CN106280890A - A kind of butadiene rubber modified epoxy anticorrosive paint of environmental protection and preparation method thereof - Google Patents
A kind of butadiene rubber modified epoxy anticorrosive paint of environmental protection and preparation method thereof Download PDFInfo
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- CN106280890A CN106280890A CN201610721423.1A CN201610721423A CN106280890A CN 106280890 A CN106280890 A CN 106280890A CN 201610721423 A CN201610721423 A CN 201610721423A CN 106280890 A CN106280890 A CN 106280890A
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- butadiene rubber
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- anticorrosive paint
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- environmental protection
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
- C08C19/06—Epoxidation
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
A kind of butadiene rubber modified epoxy anticorrosive paint of environmental protection, it is characterized in that, it is prepared from by following raw material: epoxy resin E51, butadiene rubber, propyleneglycol monobutyl ether, iodosobenzene, methyl three oxygen rhenium, sodium metaperiodate, sodium glutamate, HDI, 1,4 one butanediols, calcium nitrate solution, ammonium dibasic phosphate solution, dodecyl sodium sulfate, sodium stearate, dimethylbenzene, n-butyl alcohol, nano titanium oxide, sodium laureth sulfate, triphenylphosphine, N, N bis-(2 hydroxypropyl) aniline, chloroform, 25% appropriate ammonia.The anticorrosive paint that the present invention provides, has the advantages such as resistance to salt water is strong, antiseptic property good, asepsis environment-protecting.
Description
Technical field
The present invention relates to a kind of anticorrosive paint, the butadiene rubber modified epoxy anticorrosive paint of a kind of environmental protection and
Its preparation method.
Background technology
Anticorrosive paint kind is more, common are epoxy coating, polyurethane coating, the inorganic broken coating of richness etc..Use
Time need to be simultaneous for different corrosive environments, it is possible to by analyzing according to the suitable anticorrosive paint of different rotten candle environmental selection
Different film forming binder, solvent, filler and auxiliary agents etc. must act on exploitation played in anticorrosive paint and have anticorrosion painting targetedly
Material product.Wherein epoxy resin cured product have that mechanical property is good, chemical stability is good, electrical insulating property good and shrinkage factor is low,
Temperature tolerance is good, easily processes the advantages such as low with price, is used widely in paint field, but deposits crosslink density after hardening
Height, in tridimensional network, fragility is big, impact property is poor and first property difference etc. shortcoming, limit it to a certain extent at some
The application of high-technology field.
Author Gao Wei, in " preparation of nanometer modified epoxy anticorrosive paint and performance evaluation " literary composition, selects nano-calcium carbonate
With nano phase ag_2 o as the filler of coating, select silane coupler as the modifying agent of nanoparticle, use chemical modification and
Nanoparticle is distributed in epoxy resin by the mode that ultrasound wave dispersion combines with mechanical agitation, prepares a kind of nano modification
Anti-corrosive paint of epoxy resin.Although this anticorrosive paint anti-wear performance improves, but the adhesive force of coating is
Decline.
Summary of the invention
It is an object of the invention to provide butadiene rubber modified epoxy anticorrosive paint and the preparation side thereof of a kind of environmental protection
Method.
To achieve these goals, present invention employs following technical scheme:
The butadiene rubber modified epoxy anticorrosive paint of a kind of environmental protection, it is characterised in that it is by the raw material system of following weight portion
For forming: epoxy resin E51 200 parts, butadiene rubber 40-50 part, propyleneglycol monobutyl ether 150-200 part, iodosobenzene 8-10
Part, methyl three oxygen rhenium 2-3 part, sodium metaperiodate 3-4 part, sodium glutamate 8-10 part, HDI 12-15 part, Isosorbide-5-Nitrae one
Butanediol 5-8 part, calcium nitrate solution 100-120 part, ammonium dibasic phosphate solution 120-150 part, dodecyl sodium sulfate 5-6 part,
Sodium stearate 3-4 part, dimethylbenzene 150-200 part, n-butyl alcohol 120-150 part, nano titanium oxide 15-20 part, laureth
Sodium sulfate 6-8 part, triphenylphosphine 6-8 part, N, N-bis-(2-hydroxypropyl) aniline 5-6 part, chloroform 20-30 part, 25% ammonia are appropriate.
