours for reaction, and product acetone washs repeatedly and be centrifuged or be filtered to remove unreacted epoxy resin, is connect
The polyformaldehyde filler of branch epoxy resin, the filler can dry preservation and also save in toluene.
By the polyformaldehyde filler of 30 grams of Graft Epoxy Resins, 100 grams of 1210~244 (g.mol of epoxide equivalent-1) bisphenol-A
Type epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 1 gram of adhesion promoter, 0.1 gram of drier, 3 grams of toughener, 0.5 gram of increasing
Thick dose of investment to coating grinding equipment is handled 20 minutes, and the component A of coating is obtained after 240 mesh net filtrations, is injected canned
Storage.Then 57 grams of polyamide (650) are added into coating component A and are used as curing agent, after mixing evenly applied coating with spray gun
Loaded on metal testing plate surface, solidify two weeks at room temperature.It is added to phase with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities
It is compared in coating with formula.The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, and the water absorption rate of coating can reduce
30%, the intensity of coating can be improved 22%, the wearability of coating improves 45%, and impact resistance can be improved 55%, coating it is resistance to
The salt fog time can be improved 30%.
Embodiment 7
Install reflux condensing tube and water segregator additional on the clean closed heatproof container with agitating device, it should be tight between each component
Close connection guarantees the airtightness of device.Be added in container 200 gram particle diameters be 10 microns acefal homopolymer particle, 300 grams of toluene,
6 grams of vinyl three (2- methoxy ethoxy) silane are stirred at room temperature uniformly, are warming up to refluxing toluene, the water in removing system
Point, then 5 grams of tert-butyl hydroperoxide are added in reaction system under conditions of nitrogen protection, then react 10 at 120 DEG C
Hour prepares the polyformaldehyde particle of surface grafting silane, and toluene is evaporated under reduced pressure to spare in clean container after reaction.
30 grams of 185~208 (g.mol of epoxide equivalent are added into reaction system after steaming for toluene-1) bisphenol A type epoxy resin, heating
To 60 DEG C of reactions, reaction was completed within 10 hours, and product toluene washs repeatedly and be centrifuged or be filtered to remove unreacted epoxy resin,
The polyformaldehyde filler of Graft Epoxy Resin is obtained, which can dry preservation and also save in toluene.
By the polyformaldehyde filler of 150 grams of Graft Epoxy Resins, 100 grams of 210~244 (g.mol of epoxide equivalent-1) bisphenol-A
Type epoxy resin, 21 grams of dimethylbenzene, 9 grams of isopropanols, 0.1 light stabilizer, 0.1 mould inhibitor, 0.1 antistatic agent put into coating and grind
It grinds equipment to handle 25 minutes, the component A of coating is obtained after 200 mesh net filtrations, inject canning and storage.Then to coating A
In component be added 29 grams of phthalic anhydrides as curing agent, after mixing evenly with spray gun by paint spraying in metal testing plate table
Face is warming up at 120 DEG C 2 hours 2 hours at 80 DEG C, is warming up at 180 DEG C 4 hours, is completed the solidification of coating.With identical
The polyformaldehyde of the non-grafted epoxy resin of quality, which is added in the coating of same recipe, to be compared.The solidification of gained anticorrosive paint is received
Shrinkage can reduce by 1.1 times, and the water absorption rate of coating can reduce by 20%, and the intensity of coating can be improved 35%, the wearability of coating improves
65%, impact resistance can be improved 45%, and the salt-fog resistant time of coating can be improved 8%.
