CN107722792A - A kind of preparation method with high anticorrosive property energy epoxy coating - Google Patents
A kind of preparation method with high anticorrosive property energy epoxy coating Download PDFInfo
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- CN107722792A CN107722792A CN201711110779.2A CN201711110779A CN107722792A CN 107722792 A CN107722792 A CN 107722792A CN 201711110779 A CN201711110779 A CN 201711110779A CN 107722792 A CN107722792 A CN 107722792A
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- coating
- epoxy resin
- silane coupler
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- eteo
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- 229920006334 epoxy coating Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical class CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000012986 modification Methods 0.000 claims abstract description 25
- 230000004048 modification Effects 0.000 claims abstract description 24
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000004952 Polyamide Substances 0.000 claims abstract description 9
- 229920002647 polyamide Polymers 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 229910000077 silane Inorganic materials 0.000 claims description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- ADMWVBXCJSMQLF-UHFFFAOYSA-N C(C)O.[Si] Chemical compound C(C)O.[Si] ADMWVBXCJSMQLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 239000000945 filler Substances 0.000 abstract description 6
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 229910000975 Carbon steel Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000010962 carbon steel Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical class C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical class C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- -1 silicon Alkane Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
A kind of preparation method with high anticorrosive property energy epoxy coating of the present invention, belong to the technical field of erosion shield.2 (3,4 epoxycyclohexyl) ethyl triethoxysilanes (ETEO) are prepared using hydrosilylation, surface modification is carried out to nano silicon using ETEO；Using epoxy resin as coated substrate, the Nano-meter SiO_2 of ETEO modifications2For filler, polyamide (PA) is curing agent, prepares epoxy coating.ETEO of the present invention carries out surface modification to nano silicon makes nano particle show lipophile, it may be uniformly dispersed in epoxy resin, improve the interface compatibility between filler and epoxy resin, make coating finer and close while shielding action is increased, reduce the diffusion admittance of corrosive medium and suppress the progress of corrosion reaction process, enable coating that there is high anticorrosive property.
Description
Technical field
The invention belongs to the technical field of erosion shield, is related to a kind of epoxy resin for adding modified manometer silicon dioxide
The preparation method of coating, so as to improve the Corrosion Protection of epoxy coating.
Background technology
Carbon steel is the metal base that is most widely used in the world at present, but carbon steel in atmospheric conditions easily by moisture with
Oxygen corrodes, and seriously constrains its application and development.Organic coating has excellent barrier properties and the moon with metal coating
Pole protectiveness makes carbon steel from the harm of corrosion.The superior adhesion that its epoxy resin (EP) is formed after coating, is that other have
Machine coating is too far behind to catch up, and anticorrosive coating most widely used in the world at present.But epoxy resin is in use
Phenomena such as coating bubbling occurs, comes off, so as to have influence on protection effect of the coating to metallic matrix.So epoxy resin is entered
Row is modified, and the Corrosion Protection for strengthening coating is one of important research direction of epoxy coating.
Domestic and international numerous studies show that nano material with excellent performance due to being widely used in scientific experiment
In epoxy coating, to improve the Corrosion Protection of coating.Nano silicon has hardness height, refractive index is low, price is low
Many advantages, such as honest and clean, therefore it is often used as the filler of coating.Add after nano silicon coating abrasion performance is excellent, transparency
Height, cost are considerable, great development prospect.However, nano-silica surface there are many oh groups, its surface is presented hydrophilic
Property, cause nano silicon to be added to and situations such as reuniting, precipitating is produced in coating, coating storage characteristics difference may be caused or even lost
The problems such as effect.
The content of the invention
The technical problem to be solved in the present invention is the problem of being directed to background technology, to improve the anticorrosion of epoxy coating
Performance, nano silicon is modified using new structure silane coupler, and added it in epoxy resin-base,
The more excellent coating of Corrosion Protection is prepared on carbon steel surface.
A kind of preparation method of epoxy resin-nano silicon erosion shield provided by the invention, synthesize a kind of new
The silane coupler of type structure is modified the surface of nano silicon, so as to improve nano silicon and epoxy resin
Between compatibility it is bad the problem of, improve coating antiseptic erosion ability, avoid failure of the coating during working stock, precipitation etc.
Disadvantage.
Following specific technical scheme is provided to solve the technical problem to be solved in the present invention.