The butadiene rubber modified epoxy anticorrosive paint of described environmental protection, it is characterised in that its preparation that has the following steps
Form:
(1) butadiene rubber is joined in propyleneglycol monobutyl ether, stirs 20-30min, add iodosobenzene and methyl three oxygen rhenium,
Liter high-temperature is to 70-80 DEG C, and 10-12h is reacted in stirring；Reduction temperature, to 50-60 DEG C, adds sodium metaperiodate, and 2-3h is reacted in stirring,
Adding sodium glutamate, liter high-temperature is to 140-150 DEG C, and 18-20h is reacted in stirring, obtains polyhydroxylated butadiene rubber；
(2) polyhydroxylated butadiene rubber is equipped with agitator, thermometer reactor in, be warming up to 100-110 DEG C,
Carry out vacuum outgas 20-30min, after vacuum outgas, drop to room temperature, add HDI, be warming up to 80-90 DEG C, stir
Mix reaction 3-5h, add Isosorbide-5-Nitrae one butanediol, continue stirring reaction 6-8h, vacuum outgas 20-30min, cooling discharge；
(3) first in calcium nitrate solution, stirring instills ammonium dibasic phosphate solution, uses stirring instillation 25% in this mixed process
The method of ammonia with regulation mixed solution pH value as 10-14, after ripening 2-3h add nano titanium oxide, continue ripening, make
Hydroxyapatite separates out on nano titanium oxide surface and forming core is grown up, and forms titanium dioxide/hydroxyapatite composite mortar；Will
Precipitation in titanium dioxide/hydroxyapatite composite mortar carries out washing, being dried, and obtains titanium dioxide/hydroxyapatite and is combined
Powder；
(4) by dodecyl sodium sulfate and sodium stearate, it is dissolved in the mixed solvent of dimethylbenzene and n-butyl alcohol composition, super under room temperature
After sound wave is uniformly dispersed, under stirring, it is slowly added to titanium dioxide/the hydroxyapatite complex powder being dried, treats that powder body adds
Complete, after stirring, continue ultrasound wave dispersion 2-3h, add epoxy resin E51, be warming up to 95-105 DEG C, evacuation 30-
40min, is cooled to 50-60 DEG C, adds the product of step (2), then is warming up to 90-100 DEG C, stirring reaction 5-8h, adds Laurel
Alcohol polyethers sodium sulfate, triphenylphosphine, again by blender high speed dispersion 30-40min after ultrasound wave dispersion, be slowly added to N, N-bis-
(2-hydroxypropyl) aniline and the solution of chloroform configuration, continue stirring 2-3h, obtain anticorrosive paint.
Described butadiene rubber is Rare Earth butadiene rubber.
The concentration of described calcium nitrate solution is 0.20-0.25mol/L, and described ammonium dibasic phosphate solution concentration is
0.25-0.30mol/L。
Compared with other anti-corrosive paint of epoxy resin, there is advantages that
The present invention is first under methyl three oxygen rhenium is catalyzed, with the double bond initial ring oxidation reaction of iodosobenzene Yu butadiene rubber, then
With sodium metaperiodate catalytic pyrolysis epoxy radicals, prepare polyhydroxylated butadiene rubber；Hydroxyl in polyhydroxylated butadiene rubber
Base again with methyl diphenylene diisocyanate generation polyreaction, then by the way of chemical bond cross-links, join epoxy resin net
In network so that butadiene rubber and epoxy resin have the more preferable compatibility, substantially increase the rigidity of anti-corrosive paint of epoxy resin, painting
Layer adhesive force and thermostability；Select the light base apatite/sharp type nano titanium oxide composite powder of admiring with higher catalysis activity
End, as the filler of coating, is selected dodecyl sodium sulfate and sodium stearate as the modifying agent of nanoparticle, is used chemistry to change
Property and the mode that combines with mechanical agitation of ultrasound wave dispersion nanoparticle is distributed in epoxy resin, impart epoxy resin
Anticorrosive paint is to the NO in airxPhoto-catalysis capability, play purify air purpose；The anticorrosive paint of the present invention can quickly be consolidated
Chemical conversion film, coating has the advantage that outstanding adhesive force, resistant abrasion and Corrosion Protection is strong.
Detailed description of the invention
The butadiene rubber modified epoxy anticorrosive paint of the environmental protection of the present embodiment, it is prepared by the raw material of following weight portion
Form: epoxy resin E51 200 parts, butadiene rubber 50 parts, propyleneglycol monobutyl ether 200 parts, iodosobenzene 10 parts, methyl three oxygen rhenium
3 parts, sodium metaperiodate 4 parts, sodium glutamate 10 parts, HDI 15 parts, Isosorbide-5-Nitrae one butanediol 8 parts, calcium nitrate solution
120 parts, ammonium dibasic phosphate solution 150 parts, dodecyl sodium sulfate 6 parts, sodium stearate 4 parts, dimethylbenzene 200 parts, n-butyl alcohol 150
Part, nano titanium oxide 20 parts, sodium laureth sulfate 8 parts, triphenylphosphine 8 parts, N, N-bis-(2-hydroxypropyl) aniline 6 parts,
Chloroform 30 parts, 25% ammonia are appropriate.
