CN106893446A - A kind of epoxy radicals wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter - Google Patents
A kind of epoxy radicals wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter Download PDFInfo
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- CN106893446A CN106893446A CN201510961333.5A CN201510961333A CN106893446A CN 106893446 A CN106893446 A CN 106893446A CN 201510961333 A CN201510961333 A CN 201510961333A CN 106893446 A CN106893446 A CN 106893446A
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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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- 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
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- 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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- 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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- 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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Abstract
The invention belongs to technical field of coatings, and in particular to a kind of epoxy radicals wear resistant and impact resistant anticorrosive paint and preparation method without inorganic matter.The polyformaldehyde particulate of addition surface grafting epoxy resin is used 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 is reunited in avoiding coating, separate out, the disadvantages such as precipitation, so that polyformaldehyde filler may be homogenously dispersed in coating and paint spraying solidification after coating in, the polyformaldehyde particulate for being dispersed in coat inside assigns the consistent bulk density of coating material and in a balanced way stress distribution, suppress corrosion-inhibiting coating and brittle cracking occurs, the phenomenons such as underfilm corrosion, so as to significantly improve the mechanical obdurability of corrosion-inhibiting coating, wearability, impact resistance and anti-corrosion life.Coating of the present invention can be can be used alone using brushing, spraying, impregnating various ways application, the corrosion-inhibiting coating after coated solidified, it is also possible to be supported the use with corresponding intermediate coat or finish paint.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of epoxy radicals wear resistant and impact resistant anti-corrosion without inorganic matter
Coating and preparation method.
Background technology
Domestic and international substantial amounts of antiseptic project and scientific experiment prove that epoxy resin-matrix coating has excellent anti-corrosive properties
Can, it is the principal item of anticorrosive paint, its yield accounts for more than half of anticorrosive paint, but epoxy coating is applied
The wear-resisting and impact resistance that coating is obtained after dress solidification is not good.With science and technology development and technology progress, now
Many hardwares need wear-resisting application, impact resistance and corrosion resistant coating, to improve the wear-resisting of epoxy coating
And shock resistance, generally add substantial amounts of inorganic filler to improve the property such as the wear-resisting and shock resistance of coating in coating
Can, but the density of inorganic filler causes the overall weight of coating to be significantly increased far above the density of epoxy resin,
After the overall weight of coating increases, component or equipment heaviness will be caused, power consumption is improved, increased carbon emission etc.
Problems.
Polyformaldehyde is the engineering plastics of high comprehensive performance, by the difference of chemical constitution in its strand, can be divided into
Two kinds of acefal homopolymer and copolymerized methanal, with mechanical property high, such as intensity, modulus, wearability, toughness,
Fatigue durability and creep resistance, are one of five big general engineering plastics, are described as " supersteel " or " match steel ".It is poly-
Formaldehyde has hardness, intensity and the rigidity of metalloid, all has in the range of temperature and humidity very wide fine
Self lubricity, good fatigue durability, and springiness, in addition it also have preferable chemical-resistant.It is poly-
Formaldehyde is substituting some markets traditionally captured by metal with the cost less than other many engineering plastics,
Have been widely used for the field such as electric, mechanical, instrument, daily light industry, automobile, building materials, agricultural.
The content of the invention
It is an object of the invention to provide a kind of epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter and preparation
Method, the coating obtained after the paint spraying has good wear-resisting, impact resistance and corrosion protection effect.
The technical scheme is that：
A kind of epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, the coating is by component A and B component group
Into, in parts by mass, including following component and consumption：
(1) component A：
(2) B component：
Curing agent 0.1~100.
The described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, it is preferred that in parts by mass, bag
Include following component and consumption：
(1) component A：
(2) B component：
Curing agent 5~60.
The described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, carries two on epoxy molecule
Epoxy-functional above, epoxy molecule is aliphatic structure or aromatic structure.
The described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, auxiliary agent be defoamer, levelling agent,
Adhesion promoter, drier, toughener, thickener, pigment dispersing agent, anti-skinning agent, delustering agent, light
One or more any combination in stabilizer, mould inhibitor, antistatic additive.
The described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, dispersant be toluene, dimethylbenzene,
One or more any combination in n-butanol, ethanol, isopropanol, acetone, deionized water.
