CN106349886A - Waterproof cis-1,4-polybutadiene rubber modified epoxy resin anticorrosive paint and preparation method thereof - Google Patents

Waterproof cis-1,4-polybutadiene rubber modified epoxy resin anticorrosive paint and preparation method thereof Download PDF

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Publication number
CN106349886A
CN106349886A CN201610720866.9A CN201610720866A CN106349886A CN 106349886 A CN106349886 A CN 106349886A CN 201610720866 A CN201610720866 A CN 201610720866A CN 106349886 A CN106349886 A CN 106349886A
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butadiene rubber
add
anticorrosive paint
aniline
stirring
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CN201610720866.9A
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Chinese (zh)
Inventor
陈宗宝
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MAANSHANG CAISHIJI PAINT CO Ltd
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MAANSHANG CAISHIJI PAINT CO Ltd
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Priority to CN201610720866.9A priority Critical patent/CN106349886A/en
Publication of CN106349886A publication Critical patent/CN106349886A/en
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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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C08L2205/20—Hollow spheres

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a waterproof cis-1,4-polybutadiene rubber modified epoxy resin anticorrosive paint. The invention is characterized in that the paint is prepared from an epoxy resin E51, cis-1,4-polybutadiene rubber, dichlorobenzene, benzoyl hydroperoxide, molybdenum trioxide, sodium periodate, sodium tartrate, lysine diisocyanate, diethylaminoethanol, aniline, polystyrene hollow microspheres, phosphoric acid, ammonium persulfate, stearin, dimethylbenzene, n-butanol, nano tin oxide, nano magnesium oxide, dodecyl alcohol ether sodium sulfate, bis imidazolidinyl urea, N,N-di(2-hydroxypropyl) aniline, chloroform and a proper amount of deionized water. The anticorrosive paint provided by the invention has the advantages of high saline water resistance, favorable corrosion resistance, no toxicity and environment friendliness and the like.