The butadiene rubber modified epoxy anticorrosive paint of the environmental protection of the present embodiment, it has the following steps and is prepared from:
(1) butadiene rubber is joined in propyleneglycol monobutyl ether, stir 30min, add iodosobenzene and methyl three oxygen rhenium, raise
Temperature is to 80 DEG C, and 12h is reacted in stirring；Reduction temperature, to 60 DEG C, adds sodium metaperiodate, stirring reaction 3h, adds sodium glutamate, liter
High-temperature is to 150 DEG C, and 20h is reacted in stirring, obtains polyhydroxylated butadiene rubber；
(2) polyhydroxylated butadiene rubber is equipped with agitator, thermometer reactor in, be warming up to 110 DEG C, carry out
Vacuum outgas 30min, drops to room temperature after vacuum outgas, add HDI, be warming up to 90 DEG C, stirring reaction 5h,
Add Isosorbide-5-Nitrae one butanediol, continue stirring reaction 8h, vacuum outgas 20min, cooling discharge；
(3) first in calcium nitrate solution, stirring instills ammonium dibasic phosphate solution, uses stirring instillation 25% in this mixed process
The method of ammonia with regulation mixed solution pH value as 10-14, after ripening 3h add nano titanium oxide, continue ripening, make hydroxyl
Base apatite separates out on nano titanium oxide surface and forming core is grown up, and forms titanium dioxide/hydroxyapatite composite mortar；By two
Precipitation in titanium oxide/hydroxyapatite composite mortar carries out washing, being dried, and obtains titanium dioxide/hydroxyapatite composite powder
End；
(4) by dodecyl sodium sulfate and sodium stearate, it is dissolved in the mixed solvent of dimethylbenzene and n-butyl alcohol composition, super under room temperature
After sound wave is uniformly dispersed, under stirring, it is slowly added to titanium dioxide/the hydroxyapatite complex powder being dried, treats that powder body adds
Complete, after stirring, continue ultrasound wave dispersion 3h, add epoxy resin E51, be warming up to 105 DEG C, evacuation 40min, it is cooled to
60 DEG C, add the product of step (2), then be warming up to 100 DEG C, stirring reaction 8h, add sodium laureth sulfate, triphenyl
Phosphine, again by blender high speed dispersion 40min after ultrasound wave dispersion, is slowly added to N, N-bis-(2-hydroxypropyl) aniline and chloroform configuration
Solution, continue stirring 3h, obtain anticorrosive paint.
The salt fog of resistance to standard Neutral performance and corrosion-resistant test: use standard Neutral salt fog machine to do neutral salt spray test.By sample
Product (coated weight: 250mg/dm2) put in salt fog machine and spray at 35 DEG C with saline (concentration is 5%, and pH is 6.5-7.5), observe
Sample changed condition.Test result: sample does not occurs red rust in 1500h.
Claims (4)
1. the butadiene rubber modified epoxy anticorrosive paint of an environmental protection, it is characterised in that it is by the raw material of following weight portion
It is prepared from: epoxy resin E51 200 parts, butadiene rubber 40-50 part, propyleneglycol monobutyl ether 150-200 part, iodosobenzene 8-10
Part, methyl three oxygen rhenium 2-3 part, sodium metaperiodate 3-4 part, sodium glutamate 8-10 part, HDI 12-15 part, Isosorbide-5-Nitrae one
Butanediol 5-8 part, calcium nitrate solution 100-120 part, ammonium dibasic phosphate solution 120-150 part, dodecyl sodium sulfate 5-6 part,
Sodium stearate 3-4 part, dimethylbenzene 150-200 part, n-butyl alcohol 120-150 part, nano titanium oxide 15-20 part, laureth
Sodium sulfate 6-8 part, triphenylphosphine 6-8 part, N, N-bis-(2-hydroxypropyl) aniline 5-6 part, chloroform 20-30 part, 25% ammonia are appropriate.