The described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, curing agent is divided into two classes：The first kind
It is that, with more than two N-H structures on aminated compounds, and the molecule of aminated compounds, solidification agent molecule is
Aliphatic structure or aromatic structure；Equations of The Second Kind is binary acid, polyacid or its acid anhydrides, and solidification agent molecule is fat
Fat race structure or aromatic structure.
The preparation method of the described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, in clean container
It is interior by epoxy resin, the polyformaldehyde filler of surface grafting epoxy resin, auxiliary agent, the agitated uniform mixing of dispersant
Afterwards, then processed 10~30 minutes with coating grinding equipment, the component A of coating obtained after screen filtration,
Injection canning and storage, the component A of coating, B component is homogenously mixed together and is deployed into the coating for treating application.
The preparation method of the described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, surface grafting epoxy
The preparation process of the polyformaldehyde filler of resin is as follows：
Amino silane with double bond and polyformaldehyde particulate are reacted generation by the first step in the presence of radical initiator
The polyformaldehyde particulate of grafted silane, the specific requirement of first step reaction includes：1. room temperature to 150 DEG C reaction 0.5~
12 hours；2. the reaction bonus point powder or it is not added with dispersant；3. the material ratio for reacting is amino silane and polyformaldehyde
The mass ratio of particulate is 0.01：1~10：1；
Second step reacts the polyformaldehyde particulate of grafted silane and epoxy resin, the specific requirement bag of second step reaction
Include：1. room temperature to 180 DEG C react 0.5~24 hour；2. the reaction bonus point powder or it is not added with dispersant；3. it is anti-
The material ratio answered is 0.01 with the mass ratio of epoxy resin for polyformaldehyde particulate：1~10：1；
3rd step dispersant cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, is grafted
The polyformaldehyde filler of epoxy resin, filler drying is preserved or preserved in dispersant.
The described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, the silane with double bond meets such as simultaneously
Lower two requirements：1. more than one carbon-carbon double bond structure is carried on the molecule of amino silane；2. amino silane
At least provided with more than one alkoxide on molecule；Polyformaldehyde particulate meets following two requirements simultaneously：①
The chemical composition of polyformaldehyde particulate is acefal homopolymer or copolymerized methanal；2. the particle diameter of polyformaldehyde particulate 20 nanometers~
In 100 micrometer ranges；Radical initiator is the chemical combination that free radical can be produced under conditions of room temperature or heating
Thing；Dispersant be toluene, dimethylbenzene, n-butanol, ethanol, isopropanol, acetone in one or more
Any combination.
The preparation method of the described epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, the application work of coating
Skill is comprised the following steps：1. sandblasting or sand papering treatment are carried out to metal base, metallic substrate surface is removed
Rust and other debris, then remove degreasing using absolute ethyl alcohol or acetone cleaning metallic matrix, obtain clean after drying
Net metallic matrix is put into drier and preserves or directly use；2. using brushing, spraying or dipping prepares coating,
Coating layer thickness is controlled by application number of times, and each coating thickness is 10~150 μm；3. the coating after application is in room temperature
Lower solidification, or solidify in a heated condition.
Advantages of the present invention and beneficial effect are：
1st, epoxy radicals wear resistant and impact resistant anticorrosive paint of the present invention without inorganic matter, by component A, B component group
Into, the polyformaldehyde filler containing Graft Epoxy Resin wherein in component A, coating prepared by coating have light weight,
The characteristics of good mechanical property；B component is curing agent.Replace inorganic with low-density, high performance polyformaldehyde particulate
Filler so that coating and coating of the density of coating much smaller than addition inorganic filler after coating and coated solidified；Should
Coating is free of heavy metal, and the coating obtained after paint solidification is nontoxic, pollution-free.
2nd, epoxy resin has suitable application mobility and an excellent antiseptic property, but its wear-resisting and shock resistance etc.
Performance is not good；Polyformaldehyde be difficult to be prepared into can application flow regime, but polyformaldehyde is a kind of tough and tensile resilient
Material, has the advantages that hardness is big, modulus is high, creep resistant, wear-resisting and impact property.The present invention is using poly-
Formaldehyde microparticle surfaces Graft Epoxy Resin technology, the interface that improve between polyformaldehyde particulate and epoxy resin is compatible
Property, and then the respective performance advantage of comprehensive epoxy resin and polyformaldehyde, form one kind and have anti-corrosion, wear-resisting and anti-impact concurrently
Hit coating of function and preparation method thereof.