Embodiment 8
Install reflux condensing tube and water segregator additional on the clean closed heatproof container with agitating device, it should be tight between each component
Close connection guarantees the airtightness of device.Be added in container 90 gram particle diameters be 20 microns acefal homopolymer particle, 100 grams of toluene,
25 grams of vinyl methyl dimethoxysilanes are stirred at room temperature uniformly, are warming up to refluxing toluene, and the moisture in removing system connects
3 grams of cumyl peroxides are added in reaction systems under conditions of nitrogen protection, then react 10 hours and make at 120 DEG C
Toluene, is evaporated under reduced pressure to spare in clean container by the polyformaldehyde particle of standby surface grafting silane after reaction.Toluene steams
30 grams of 455~556 (g.mol of epoxide equivalent are added after out into reaction system-1) bisphenol A type epoxy resin, be warming up to 60 DEG C
Reaction was completed within 10 hours for reaction, and product toluene washs repeatedly and be centrifuged or be filtered to remove unreacted epoxy resin, is connect
The polyformaldehyde filler of branch epoxy resin, the filler can dry preservation and also save in toluene.
By the polyformaldehyde filler of 70 grams of Graft Epoxy Resins, 100 grams of 210~244 (g.mol of epoxide equivalent-1) bisphenol A-type
Epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 0.05 gram of defoaming agent, 0.05 gram of levelling agent are put into coating grinding equipment processing
20 minutes, the component A of coating is obtained after 200 mesh net filtrations, injects canning and storage.Then it is added into coating component A
47 grams of polyamide (650) are used as curing agent, after mixing evenly with spray gun by paint spraying in metal testing plate surface, it is solid at room temperature
Change two weeks.It is added in the coating of same recipe with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities and is compared.Gained is anti-
The cure shrinkage of rotten coating can reduce by 1.2 times, and the water absorption rate of coating can reduce by 25%, and the intensity of coating can be improved 38%, it applies
The wearability of layer improves 67%, and impact resistance can be improved 49%, and the salt-fog resistant time of coating can be improved 12%.
Embodiment 9
The acefal homopolymer particle, 100 that 60 gram particle diameters are 30 microns are added in the clean heatproof container with agitating device
Gram deionized water, 20 grams of vinyltriethoxysilane, 2 grams of potassium peroxydisulfates are stirred at room temperature uniformly, are warming up to 60 DEG C of reactions 5
Hour prepares the polyformaldehyde particle of surface grafting silane, is washed with acetone repeatedly remove unreacted silane after reaction, connect
Into reaction system be added 80 grams of 455~556 (g.mol of epoxide equivalent-1) bisphenol f type epoxy resin, 60 DEG C of reactions are 10 small
When reaction was completed, product acetone washs repeatedly and is centrifuged or is filtered to remove unreacted epoxy resin, obtains grafted epoxy tree
The polyformaldehyde filler of rouge, the filler can dry preservation and also save in acetone.
By the polyformaldehyde filler of 40 grams of Graft Epoxy Resins, 100 grams of 210~244 (g.mol of epoxide equivalent-1) bisphenol A-type
Epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 0.05 gram of defoaming agent, 0.05 gram of adhesion promoter put into grinding coatings and set
Standby processing 20 minutes, obtains the component A of coating after 200 mesh net filtrations, injects canning and storage.Then to coating component A
49 grams of cashew nut shell amine are then added as curing agent, after mixing evenly with spray gun by paint spraying in middle addition into coating component A
In metal testing plate surface, solidify two weeks at room temperature.It is added to the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities identical
It is compared in the coating of formula.The cure shrinkage of gained anticorrosive paint can reduce by 1.3 times, and the water absorption rate of coating can reduce
21%, the intensity of coating can be improved 7%, and the wearability of coating improves 75%, and impact resistance can be improved 82%, the salt tolerant of coating
The mist time can be improved 7%.
Embodiment 10
The copolymerized methanal particle, 200 that 110 gram particle diameters are 5 microns are added in the clean heatproof container with agitating device
Gram ethyl alcohol, 12 grams of vinyltriisopropenyloxysilanes, 6 grams of azodiisobutyronitriles are stirred at room temperature uniformly, are warming up to ethyl alcohol
Reflux, reaction prepares the polyformaldehyde particle of surface grafting silane for 8 hours under the conditions of alcohol reflux, anti-with acetone after reaction
Unreacted silane is washed away in after backwashing, and 90 grams of 455~556 (g.mol of epoxide equivalent are then added into reaction system-1) bis-phenol
A type epoxy resin, reaction was completed within 12 hours for 40 DEG C of reactions, and product acetone washs repeatedly and is centrifuged or is filtered to remove unreacted
Epoxy resin, obtain the polyformaldehyde filler of Graft Epoxy Resin, which can dry preservation and also save in acetone.