The butadiene rubber modified epoxy anticorrosive paint of environmental protection the most according to claim 1, it is characterised in that its just like
Lower step is prepared from:
(1) butadiene rubber is joined in propyleneglycol monobutyl ether, stirs 20-30min, add iodosobenzene and methyl three oxygen rhenium,
Liter high-temperature is to 70-80 DEG C, and 10-12h is reacted in stirring；Reduction temperature, to 50-60 DEG C, adds sodium metaperiodate, and 2-3h is reacted in stirring,
Adding sodium glutamate, liter high-temperature is to 140-150 DEG C, and 18-20h is reacted in stirring, obtains polyhydroxylated butadiene rubber；
(2) polyhydroxylated butadiene rubber is equipped with agitator, thermometer reactor in, be warming up to 100-110 DEG C,
Carry out vacuum outgas 20-30min, after vacuum outgas, drop to room temperature, add HDI, be warming up to 80-90 DEG C, stir
Mix reaction 3-5h, add Isosorbide-5-Nitrae one butanediol, continue stirring reaction 6-8h, vacuum outgas 20-30min, cooling discharge；
(3) first in calcium nitrate solution, stirring instills ammonium dibasic phosphate solution, uses stirring instillation 25% in this mixed process
The method of ammonia with regulation mixed solution pH value as 10-14, after ripening 2-3h add nano titanium oxide, continue ripening, make
Hydroxyapatite separates out on nano titanium oxide surface and forming core is grown up, and forms titanium dioxide/hydroxyapatite composite mortar；Will
Precipitation in titanium dioxide/hydroxyapatite composite mortar carries out washing, being dried, and obtains titanium dioxide/hydroxyapatite and is combined
Powder；
(4) by dodecyl sodium sulfate and sodium stearate, it is dissolved in the mixed solvent of dimethylbenzene and n-butyl alcohol composition, super under room temperature
After sound wave is uniformly dispersed, under stirring, it is slowly added to titanium dioxide/the hydroxyapatite complex powder being dried, treats that powder body adds
Complete, after stirring, continue ultrasound wave dispersion 2-3h, add epoxy resin E51, be warming up to 95-105 DEG C, evacuation 30-
40min, is cooled to 50-60 DEG C, adds the product of step (2), then is warming up to 90-100 DEG C, stirring reaction 5-8h, adds Laurel
Alcohol polyethers sodium sulfate, triphenylphosphine, again by blender high speed dispersion 30-40min after ultrasound wave dispersion, be slowly added to N, N-bis-
(2-hydroxypropyl) aniline and the solution of chloroform configuration, continue stirring 2-3h, obtain anticorrosive paint.
The butadiene rubber modified epoxy anticorrosive paint of environmental protection the most according to claim 1 and 2, it is characterised in that institute
The butadiene rubber stated is Rare Earth butadiene rubber.
The butadiene rubber modified epoxy anticorrosive paint of environmental protection the most according to claim 1 and 2, it is characterised in that institute
The concentration of the calcium nitrate solution stated is 0.20-0.25mol/L, and described ammonium dibasic phosphate solution concentration is 0.25-0.30mol/
L。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610721423.1A CN106280890A (en) | 2016-08-25 | 2016-08-25 | A kind of butadiene rubber modified epoxy anticorrosive paint of environmental protection and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610721423.1A CN106280890A (en) | 2016-08-25 | 2016-08-25 | A kind of butadiene rubber modified epoxy anticorrosive paint of environmental protection and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069879A (en) * | 2013-03-25 | 2014-10-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method for titanium dioxide/hydroxyapatite composite photocatalyst |
| CN104610845A (en) * | 2015-01-28 | 2015-05-13 | 芜湖县双宝建材有限公司 | Modified epoxy resin anticorrosive paint |
| CN105601770A (en) * | 2016-02-01 | 2016-05-25 | 浙江大学 | Polyhydroxy polybutadiene liquid rubber and controllable preparation method thereof |
-
2016
- 2016-08-25 CN CN201610721423.1A patent/CN106280890A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069879A (en) * | 2013-03-25 | 2014-10-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method for titanium dioxide/hydroxyapatite composite photocatalyst |
| CN104610845A (en) * | 2015-01-28 | 2015-05-13 | 芜湖县双宝建材有限公司 | Modified epoxy resin anticorrosive paint |
| CN105601770A (en) * | 2016-02-01 | 2016-05-25 | 浙江大学 | Polyhydroxy polybutadiene liquid rubber and controllable preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 机械工业部科学技术司: "《机械工业胶接密封技术》", 31 August 1984, 机电工程编辑部 * |
| 钱苗根: "《现代表面工程》", 30 September 2012, 上海交通大学出版社 * |
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