3rd, the production of the coating of application claims, coating process and common epoxy coating are essentially identical, coating storage
Deposit and have good stability, the wear-resisting of coating, shock resistance and Corrosion Protection are excellent after paint solidification.
4th, the present invention mitigates corrosion-inhibiting coating body because the density of dab layer can be greatly reduced in coating without inorganic matter
The overall weight of system, is conducive to being protected metal material lightweight, so as to play it is spry and light, reduce power consumption,
Many beneficial effects such as energy-saving and emission-reduction.
Specific embodiment
In specific implementation process, in epoxy radicals wear resistant and impact resistant anticorrosive paint of the present invention without inorganic matter, add
The polyformaldehyde particulate of surface grafting epoxy resin is added as filler, the epoxy resin of polyformaldehyde microparticle surfaces grafting
Compatibility is good between the epoxy resin in coating, solves polyformaldehyde filler with epoxy resin because molten to each other
The not good problem of interface compatibility caused by degree parameter differences are larger, it is to avoid in coating filler reunite, separate out,
The disadvantages such as precipitation so that polyformaldehyde filler may be homogenously dispersed in coating and paint spraying solidification after painting
In layer, the polyformaldehyde particulate for being dispersed in coat inside assigns the consistent bulk density of coating material and in a balanced way
Stress distribution, suppresses corrosion-inhibiting coating and the phenomenons such as brittle cracking, underfilm corrosion occurs, and is applied so as to significantly improve anti-corrosion
The mechanical obdurability of layer, wearability, impact resistance and anti-corrosion life.
It is prepared by paint spraying and coating：
The component A of coating, B component are homogenously mixed together and are deployed into the coating for treating application, the application of coating
Technique is comprised the following steps：1. sandblasting or sand papering treatment are carried out to metal base, metallic substrate surface is removed
Rust and other debris, then using absolute ethyl alcohol or acetone cleaning metallic matrix remove degreasing, obtained after drying
Clean metallic matrix is put into drier and preserves or directly use.2. using brushing, spraying, impregnating mode
Prepares coating, coating layer thickness is controlled by application number of times, and each coating thickness is about 10~150 μm, can repeatedly be applied
Dress.3. the coating after application can at room temperature solidify and also solidify under conditions of heating.It is anti-after coated solidified
Rotten coating can be used alone, it is also possible to be supported the use with corresponding intermediate coat or finish paint.
Below, the present invention is further detailed explanation in conjunction with the embodiments.
Embodiment 1
Installed additional between reflux condensing tube and water knockout drum, each part on the clean closed heatproof container with agitating device
The seal for ensureing device should closely be connected.The acefal homopolymer for adding 10 gram particle footpaths to be 20 nanometers in container is micro-
Grain, 100 grams of toluene, 0.1 gram of VTES are stirred at room temperature uniformly, are warming up to refluxing toluene,
Moisture in removing system, then adds 1 gram of cumyl peroxide under conditions of nitrogen protection in three times
In reaction system, the polyformaldehyde particulate for preparing surface grafting silane for 3 hours, reaction knot are then reacted at 120 DEG C
Will be standby in toluene vacuum distillation to clean container after beam.Toluene steams and 1000 is added in backward reaction system
Gram (the g.mol of epoxide equivalent 160~180-1) bisphenol f type epoxy resin, be warming up to 180 DEG C reaction 0.5 hour tie
Shu Fanying, product toluene cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, is grafted
The polyformaldehyde filler of epoxy resin, the filler can dry preservation and also be preserved in toluene.
By 5 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 185~208-1) it is double
Phenol A types epoxy resin, 8 grams of toughener, 0.5 gram of defoamer, 0.5 gram of levelling agent, 0.3 gram of antistatic additive,
0.5 gram of pigment dispersing agent puts into coating grinding equipment and processes 30 minutes, is obtained after 300 mesh sieve net filtrations
The component A of coating, injects canning and storage.Then to 60 grams of cashew nut shell amine of addition in coating component A as solid
Agent, after stirring with brush by paint spraying in metal testing plate surface, solidify two weeks at room temperature.With phase
The polyformaldehyde of the non-grafted epoxy resin of homogenous quantities is added in the coating of same recipe and contrasts.Gained anti-corrosion is applied
The cure shrinkage of material can reduce by 1.1 times, and the water absorption rate of coating can reduce by 55%, and the intensity of coating can be improved
12%, the wearability of coating improves 45%, and impact resistance can improve 51%, and the salt-fog resistant time of coating can
Improve 35%.