A kind of preparation method with high anticorrosive property energy epoxy coating, there is the nanometer for preparing silane coupler modification
Silica dioxide granule, the process for preparing composite epoxy resin coating；
The described nanometer silicon dioxide particle for preparing silane coupler modification has following steps：
A. weigh 2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane (ETEO) and be used as silane coupler；
B. nano grade silica particles are added in absolute ethyl alcohol, are uniformly mixed to obtain nano silicon-second
Alcohol suspension；
C. the pH to 2~3 of nano silicon-alcohol suspension is adjusted, in N2Silane coupler is added dropwise under atmosphere and goes
Ionized water simultaneously reacts 6h in 65 DEG C of water-baths, and reaction obtains silane coupler modification nano silicon-ethanol after terminating hangs
Supernatant liquid；Wherein the mass ratio of nano silicon and silane coupler is 10:5.3~5.5；
D. nano silicon-alcohol suspension of silane coupler modification is positioned over 60 DEG C of bakings after washing centrifuges
24h is dried in case, the nano grade silica particles for obtaining silane coupler modification (are labeled as ETEO-SiO2)；
The described composite epoxy resin erosion shield for preparing has following steps：
E. 100 mass parts epoxy resin (being labeled as EP) are dissolved in organic solvent；
F. the nano grade silica particles of 5 mass parts silane couplers modification are weighed, are added in epoxy resin, at a high speed
Cutter stirs 30min, obtains well mixed composite epoxy resin paint and (is labeled as ETEO-SiO2/EP)；
G. 40~70 mass parts polyamide curing agents, 1~3 mass parts levelling agent are taken, 2~5 mass parts defoamers are added to
In composite epoxy resin paint；Stirring is sprayed on the surface of steel plate cleaned up until after well mixed under high-speed shearing machine,
Solidify 4h at 60 DEG C again, obtain with high anticorrosive property energy epoxy coating.
The above method is obtained, and there is high anticorrosive property energy epoxy coating mainly to be gathered by matrix epoxy resin, curing agent
Acid amides, the nano silicon composition of filler 2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane (ETEO) modification.Into
Coating has remarkable Corrosion Protection and excellent water resistance after film.Coating of the present invention is free of heavy metal, coating
It is nontoxic after solidification, pollution-free.The nanometer titanium dioxide of 2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane (ETEO) modification
Silicon is excellent in compatibility in the epoxy, ensure that the chemical stability of coating.
The present invention is that one kind can strengthen nano-silicon dioxide particle and compatibility and give full play to its anti-corrosion in organic matrix
Lose the method for effect.This method preparation technology is simple, and environment will not be polluted.In particular to so far, with 2- (3,4-
7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane (ETEO) modification Nano-meter SiO_22Technology is there has been no disclosure, more not by this silicon
The nano grade silica particles of alkane coupling agent modification form coating together as filler and epoxy resin-base, curing agent, are used for
Improve this field of carbon steel face coat Corrosion Protection.
2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane (ETEO) as silane coupler can use existing
Some products, but coating of the invention is more suitable for using the homemade ETEO of silicon-hydrogen additive reaction method of the present invention.The present invention's
Silane coupler can be prepared by following processes：1,2- epoxy -4- vinyl cyclohexanes are dissolved in toluene, are put into container；
In N2Under atmosphere, Karstedt catalyst is added, while reaction temperature is risen to 60~65 DEG C, then triethoxysilane is added dropwise
Into 1,2- epoxies -4- vinyl cyclohexanes-toluene reaction solution, after being added dropwise, high-speed stirred 6h, reaction product dissolving are kept
In toluene；After toluene rotary distillation is gone out, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane (ETEO) nothing is obtained
Color transparency liquid；Wherein the mass ratio of 1,2- epoxies -4- vinyl cyclohexanes and triethoxysilane is 5:7.2~7.3,
Karstedt catalyst amounts are reactant (1,2- epoxy -4- vinyl cyclohexanes and triethoxysilane) gross masses
0.001%.Karstedt catalyst components are 1,3- divinyl -1,1,3,3- tetramethyl disiloxanes platinum (0).
The method that the present invention prepares 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane (ETEO), belongs to pioneering,
Not only process is simple, prepares cost is less than existing product, and ETEO is particularly suited for the preparation of epoxy coating of the present invention,
Have the function that to raising epoxy coating Corrosion Protection positive.