Description

A kind of butadiene rubber modified epoxy anticorrosive paint of waterproof and preparation method thereof
Technical field
The present invention relates to a kind of anticorrosive paint, the butadiene rubber modified epoxy anticorrosive paint of especially a kind of waterproof and Its preparation method.
Background technology
Anticorrosive paint species is more, common are epoxy coating, polyurethane coating, inorganic rich broken coating etc..Use When different corrosive environments need to be simultaneous for according to the suitable anticorrosive paint of different rotten candle environmental selection, also can be by analysis Different film forming binder, solvent, filler and auxiliary agent etc. must act on exploitation played in anticorrosive paint and have targetedly anti-corrosion painting 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, easy processing and the low advantage of 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 the shortcomings of, limit it to a certain extent some The application of high-technology field.
Author Gao Wei in " preparation of nanometer modified epoxy anticorrosive paint and performance evaluation " literary composition, from nano-calcium carbonate With nano phase ag_2 o as coating filler, from silane coupler as nanoparticle modifying agent, using chemical modification and Nanoparticle is distributed in epoxy resin the mode that ultrasound wave dispersion is combined with mechanical agitation, prepares a kind of nano modification Anti-corrosive paint of epoxy resin.Although this anticorrosive paint anti-wear performance improves, the adhesive force of coating is but Decline.
Content of the invention
It is an object of the invention to provide a kind of butadiene rubber modified epoxy anticorrosive paint of waterproof and its preparation side Method.
To achieve these goals, present invention employs following technical scheme:
A kind of butadiene rubber modified epoxy anticorrosive paint of waterproof it is characterised in that its by following weight portion raw material system Standby form: 200 parts of epoxy resin e51, butadiene rubber 40-50 part, dichloro-benzenes 150-200 part, benzoyl hydroperoxide 8-10 part, three Molybdenum oxide 2-3 part, sodium metaperiodate 3-4 part, sodium tartrate 8-10 part, lysinediisocyanate 12-15 part, diethylaminoethanol 5-8 part, aniline 10-12 part, polystyrene hollow microsphere 5-6 part, phosphoric acid 5-6 part, Ammonium persulfate. 2-3 part, tristerin 5-6 part, dimethylbenzene 150-200 part, n-butyl alcohol 120-150 part, nano tin dioxide 12-15 part, nano magnesia 15-20 part, ten Dialkyl group ether sulfate 6-8 part, double imidazolidinyl urea 6-8 part, n, n- bis- (2- hydroxypropyl) aniline 5-6 part, chloroform 20-30 Part, appropriate deionized water.
Butadiene rubber modified epoxy anticorrosive paint preparation it is characterised in that it has the following steps of described waterproof Form:
(1) butadiene rubber is added in dichloro-benzenes, stirs 20-30min, add benzoyl hydroperoxide and molybdenum trioxide, rise high temperature Spend to 70-80 DEG C, stirring reaction 10-12h；Reduce temperature to 50-60 DEG C, add sodium metaperiodate, stirring reaction 2-3h, add wine Stone acid sodium, rises high-temperature to 140-150 DEG C, and stirring reaction 18-20h obtains polyhydroxylated butadiene rubber；
(2) by polyhydroxylated butadiene rubber add equipped with agitator, thermometer reactor in, be warming up to 100-110 DEG C, Carry out vacuum outgass 20-30min, after vacuum outgass, drop to room temperature, add lysinediisocyanate, be warming up to 80-90 DEG C, stir Mix reaction 3-5h, add diethylaminoethanol, continue stirring reaction 6-8h, vacuum outgass 20-30min, cooling discharge；
(3) by aniline, polystyrene hollow microsphere, phosphoric acid and the deionized water mixing being equivalent to 8-10 times of aniline weight portion, stir Mix uniformly, add nano magnesia and nano tin dioxide, after stirring 1-2h, add Ammonium persulfate., continue stirring 20-24h, obtain Hydrophobic nanoparticles；
(4) by tristerin, it is dissolved in dimethylbenzene and the mixed solvent of n-butyl alcohol composition, under room temperature, ultrasound wave is uniformly dispersed Afterwards, it is slowly added to the hydrophobic nanoparticles of drying under stirring, treats that nano-particle adds, after stirring, continue ultrasonic Wavelength-division dissipates 2-3h, adds epoxy resin e51, is warming up to 95-105 DEG C, and evacuation 30-40min is cooled to 50-60 DEG C, adds step Suddenly the product of (2), then it is warming up to 90-100 DEG C, stirring reaction 5-8h, add dodecyl ether sulfate, double imidazolidinyl Urea, disperses 30-40min at a high speed with blender again after ultrasound wave dispersion, is slowly added to n, n- bis- (2- hydroxypropyl) aniline and chloroform The solution of configuration, continues stirring 2-3h, obtains anticorrosive paint.