Embodiment 2
The copolymerized methanal for adding 200 gram particle footpaths to be 50 microns in the clean heatproof container with agitating device is micro-
Grain, 100 grams of toluene, 2000 grams of vinyltrimethoxy silanes, 30 grams of methyl ethyl ketone peroxides are stirred at room temperature
Uniformly, 125 DEG C are warming up to and react the polyformaldehyde particulate for preparing surface grafting silane for 2 hours, reaction is used after terminating
Toluene cyclic washing removes unreacted silane, then to 20 grams of epoxide equivalents 165~185 of addition in reaction system
(g.mol-1) bisphenol f type epoxy resin, room temperature reaction 24 hours terminates reaction, product toluene cyclic washing,
And be centrifuged or be filtered to remove unreacted epoxy resin, obtain the polyformaldehyde filler of Graft Epoxy Resin, the filler
Preservation can be dried also to be preserved in toluene.
By 200 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 185~208-1)
Bisphenol A type epoxy resin, 19 grams of toughener, 0.3 gram of defoamer, 0.2 gram of adhesion promoter, 0.3 gram of increasing
Thick dose, 0.2 gram of mould inhibitor put into coating grinding equipment and process 30 minutes, obtained final product after 120 mesh sieve net filtrations
To the component A of coating, canning and storage is injected.Then to 5 grams of diethyl triolefins of addition in coating component A as solid
Agent, after stirring with brush by paint spraying in metal testing plate surface, solidify one week at room temperature.With phase
The polyformaldehyde of the non-grafted epoxy resin of homogenous quantities is added in the coating of same recipe and contrasts.Gained anti-corrosion is applied
The cure shrinkage of material can reduce by 1.3 times, and the water absorption rate of coating can reduce by 5%, and the intensity of coating can improve 8%,
The wearability of coating improves 40%, and impact resistance can improve 35%, and the salt-fog resistant time of coating can improve 5%.
Embodiment 3
Installed additional between reflux condensing tube and water knockout drum, each part on the clean closed heatproof container with agitating device
The seal for ensureing device should closely be connected.Added in container acefal homopolymer particulate that 50 gram particle footpaths are 1 micron,
100 grams of dimethylbenzene, 0.1 gram of vinyl methyl diethoxy silane are stirred at room temperature uniformly, are warming up to dimethylbenzene
Backflow, the moisture in removing system, then by 5 grams of cumyl peroxides point three under conditions of nitrogen protection
In secondary addition reaction system, the polyformaldehyde particulate for preparing surface grafting silane for 12 hours is then reacted at 50 DEG C,
Reaction will be standby in dimethylbenzene vacuum distillation to clean container after terminating.Dimethylbenzene is steamed in backward reaction system
Add 100 grams of (g.mol of epoxide equivalent 200~220-1) aliphatic epoxy resin, at room temperature react 24 hours
Terminate reaction, product dimethylbenzene cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, obtains
The polyformaldehyde filler of Graft Epoxy Resin, the filler can dry preservation and also be preserved in dimethylbenzene.
By 10 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 455~556-1) it is double
Phenol F types epoxy resin, 0.5 gram of defoamer, 0.5 gram of levelling agent, 0.1 gram of anti-skinning agent, 0.3 gram of delustering agent,
0.2 gram of light stabilizer, 50 grams of dimethylbenzene, 10 grams of isopropanols put into coating grinding equipment and process 30 minutes, warp
The component A of coating is obtained after 200 mesh sieve net filtrations, canning and storage is injected.Then add in coating component A
Enter 15 grams of TEPAs curing agent, after stirring with infusion process by paint spraying in metal testing plate table
Face, solidifies two weeks at room temperature.Same recipe is added to the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities
Coating in contrast.The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, and the water absorption rate of coating can drop
Low by 35%, the intensity of coating can improve 32%, the wearability of coating improves 55%, and impact resistance can be improved
65%, the salt-fog resistant time of coating can improve 30%.
Embodiment 4
The acefal homopolymer for adding 150 gram particle footpaths to be 50 microns in the clean heatproof container with agitating device is micro-
Grain, 30 grams of ethanol, 30 grams of isopropanols, 10 grams of n-butanols, 40 grams of deionized waters, 20 grams of vinyl methyls two
Methoxy silane, 3 grams of potassium peroxydisulfates are stirred at room temperature uniformly, and room temperature reaction prepares surface grafting silicon in 4 hours
The polyformaldehyde particulate of alkane, reaction removes unreacted silane after terminating with acetone cyclic washing, then to reactant
80 grams of (g.mol of epoxide equivalent 185~195 are added in system-1) novolac epoxy resin, 180 DEG C react 0.5 hour
Terminate reaction, product acetone cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, connect
The polyformaldehyde filler of branch epoxy resin, the filler can dry preservation and also preserve in acetone.