In b step, nano grade silica particles are added into absolute ethyl alcohol can be by every gram of nano grade silica particles
With 20mL absolute ethyl alcohols preferably.
The most handy glacial acetic acid of pH value is adjusted in step c.
In step e, the organic solvent of dissolved epoxy compounds the solution of n-butanol for dimethylbenzene, V in solutionDimethylbenzene:
VN-butanol=3:1.In step e, described epoxy resin, model E-51 epoxy resin can be selected.
In g steps, the molecular weight of polyamide curing agent is Mw=650；The rotating speed of high-speed shearing machine could be arranged to 800
Rev/min.
The present invention is prepared for 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane using hydrosilylation, is used for
Modified manometer silicon dioxide, using the chemical group containing amphiphilic in organosilane molecules, mineral surfaces can both be carried out
Modification, chemical reaction can occur with polymer again or form the characteristic of hydrogen bond action, the surface of nano silicon is carried out
It is modified, its surface is changed into lipophile by hydrophily, so as to improve the interface between nano silicon and epoxy resin-base
Compatibility.This preparation process is succinctly environmentally friendly, solves the problem of common fillers bad dispersibility in coating material.Organosilan
Organic material and inorganic material are used into silane coupler as tie, it is by chemical bonds that nano particle is fine with matrix
Connect, interaction and dissolubility between reinforcer and coated substrate (epoxy resin), in increase shielding action
Increase the crosslink density of coating simultaneously, make coating finer and close, reduce the diffusion admittance of corrosive medium and suppress corrosion reaction
The progress of journey, so as to reach more preferably anticorrosion ability, efficiently solve failure of the epoxy coating during storage
Problem.
Brief description of the drawings
Fig. 1 is the proton magnetic of 2- made from embodiment 1 (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane (ETEO)
Resonance spectrogram (1) and chemical formula H-NMR.
Fig. 2 is the ETEO-SiO of embodiment 22Synthesis mechanism figure.
Fig. 3 is ETEO-SiO made from embodiment 22X-ray photoelectron spectroscopic analysis figure (XPS).A is score, b C
1s peaks, c are O 1s peaks, and d is Si 2p peaks.
Fig. 4 is ETEO-SiO made from embodiment 22With Nano-meter SiO_22Sedimentation experiment macroscopical picture, wherein Nano-meter SiO_22
With being respectively figure a and figure b in toluene in water；ETEO-SiO2With being respectively figure c and figure d in toluene in water.
Fig. 5 is ETEO-SiO made from embodiment 32SiO made from/EP, embodiment 42/ EP and EP tri- made from embodiment 5
Kind coating soaks the comparison diagram of the electrochemical impedance spectroscopy of 500 hours in 3.5%NaCl solution.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.
The preparation of the silane coupler 2- of embodiment 1 (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane
5g 1 is weighed, 2- epoxy -4- vinyl cyclohexanes are dissolved in appropriate toluene, are added in 250ml three-necked flasks.
In N2Under atmosphere, add 10ppm Karstedt catalyst and reaction temperature is risen to 65 DEG C simultaneously, then by 7.24g triethoxysilicanes
Alkane is added dropwise in reaction solution, after being added dropwise, keeps 800 revs/min of high-speed stirred 6h, reaction product is dissolved in toluene；Will
After toluene rotary distillation goes out, the target production of 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane colourless transparent liquid is obtained
Thing.
Fig. 1 provides the proton of 2- made from the present embodiment (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane (ETEO)
Magnetic resonance spectrogram (1) and chemical formula H-NMR.The δ 0.5 occurred in product is-CH2- Si- multiplet, 2- (3,4- epoxy hexamethylenes
Alkyl) ethyl triethoxysilane successfully synthesizes.