Described butadiene rubber is Rare Earth butadiene rubber, and the concentration of described phosphoric acid is 1-1.2mol/l.
Compared with other anti-corrosive paint of epoxy resin, the invention has the following beneficial effects:
First under molybdenum trioxide catalysis, there is epoxidation reaction with the double bond of benzoyl hydroperoxide and butadiene rubber in the present invention, then With sodium metaperiodate catalytic pyrolysiss epoxy radicals, prepare polyhydroxylated butadiene rubber；Hydroxyl in polyhydroxylated butadiene rubber There is polyreaction with lysinediisocyanate in base, then be added to epoxy networks again by way of chemical bond crosslinking In so that butadiene rubber and epoxy resin have the more preferable compatibility, substantially increase rigidity, the coating of anti-corrosive paint of epoxy resin Adhesive force and thermostability；From nano tin dioxide and nano magnesia as the filler of coating, and its surface is done at hydrophobization Reason, by the way of chemical modification and ultrasound wave dispersion are combined with mechanical agitation, nanoparticle is distributed in epoxy resin, Enhance the hydrophobic performance of anti-corrosive paint of epoxy resin, reach waterproof effect；The anticorrosive paint energy fast setting film forming of the present invention, Coating has the advantages that outstanding adhesive force, resistant abrasion and Strong corrosion resistant.
Specific embodiment
The butadiene rubber modified epoxy anticorrosive paint of the waterproof of the present embodiment, it is by the raw material preparation of following weight portion Form: 200 parts of epoxy resin e51,50 parts of butadiene rubber, 200 parts of dichloro-benzenes, 10 parts of benzoyl hydroperoxide, 3 parts of molybdenum trioxide, height 4 parts of sodium iodate, 10 parts of sodium tartrate, 15 parts of lysinediisocyanate, 8 parts of diethylaminoethanol, 12 parts of aniline, polystyrene 6 parts of hollow microsphere, 6 parts of phosphoric acid, 3 parts of Ammonium persulfate., 6 parts of tristerin, 200 parts of dimethylbenzene, n-butyl alcohol 150 part, nanometer 15 parts of stannum oxide, 20 parts of nano magnesia, 8 parts of dodecyl ether sulfate, 8 parts of double imidazolidinyl urea, n, n- bis- (2- hydroxypropyl Base) 6 parts of aniline, 30 parts of chloroform, appropriate deionized water.
The butadiene rubber modified epoxy anticorrosive paint of the waterproof of the present embodiment, it has the following steps and is prepared from:
(1) butadiene rubber is added in dichloro-benzenes, stirs 30min, add benzoyl hydroperoxide and molybdenum trioxide, rise high-temperature extremely 80 DEG C, stirring reaction 12h；Reduce temperature to 60 DEG C, add sodium metaperiodate, stirring reaction 3h, add sodium tartrate, rise high-temperature To 150 DEG C, stirring reaction 20h, obtain polyhydroxylated butadiene rubber；
(2) by polyhydroxylated butadiene rubber add equipped with agitator, thermometer reactor in, be warming up to 110 DEG C, carry out Vacuum outgass 30min, drops to room temperature after vacuum outgass, add lysinediisocyanate, be warming up to 90 DEG C, stirring reaction 5h, Add diethylaminoethanol, continue stirring reaction 8h, vacuum outgass 30min, cooling discharge；
(3) by aniline, polystyrene hollow microsphere, phosphoric acid and the deionized water mixing being equivalent to 10 times of aniline weight portion, stirring Uniformly, add nano magnesia and nano tin dioxide, after stirring 2h, add Ammonium persulfate., continue stirring 24h, obtain hydrophobic receiving Rice grain；
(4) by tristerin, it is dissolved in dimethylbenzene and the mixed solvent of n-butyl alcohol composition, under room temperature, ultrasound wave is uniformly dispersed Afterwards, it is slowly added to the hydrophobic nanoparticles of drying under stirring, treats that nano-particle adds, after stirring, continue ultrasonic Wavelength-division dissipates 3h, adds epoxy resin e51, is warming up to 105 DEG C, and evacuation 40min is cooled to 60 DEG C, adds the product of step (2) Thing, then it is warming up to 100 DEG C, stirring reaction 8h, add dodecyl ether sulfate, double imidazolidinyl urea, after ultrasound wave dispersion Disperse 40min at a high speed with blender again, be slowly added to n, the solution of n- bis- (2- hydroxypropyl) aniline and chloroform configuration, continue stirring 3h, obtains anticorrosive paint.
The salt fog of resistance to standard Neutral performance and corrosion-resistant test: neutral salt spray test is done using standard Neutral salt fog machine.By sample Product (coated weight: 250mg/dm2) put into and in salt fog machine, use saline (concentration is 5%, ph is 6.5-7.5) to spray at 35 DEG C, observe Sample changed condition.Test result: sample red rust in 1500h.