By 140 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 215~230-1)
Novolac epoxy resin, 0.8 gram of defoamer, 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 coating grinding equipment and process 30 minutes, and coating is obtained after 100 mesh sieve net filtrations
Component A, inject canning and storage.Then to 50 grams of Mannich polyamines of addition in coating component A as solidification
Agent, after stirring with infusion process by paint spraying in metal testing plate surface, solidify two weeks at room temperature.With phase
The polyformaldehyde of the non-grafted epoxy resin of homogenous quantities is added in the coating of same recipe and contrasts.Gained anti-corrosion is applied
The cure shrinkage of material can reduce by 1.2 times, and the water absorption rate of coating can reduce by 25%, and the intensity of coating can improve 9%,
The wearability of coating improves 70%, and impact resistance can improve 85%, and the salt-fog resistant time of coating can improve 15%.
Embodiment 5
Added in the clean heatproof container with agitating device copolymerized methanal particulate that 120 gram particle footpaths are 2 microns,
70 grams of acetone, 9 grams of vinyl triacetyl oxosilanes, 5 grams of azodiisobutyronitriles are stirred at room temperature uniformly, 64 DEG C
Reaction prepares the polyformaldehyde particulate of surface grafting silane for 6 hours, and reaction is removed not after terminating with acetone cyclic washing
The silane of reaction, then to 90 grams of (g.mol of epoxide equivalent 210~244 of addition in reaction system-1) bisphenol-A
Type epoxy resin, 140 DEG C reaction 2 hours terminate reaction, product acetone cyclic washing and be centrifuged or cross filter
Unreacted epoxy resin is removed, the polyformaldehyde filler of Graft Epoxy Resin is obtained, the filler can dry preservation
Preserve in acetone.
By 100 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 215~230-1)
Novolac epoxy 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 additive, 30 grams of dimethylbenzene, inputs to coating grinding equipment are processed 30 minutes, through 200 eye mesh screens
The component A of coating is obtained after filtering, canning and storage is injected.Then to 35 grams of addition in coating component A
Acid dianhydride as curing agent, after stirring with spray gun by paint spraying in metal testing plate surface, in 200 DEG C
Lower solidification 24 hours.Same recipe is added to the nano silicon of the non-grafted epoxy resin of phase homogenous quantities
Contrasted in coating.The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, and the water absorption rate of coating can be reduced
10%, the intensity of coating can improve 18%, and the wearability of coating improves 75%, and impact resistance can improve 80%,
The salt-fog resistant time of coating can improve 2%.
Embodiment 6
Installed additional between reflux condensing tube and water knockout drum, each part on the clean closed heatproof container with agitating device
The seal for ensureing device should closely be connected.The copolymerized methanal for adding 50 gram particle footpaths to be 70 nanometers in container is micro-
Grain, 100 grams of toluene, 0.1 gram of vinyltriisopropenyloxysilane are stirred at room temperature uniformly, are warming up to toluene
Backflow, the moisture in removing system then adds instead 5 grams of benzoyl peroxides under conditions of nitrogen protection
Answer in system, the polyformaldehyde particulate for preparing surface grafting silane for 3 hours is then reacted at 105 DEG C, reaction terminates
Afterwards will be standby in toluene vacuum distillation to clean container.Toluene steams and 30 grams of epoxies is added in backward reaction system
(the g.mol of equivalent 455~556-1) bisphenol A type epoxy resin, be warming up to 120 DEG C reaction 5 hours terminate reaction,
Product acetone cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, obtains Graft Epoxy Resin
Polyformaldehyde filler, the filler can dry preservation also in toluene preserve.
By 30 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 1210~244-1)
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 thickener put into coating grinding equipment and process 20 minutes, through 240 mesh sieve net filtrations
The component A of coating is obtained afterwards, injects canning and storage.Then to 57 grams of polyamide of addition in coating component A
(650) as curing agent, after stirring 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 contrasted.