By the polyformaldehyde filler of 100 grams of Graft Epoxy Resins, 100 grams of 210~244 (g.mol of epoxide equivalent-1) bisphenol-A
Type epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 0.05 gram of defoaming agent, 0.05 gram of levelling agent are put into coating grinding equipment
Reason 25 minutes obtains the component A of coating after 200 mesh net filtrations, injects canning and storage.Then add into coating component A
Enter then to be added 53 grams of polyamide (650) into coating component A as curing agent, after mixing evenly with spray gun by paint spraying in
Metal testing plate surface solidifies two weeks at room temperature.It is added to identical match with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities
It is compared in the coating of side.The cure shrinkage of gained anticorrosive paint can reduce by 1.1 times, and the water absorption rate of coating can reduce by 11%,
The intensity of coating can be improved 15%, and the wearability of coating improves 35%, and impact resistance can be improved 83%, when the salt spray resistance of coating
Between can be improved 12%.
Embodiment the result shows that, the present invention use polyformaldehyde microparticle surfaces Graft Epoxy Resin technology, improve polyformaldehyde
The interface compatibility between polymer that particle and epoxy resin both solubility parameters differ greatly, and then comprehensive epoxy resin
With the respective performance advantage of polyformaldehyde.In addition, the present invention claims coating storage stability it is good, the production of coating, construction technology
Essentially identical with common epoxy coating, the wear-resisting of coating, shock resistance and Corrosion Protection are excellent after paint solidification.
In addition, described above, it is only a preferred and feasible embodiment of the present invention, and the right of the present invention cannot be limited to this
A kind of range, epoxy group wear resistant and impact resistant anticorrosive paint and preparation method thereof without inorganic matter, applies also for other
Organic coating.Therefore, technical solution and technical thought under this invention make various other corresponding changes and modifications, still belong to this
It invents within covered protection scope.
Claims (7)
1. a kind of epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter, which is characterized in that the coating is by component A and B group
Part composition, in parts by mass, including following component and dosage:
(1) component A:
(2) B component:
Curing agent 0.1~100；
More than two epoxy-functionals are had on epoxy molecule, epoxy molecule is aliphatic structure or aromatic series knot
Structure；
Dispersing agent is one or more of toluene, dimethylbenzene, n-butanol, ethyl alcohol, isopropanol, acetone, deionized water
Any combination；
The preparation process of the polyformaldehyde filler of surface grafting epoxy resin is as follows:
Amino silane with double bond is reacted generation grafting silicon by the first step with polyformaldehyde particle under the action of radical initiator
The polyformaldehyde particle of alkane, the first step reaction specific requirement include: 1. room temperature to 150 DEG C react 0.5~12 hour；2. this is anti-
It answers bonus point powder or dispersing agent is not added；3. the mass ratio that the material ratio reacted is amino silane and polyformaldehyde particle be 0.01:1~
10:1；
Second step reacts the polyformaldehyde particle of grafted silane with epoxy resin, and the specific requirement of second step reaction includes: 1. to exist
Room temperature to 180 DEG C react 0.5~24 hour；2. dispersing agent is not added in the reaction bonus point powder；3. the material ratio reacted is poly- first
The mass ratio of aldehyde particle and epoxy resin is 0.01:1~10:1；
Third step dispersing agent washs repeatedly and is centrifuged or is filtered to remove unreacted epoxy resin, obtains Graft Epoxy Resin
Polyformaldehyde filler, the filler drying save or saved in dispersing agent.
2. the epoxy group wear resistant and impact resistant anticorrosive paint described in accordance with the claim 1 without inorganic matter, which is characterized in that press matter
Measure part meter, including following component and dosage:
(1) component A:
(2) B component:
Curing agent 5~60.