The surface modification of the nano silicon of embodiment 2
By 10g Nano particles of silicon dioxide, high rotating speed stirs in 200ml ethanol at ambient temperature.Treat silica point
After dissipating uniformly, nano silicon-alcohol suspension pH value is adjusted to 2~3 using glacial acetic acid.In N2Under atmosphere, by 5.4g silicon
Alkane coupling agent is slowly added dropwise into nano silicon-alcohol suspension with appropriate amount of deionized water, by temperature liter after being added dropwise
To 60 DEG C, 12h is heated in holding under reflux conditions.After reaction terminates, by nano silicon-alcohol suspension of ETEO modifications
Repeatedly centrifugation, vacuum drying chamber drying 48h is put into after being washed using ethanol, had both obtained modified nanometer silicon dioxide particle
(before namely involved " nano grade silica particles of ETEO modifications ", labeled as ETEO-SiO2)。
The silane coupler that the present embodiment uses, make 2- made from the process of embodiment 1 (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl
Triethoxysilane.
Fig. 2 provides the ETEO-SiO of the present embodiment2Synthesis mechanism figure.
Fig. 3 provides ETEO-SiO made from the present embodiment2X-ray photoelectron spectroscopic analysis figure (XPS).A is score, b
For C 1s peaks, c is O 1s peaks, and d is Si 2p peaks.Nano silicon after the processing of Fig. 3 display surfaces has C 1s, O 1s, Si
The appearance of the key mappings such as 2p characteristic peak, C-O-C, Si-C, C-O-C demonstrates the presence of silane coupler, the nanometer that surface is modified
Silica is successfully prepared.
Fig. 4 provides Nano-meter SiO_22The ETEO-SiO obtained with the present embodiment2Sedimentation experiment macroscopical picture, wherein nanometer
SiO2With being respectively figure a and figure b in toluene in water；ETEO-SiO2With being respectively figure c and figure d in toluene in water.Can by Fig. 4
To see, the nano silicon (ETES-SiO after silane coupler is handled2) more stable in dimethylbenzene, without place
The Nano-meter SiO_2 of reason2It is more stable in water.After surface treatment, the hydrophobicity increase of nano silicon, it can stablize and deposit
In organic solvent.
The preparation of the epoxy resin composite coating of embodiment 3
100g epoxy resin is added in the complex solvent of appropriate n-butanol and dimethylbenzene, is separately added into 5g ETEO
Nano grade silica particles, the 40~70g polyamide curing agent high-speed stirreds 30min of modification.After stirring terminates, steel plate is carried out
Steel plate is then put into 60 DEG C of baking ovens by spraying solidifies 4h, and it is 80~100 μm that coating layer thickness, which is made,.
In the complex solvent of n-butanol and dimethylbenzene, with adding curing agent while 1~3g levelling agents can also be added, 2
~5g defoamers.
The plain steel that experiment uses is Q235 steel plates, and obtained plate size is after processed：12cm×5cm×2mm.
Surface of steel plate is cleaned up with ethanol using preceding, dried in vacuum drying chamber.
Because this experiment coated substrate is epoxy resin, therefore select dimethylbenzene and n-butanol complex solvent, specific ratio
It is by volume：Dimethylbenzene:N-butanol=3:1.
Embodiment 4 is used as comparative example --- Nano-meter SiO_22Particle does not carry out surface modification
100g epoxy resin is added in appropriate solvent (n-butanol and dimethylbenzene), is separately added into 5g SiO2Nanometer
Particle and 40~70g polyamide curing agent high-speed stirreds 30min.After stirring terminates, steel plate is sprayed and then put steel plate
Enter in 60 DEG C of baking ovens and solidify 4h, it is 80~100 μm that coating layer thickness, which is made,.
The plain steel that experiment uses is Q235 steel plates, and obtained plate size is after processed：12cm×5cm×2mm.
Surface of steel plate is cleaned up with ethanol using preceding, dried in vacuum drying chamber.
The dimethylbenzene of experimental selection similarly to Example 3 and n-butanol complex solvent.
Embodiment 5：As comparative example --- do not add Nano-meter SiO_22Particle
100g epoxy resin is added in appropriate solvent (n-butanol and dimethylbenzene), both without addition ETES-SiO2
Nano particle, also without addition SiO2Nano particle, add 40~70g polyamide curing agent high-speed stirreds 30min.Stirring terminates
Afterwards, steel plate is sprayed that then steel plate is put into 60 DEG C of baking ovens and solidifies 4h, it is 80~100 μm that coating layer thickness, which is made,.
Test the plain steel that uses and to the cleaning treatment of matrix with embodiment 3,4.
Experimental selection dimethylbenzene same as Example 3 and n-butanol complex solvent.