The cure shrinkage of gained anticorrosive paint can reduce by 1.2 times, and the water absorption rate of coating can reduce by 30%, coating it is strong
Degree can improve 22%, the wearability of coating improves 45%, and impact resistance can improve 55%, the salt tolerant of coating
The mist time can improve 30%.
Embodiment 7
Installed additional between reflux condensing tube and water knockout drum, each part on the clean closed heatproof container with agitating device
The seal for ensureing device should closely be connected.The acefal homopolymer for adding 200 gram particle footpaths to be 10 microns in container is micro-
Grain, 300 grams of toluene, 6 grams of vinyl three (2- methoxy ethoxies) silane are stirred at room temperature uniformly, heat up
To refluxing toluene, the moisture in removing system, then by 5 grams of tert-butyl hydroperoxides under conditions of nitrogen protection
Hydrogen is added in reaction system, and the polyformaldehyde particulate for preparing surface grafting silane for 10 hours is then reacted at 120 DEG C,
Reaction will be standby in toluene vacuum distillation to clean container after terminating.Toluene is steamed in backward reaction system and added
30 grams of (g.mol of epoxide equivalent 185~208-1) bisphenol A type epoxy resin, be warming up to 60 DEG C react 10 hours
Terminate reaction, product toluene cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, connect
The polyformaldehyde filler of branch epoxy resin, the filler can dry preservation and also be preserved in toluene.
By 150 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 210~244-1)
Bisphenol A type epoxy resin, 21 grams of dimethylbenzene, 9 grams of isopropanols, 0.1 light stabilizer, 0.1 mould inhibitor, 0.1
Antistatic additive is put into coating grinding equipment and processes 25 minutes, and the A of coating is obtained after 200 mesh sieve net filtrations
Component, injects canning and storage.Then to 29 grams of phthalic anhydrides of addition in coating component A as curing agent,
After stirring with spray gun by paint spraying in metal testing plate surface, in 2 hours at 80 DEG C, be warming up to 120 DEG C
Lower 2 hours, 4 hours at being warming up to 180 DEG C, complete the solidification of coating.With the non-grafted epoxy of phase homogenous quantities
The polyformaldehyde of resin is added in the coating of same recipe and contrasts.The cure shrinkage of gained anticorrosive paint can drop
Low 1.1 times, the water absorption rate of coating can reduce by 20%, and the intensity of coating can improve 35%, the wearability of coating is carried
High by 65%, impact resistance can improve 45%, and the salt-fog resistant time of coating can improve 8%.
Embodiment 8
Installed additional between reflux condensing tube and water knockout drum, each part on the clean closed heatproof container with agitating device
The seal for ensureing device should closely be connected.The acefal homopolymer for adding 90 gram particle footpaths to be 20 microns in container is micro-
Grain, 100 grams of toluene, 25 grams of vinyl methyl dimethoxysilanes are stirred at room temperature uniformly, are warming up to toluene
Backflow, the moisture in removing system then adds 3 grams of cumyl peroxides under conditions of nitrogen protection
In reaction system, the polyformaldehyde particulate for preparing surface grafting silane for 10 hours, reaction knot are then reacted at 120 DEG C
Will be standby in toluene vacuum distillation to clean container after beam.Toluene steams and 30 grams of rings is added in backward reaction system
(the g.mol of oxygen equivalent 455~556-1) bisphenol A type epoxy resin, be warming up to 60 DEG C of reactions and terminate within 10 hours anti-
Should, product toluene cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, obtains grafted epoxy
The polyformaldehyde filler of resin, the filler can dry preservation and also be preserved in toluene.
By 70 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 210~244-1) it is double
Phenol A types epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 0.05 gram of defoamer, 0.05 gram of levelling agent input
Processed 20 minutes to coating grinding equipment, the component A of coating, injection are obtained after 200 mesh sieve net filtrations
Canning and storage.Then to adding 47 grams of polyamide (650) as curing agent in coating component A, stir
Afterwards with spray gun by paint spraying in metal testing plate surface, solidify two weeks at room temperature.With the non-grafted of phase homogenous quantities
The polyformaldehyde of epoxy resin is added in the coating of same recipe and contrasts.The cure shrinkage of gained anticorrosive paint
1.2 times can be reduced, the water absorption rate of coating can reduce by 25%, and the intensity of coating can improve 38%, coating it is wear-resisting
Property improve 67%, impact resistance can improve 49%, and the salt-fog resistant time of coating can improve 12%.