3. the epoxy group wear resistant and impact resistant anticorrosive paint described in accordance with the claim 1 without inorganic matter, which is characterized in that auxiliary agent
For defoaming agent, levelling agent, adhesion promoter, drier, toughener, thickener, pigment dispersing agent, anti-skinning agent, delustering agent,
Any combination of one or more of light stabilizer, mould inhibitor, antistatic agent.
4. the epoxy group wear resistant and impact resistant anticorrosive paint described in accordance with the claim 1 without inorganic matter, which is characterized in that solidification
Agent is divided into two classes: the first kind is aminated compounds, and more than two N-H structures are had on the molecule of aminated compounds, solidification
Agent molecule is aliphatic structure or aromatic structure；Second class is binary acid, polyacid or its acid anhydrides, and solidification agent molecule is fat
Race's structure or aromatic structure.
5. a kind of preparation method of the epoxy group wear resistant and impact resistant anticorrosive paint described in claim 1 without inorganic matter, special
Sign is, by epoxy resin, the polyformaldehyde filler of surface grafting epoxy resin, auxiliary agent, dispersing agent through stirring in clean container
It mixes after evenly mixing, is then handled 10~30 minutes with coating grinding equipment, the component A of coating is obtained after the screen to filtrate, infuse
Enter canning and storage, the component A of coating, B component are homogenously mixed together to the coating being deployed into coating.
6. the preparation method of the epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter according to claim 5, special
Sign is that the silane with double bond meets following two requirements simultaneously: 1. with more than one carbon carbon on the molecule of amino silane
Double bond structure；2. at least provided with more than one alkoxide on the molecule of amino silane；Polyformaldehyde particle meets such as simultaneously
Lower two requirements: 1. the chemical composition of polyformaldehyde particle is acefal homopolymer or copolymerized methanal；2. the partial size of polyformaldehyde particle is 20
In nanometer~100 micron ranges；Radical initiator is the compound that can be generated free radicals under conditions of room temperature or heating.
7. the preparation method of the epoxy group wear resistant and impact resistant anticorrosive paint without inorganic matter according to claim 5, special
Sign is 1. the coating process of coating is the following steps are included: carry out sandblasting or sand paper grinding process, removing metal to metal base
Then the rust of substrate surface and other sundries remove degreasing using dehydrated alcohol or acetone cleaning metallic matrix, obtain after drying
Clean metallic matrix, which is put into drier, to be saved or directly uses；2. applying thickness using brushing, spraying or impregnating prepares coating
Degree is controlled by coating number, and each coating thickness is 10~150 μm；3. the coating after coating solidifies at room temperature, or is heating
Under the conditions of solidify.
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| CN101125995A (en) * | 2007-09-28 | 2008-02-20 | 王新虎 | Screw thread adhesion abrasion resisting self-lubricating coating and preparation method thereof |
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| CN102532795A (en) * | 2011-12-23 | 2012-07-04 | 四川大学 | End-capped modified polyformaldehyde resin and preparation method thereof |
| CN102702458A (en) * | 2012-05-23 | 2012-10-03 | 北京旭阳化工技术研究院有限公司 | High-performance modified polyformaldehyde and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100970461B1 (en) * | 2010-02-09 | 2010-07-16 | 엘베스트지에이티 주식회사 | Organic inorganic hybrid type composition of coating agent for anticorrosion and manufacturing method of the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125995A (en) * | 2007-09-28 | 2008-02-20 | 王新虎 | Screw thread adhesion abrasion resisting self-lubricating coating and preparation method thereof |
| CN101343505A (en) * | 2008-08-08 | 2009-01-14 | 溧阳佳山电子材料有限公司 | Preparation method for fire resistant environment-friendly varnished wire hot melt self-adhering paint |
| CN102532449A (en) * | 2010-12-24 | 2012-07-04 | 上海美东生物材料有限公司 | Preparation method of mixed cresol modified meta-xylylene diamine epoxy resin curing agent |
| CN102532795A (en) * | 2011-12-23 | 2012-07-04 | 四川大学 | End-capped modified polyformaldehyde resin and preparation method thereof |
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