Embodiment 4,5 is with embodiment 3 with the coating of epoxy resin making coatings matrix through soaking 500h in 3.5%NaCl solution
The comparison of low-frequency impedance modulus provided by Fig. 5.Three kinds of coatings are in the low-frequency impedance that soak time is 500h as can be seen from Figure 5
Modulus is reduced to 6.4 × 10 with the increase of soak time, the EP coatings of embodiment 58Ω；The SiO of embodiment 42/ EP coatings drop
It is low to 4.4 × 109Ω；And the ETEO-SiO of embodiment 32Its value of/EP coatings is still stablized 3 × 1010More than Ω.This result
Also indicate that ETEO-SiO of the present invention2/ EP coatings can provide stronger corrosion protection ability.
Claims (5)
1. a kind of preparation method with high anticorrosive property energy epoxy coating, there is the nanometer two for preparing silane coupler modification
Silicon oxide particle, the process for preparing composite epoxy resin coating；
The described nanometer silicon dioxide particle for preparing silane coupler modification has following steps：
A. 2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl triethoxysilane is weighed as silane coupler；
B. nano grade silica particles are added in absolute ethyl alcohol, are uniformly mixed to obtain nano silicon-ethanol and hang
Supernatant liquid；
C. the pH to 2~3 of nano silicon-alcohol suspension is adjusted, in N2Silane coupler and deionized water are added dropwise under atmosphere
And 6h is reacted in 65 DEG C of water-baths, reaction obtains nano silicon-alcohol suspension of silane coupler modification after terminating；Its
The mass ratio of middle nano silicon and silane coupler is 10:5.3~5.5；
D. nano silicon-alcohol suspension of silane coupler modification is positioned in 60 DEG C of baking ovens after washing centrifuges
24h is dried, obtains the nano grade silica particles of silane coupler modification；
The described composite epoxy resin coating for preparing has following steps：
E. 100 mass parts epoxy resin are dissolved in organic solvent；
F. the nano grade silica particles of 5 mass parts silane couplers modification are weighed, are added in epoxy resin, in high speed shear
Machine stirs 30min, obtains well mixed composite epoxy resin paint；
G. 40~70 mass parts polyamide curing agents, 1~3 mass parts levelling agent are taken, 2~5 mass parts defoamers are added to compound
In epoxy coating；Stirring is sprayed on the surface of steel plate cleaned up until after well mixed, then solidifies 4h at 60 DEG C,
Obtain the epoxy coating with high anticorrosive property energy.
2. the preparation method according to claim 1 with high anticorrosive property energy epoxy coating, it is characterised in that institute
The silane coupler stated, prepared by following processes：1,2- epoxy -4- vinyl cyclohexanes are dissolved in toluene, are put into container
In；In N2Under atmosphere, add Karstedt catalyst and reaction temperature is risen to 60~65 DEG C simultaneously, then triethoxysilane is dripped
Add in 1,2- epoxies -4- vinyl cyclohexanes-toluene reaction solution, after being added dropwise, keep high-speed stirred 6h, reaction product is molten
Solution is in toluene；After toluene rotary distillation is gone out, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane (ETEO) is obtained
Colourless transparent liquid；Wherein the mass ratio of 1,2- epoxies -4- vinyl cyclohexanes and triethoxysilane is 5:7.2~7.3,
Karstedt catalyst amounts are the 0.001% of reactant gross mass.
3. the preparation method according to claim 1 with high anticorrosive property energy epoxy coating, it is characterised in that
In step e, described epoxy resin, model E-51；Described organic solvent compounds the solution of n-butanol, solution for dimethylbenzene
Middle VDimethylbenzene:VN-butanol=3:1.
4. the preparation method according to claim 1 or 2 with high anticorrosive property energy epoxy coating, its feature exist
In, it is described in step c, adjust pH value with glacial acetic acid.
5. the preparation method according to claim 1 or 2 with high anticorrosive property energy epoxy coating, its feature exist
In, in g steps, described polyamide curing agent, molecular weight Mw=650.
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| CN108753100A (en) * | 2018-05-03 | 2018-11-06 | 东南大学 | A kind of water-base epoxy concrete repair interfacial agents and preparation method thereof |
| CN109233562A (en) * | 2018-08-09 | 2019-01-18 | 苏州市泽镁新材料科技有限公司 | A kind of anticorrosive coating for metal surface |
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