Embodiment 9
Added in the clean heatproof container with agitating device acefal homopolymer particulate that 60 gram particle footpaths are 30 microns,
100 grams of deionized waters, 20 grams of VTESs, 2 grams of potassium peroxydisulfates are stirred at room temperature uniformly,
Be warming up to 60 DEG C and react and prepare within 5 hours the polyformaldehyde particulate of surface grafting silane, reaction terminate after with acetone repeatedly
Washing removes unreacted silane, then to 80 grams of (g.mol of epoxide equivalent 455~556 of addition in reaction system-1)
Bisphenol f type epoxy resin, 60 DEG C reaction 10 hours terminate reaction, product with acetone cyclic washing and from
The heart is filtered to remove unreacted epoxy resin, obtains the polyformaldehyde filler of Graft Epoxy Resin, and the filler can dry
Dry preservation can also be preserved in acetone.
By 40 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 210~244-1) it is double
Phenol A types epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 0.05 gram of defoamer, 0.05 gram of adhesive force promote
Agent is put into coating grinding equipment and processes 20 minutes, and the component A of coating is obtained after 200 mesh sieve net filtrations,
Injection canning and storage.Then to added in coating component A then in coating component A add 49 grams of cashew nut shells
Amine as curing agent, after stirring with spray gun by paint spraying in metal testing plate surface, two are solidified at room temperature
Week.It is added in the coating of same recipe with the polyformaldehyde of the non-grafted epoxy resin of phase homogenous quantities and is contrasted.Institute
The cure shrinkage for obtaining anticorrosive paint can reduce by 1.3 times, and the water absorption rate of coating can reduce by 21%, the intensity of coating
7% can be improved, the wearability of coating improves 75%, and impact resistance can improve 82%, during the salt spray resistance of coating
Between can improve 7%.
Embodiment 10
Added in the clean heatproof container with agitating device copolymerized methanal particulate that 110 gram particle footpaths are 5 microns,
200 grams of ethanol, 12 grams of vinyltriisopropenyloxysilanes, 6 grams of azodiisobutyronitriles are stirred at room temperature
It is even, alcohol reflux is warming up to, reaction prepares the polyformaldehyde of surface grafting silane for 8 hours under the conditions of alcohol reflux
Particulate, reaction removes unreacted silane after terminating with acetone cyclic washing, then to adding 90 in reaction system
Gram (the g.mol of epoxide equivalent 455~556-1) bisphenol A type epoxy resin, 40 DEG C reaction 12 hours terminate reaction,
Product acetone cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, obtains Graft Epoxy Resin
Polyformaldehyde filler, the filler can dry preservation also preserve in acetone.
By 100 grams of polyformaldehyde fillers of Graft Epoxy Resin, 100 grams of (g.mol of epoxide equivalent 210~244-1)
Bisphenol A type epoxy resin, 7 grams of dimethylbenzene, 3 grams of n-butanols, 0.05 gram of defoamer, 0.05 gram of levelling agent are thrown
Enter to coating grinding equipment and process 25 minutes, the component A of coating, note are obtained after 200 mesh sieve net filtrations
Enter canning and storage.Then to added in coating component A then in coating component A add 53 grams of polyamide
(650) as curing agent, after stirring 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 contrasted.
The cure shrinkage of gained anticorrosive paint can reduce by 1.1 times, and the water absorption rate of coating can reduce by 11%, coating it is strong
Degree can improve 15%, and the wearability of coating improves 35%, and impact resistance can improve 83%, the salt spray resistance of coating
Time can improve 12%.
Embodiment result shows that the present invention uses polyformaldehyde microparticle surfaces Graft Epoxy Resin technology, improves poly-
Interface compatibility between the polymer that formaldehyde particulate and epoxy resin both solubility parameters differ greatly, and then
The respective performance advantage of comprehensive epoxy resin and polyformaldehyde.In addition, the coating storage stability of application claims is good,
The production of coating, construction technology and common epoxy coating are essentially identical, and coating is wear-resisting, anti-after paint solidification
Impact and Corrosion Protection are excellent.
In addition, the above, is only preferably feasible embodiment of the invention, it is impossible to limit to the present invention with this
Interest field, a kind of epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter and preparation method thereof,
Apply also for other organic coatings.Therefore, to make other various for technical scheme under this invention and technical thought
It is corresponding to change and deform, still belong within the protection domain that the present invention is covered.