Claims (3)

1. a kind of waterproof butadiene rubber modified epoxy anticorrosive paint it is characterised in that its by following weight portion raw material Be prepared from: 200 parts of epoxy resin e51, butadiene rubber 40-50 part, dichloro-benzenes 150-200 part, benzoyl hydroperoxide 8-10 part, Molybdenum trioxide 2-3 part, sodium metaperiodate 3-4 part, sodium tartrate 8-10 part, lysinediisocyanate 12-15 part, lignocaine second Alcohol 5-8 part, aniline 10-12 part, polystyrene hollow microsphere 5-6 part, phosphoric acid 5-6 part, Ammonium persulfate. 2-3 part, glycerol stearate Ester 5-6 part, dimethylbenzene 150-200 part, n-butyl alcohol 120-150 part, nano tin dioxide 12-15 part, nano magnesia 15-20 part, Dodecyl ether sulfate 6-8 part, double imidazolidinyl urea 6-8 part, n, n- bis- (2- hydroxypropyl) aniline 5-6 part, chloroform 20-30 Part, appropriate deionized water.
2. waterproof according to claim 1 butadiene rubber modified epoxy anticorrosive paint it is characterised in that its just like Lower step is prepared from:
(1) butadiene rubber is added in dichloro-benzenes, stirs 20-30min, add benzoyl hydroperoxide and molybdenum trioxide, rise high temperature Spend to 70-80 DEG C, stirring reaction 10-12h；Reduce temperature to 50-60 DEG C, add sodium metaperiodate, stirring reaction 2-3h, add wine Stone acid sodium, rises high-temperature to 140-150 DEG C, and stirring reaction 18-20h obtains polyhydroxylated butadiene rubber；
(2) by polyhydroxylated butadiene rubber add equipped with agitator, thermometer reactor in, be warming up to 100-110 DEG C, Carry out vacuum outgass 20-30min, after vacuum outgass, drop to room temperature, add lysinediisocyanate, be warming up to 80-90 DEG C, stir Mix reaction 3-5h, add diethylaminoethanol, continue stirring reaction 6-8h, vacuum outgass 20-30min, cooling discharge；
(3) by aniline, polystyrene hollow microsphere, phosphoric acid and the deionized water mixing being equivalent to 8-10 times of aniline weight portion, stir Mix uniformly, add nano magnesia and nano tin dioxide, after stirring 1-2h, add Ammonium persulfate., continue stirring 20-24h, obtain Hydrophobic nanoparticles；
(4) by tristerin, it is dissolved in dimethylbenzene and the mixed solvent of n-butyl alcohol composition, under room temperature, ultrasound wave is uniformly dispersed Afterwards, it is slowly added to the hydrophobic nanoparticles of drying under stirring, treats that nano-particle adds, after stirring, continue ultrasonic Wavelength-division dissipates 2-3h, adds epoxy resin e51, is warming up to 95-105 DEG C, and evacuation 30-40min is cooled to 50-60 DEG C, adds step Suddenly the product of (2), then it is warming up to 90-100 DEG C, stirring reaction 5-8h, add dodecyl ether sulfate, double imidazolidinyl Urea, disperses 30-40min at a high speed with blender again after ultrasound wave dispersion, is slowly added to n, n- bis- (2- hydroxypropyl) aniline and chloroform The solution of configuration, continues stirring 2-3h, obtains anticorrosive paint.
3. the butadiene rubber modified epoxy anticorrosive paint of waterproof according to claim 1 and 2 is it is characterised in that institute The butadiene rubber stated is Rare Earth butadiene rubber, and the concentration of described phosphoric acid is 1-1.2mol/l.
CN201610720866.9A 2016-08-25 2016-08-25 Waterproof cis-1,4-polybutadiene rubber modified epoxy resin anticorrosive paint and preparation method thereof Pending CN106349886A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
Title
机械工业部科学技术司: "《机械工业胶接密封技术》", 31 August 1984 *
钱苗根: "《现代表面工程》", 30 September 2012 *

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Application publication date: 20170125