Claims (10)
1. a kind of epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter, it is characterised in that the coating is by A
Component and B component are constituted, in parts by mass, including following component and consumption：
(1) component A：
(2) B component：
Curing agent 0.1~100.
2. according to the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 1, its feature
It is, it is preferred that in parts by mass, including following component and consumption：
(1) component A：
(2) B component：
Curing agent 5~60.
3. according to the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 1, its feature
It is that more than two epoxy-functionals are carried on epoxy molecule, epoxy molecule is aliphatic structure
Or aromatic structure.
4. according to the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 1, its feature
It is that auxiliary agent is defoamer, levelling agent, adhesion promoter, drier, toughener, thickener, pigment
One or more in dispersant, anti-skinning agent, delustering agent, light stabilizer, mould inhibitor, antistatic additive
Any combination.
5. according to the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 1, its feature
It is that dispersant is in toluene, dimethylbenzene, n-butanol, ethanol, isopropanol, acetone, deionized water
Plant or two or more any combination.
6. according to the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 1, its feature
It is that curing agent is divided into two classes：The first kind is that two are carried on aminated compounds, and the molecule of aminated compounds
N-H structures above, solidification agent molecule is aliphatic structure or aromatic structure；Equations of The Second Kind is binary acid, many
First acid or its acid anhydrides, solidification agent molecule are aliphatic structure or aromatic structure.
7. the preparation side of the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in a kind of claim 1
Method, it is characterised in that in clean container by epoxy resin, the polyformaldehyde filler of surface grafting epoxy resin,
After the agitated uniform mixing of auxiliary agent, dispersant, then processed 10~30 minutes with coating grinding equipment, through screen cloth
The component A of coating is obtained after filtering, canning and storage is injected, the component A of coating, B component are evenly mixed in
The coating for treating application is deployed into together.
8. according to the preparation side of the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 7
Method, it is characterised in that the preparation process of the polyformaldehyde filler of surface grafting epoxy resin is as follows：
Amino silane with double bond and polyformaldehyde particulate are reacted generation by the first step in the presence of radical initiator
The polyformaldehyde particulate of grafted silane, the specific requirement of first step reaction includes：1. room temperature to 150 DEG C reaction 0.5~
12 hours；2. the reaction bonus point powder or it is not added with dispersant；3. the material ratio for reacting is amino silane and polyformaldehyde
The mass ratio of particulate is 0.01：1~10：1；
Second step reacts the polyformaldehyde particulate of grafted silane and epoxy resin, the specific requirement bag of second step reaction
Include：1. room temperature to 180 DEG C react 0.5~24 hour；2. the reaction bonus point powder or it is not added with dispersant；3. it is anti-
The material ratio answered is 0.01 with the mass ratio of epoxy resin for polyformaldehyde particulate：1~10：1；
3rd step dispersant cyclic washing is simultaneously centrifuged or is filtered to remove unreacted epoxy resin, is grafted
The polyformaldehyde filler of epoxy resin, filler drying is preserved or preserved in dispersant.
9. according to the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 7, its feature
It is that the silane with double bond meets following two requirements simultaneously：1. more than one is carried on the molecule of amino silane
Carbon-carbon double bond structure；2. at least provided with more than one alkoxide on the molecule of amino silane；Polyformaldehyde
Particulate meets following two requirements simultaneously：1. the chemical composition of polyformaldehyde particulate is acefal homopolymer or copolymerized methanal；
2. the particle diameter of polyformaldehyde particulate is in 20 nanometers~100 micrometer ranges；Radical initiator is in room temperature or heating
Under conditions of can produce the compound of free radical；Dispersant is toluene, dimethylbenzene, n-butanol, ethanol, different
One or more any combination in propyl alcohol, acetone.
10. according to the preparation of the epoxy radicals wear resistant and impact resistant anticorrosive paint without inorganic matter described in claim 7
Method, it is characterised in that the coating process of coating is comprised the following steps：1. sandblasting or sand are carried out to metal base
Paper grinding process, removes the rust and other debris of metallic substrate surface, is then cleaned using absolute ethyl alcohol or acetone
Metallic matrix removes degreasing, and the metallic matrix that cleaning is obtained after drying is put into the interior preservation of drier or directly uses；
2. using brushing, spraying or impregnate prepares coating, coating layer thickness is controlled by application number of times, and each coating thickness is
10~150 μm；3. the coating after application solidifies at room temperature, or solidifies in a heated condition.
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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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