CN108715703A - A kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint - Google Patents
A kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint Download PDFInfo
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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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
- C09D7/60—Additives non-macromolecular
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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
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Abstract
The invention discloses a kind of preparation methods of porous silica Si modification waterproof inorganic zinc rich paint, belong to environmental protection coating material preparing technical field.Although epoxidized soybean oil dosage is fewer than the aqueous solvent dosage of modified doping epoxy resin in inorganic zinc rich paint in the present invention, epoxidized soybean oil is stronger in the reactivity of maleic anhydride epoxide epoxy group group, aqueous solvent inside porous silica quickly volatilizees, accelerate the solidification rate of inorganic zinc rich paint, the protective agent in waterproof duct is phenol-formaldehyde resin modified in porous silica in the present invention, brightness molybdenum mountain flour and atoleine are added in the protective agent of duct, using infusion process, with polyethyleneimine and tetraethylenepentamine for amino modified dose, prepare the porous silica being modified for inorganic zinc rich paint, the solvent volatilization efficiency of inorganic zinc rich paint is improved by inner hydrophobic porous silica, and zinc powder is enable to be uniformly distributed in enamelled coating, improve enamelled coating intensity, with lasting water resistance and electrochemical anti-corrosive performance, it has a extensive future.
Description
Technical field
The invention discloses a kind of preparation methods of porous silica Si modification waterproof inorganic zinc rich paint, belong to environmental protection coating material
Preparing technical field.
Background technology
Inorganic zinc rich paint is with inorganic polymer（Such as silicate, phosphate, bichromate）For film forming matter, zinc powder with
Reaction, metal surface formed zinc-iron complex compound, form solid protection film.It is viscous that inorganic zinc rich paint, which refers to inorganic matter,
Mixture is subject to plasticizer, anti-settling agent, levelling agent, thixotropic agent, zinc powder etc..Silicic acid second vinegar or its oligomer, in acid condition by
Ketone or alcohols make solvent, and the water for absorbing the moisture in air or adding people a small amount of in reaction solution hydrolyzes, through condensation reaction
Generate bigger molecule polymer.
Inorganic zinc rich paint has electro-chemical protection to steel, and rustless property is excellent, sea water resistance, oil resistant, solvent resistant, salt
Class and atmospheric corrosion.And can be used in 400 DEG C of environment for a long time, thus it is widely used in shipbuilding industry, petrochemical industry, sea
Facility heat distribution pipeline, chimney, bridge etc..
Zinc-rich coating includes mainly waterborne inorganic einc-rich primer and alcohol-soluble zinc-rich coating two major classes.Alcohol-soluble
There is zinc-rich coating excellent anticorrosion, oil resistant, the performances such as solvent resistant high temperature resistant to be widely used in petrochemical equipment,
The protective coating on the surfaces such as bridge, pipeline, offshore platform and storage tank.For at present, using solvent type epoxy zinc rich primer as representative
Organic polymer solvent-based paints, be applied to various pre-coated metal building materials；But it is arranged with to VOC volatile organic compounds
The limitation put is increasingly stringent, and the solvent type fluorocarbon coating application of a large amount of VOC volatilizations is caused above to be subject to certain restrictions.Alcohol-soluble without
The good construction adaptability of machine zinc rich primer, can with the aqueous vapor in air in conjunction with and cure, have under super-humid conditions in south China
Preferable applicability.But the alcohol-soluble inorganic zinc rich paint prepared at present uses in the environment of some northern low temperature dryings in winter
When, curing of coatings speed is very slow, seriously affects construction period.Aqueous inorganic zinc-enriched coating is the longest gold of current service life
Belong to one of anticorrosive coating, because of itself environmental protection characteristic and excellent Corrosion Protection, in the heavy antisepsis such as air and ocean field
Achieve extensive use.At present using single aqueous silicic acid potassium, sodium metasilicate, water silica sol as the watery anti-corrosion priming paint of representative
Some are applied on large-scale steel structure, there is also some problems in performance in such aqueous inorganic silicon coating, such as resistance to
It is problematic in that in terms of aqueous and workability.
Therefore, it invents a kind of porous silica Si modification waterproof inorganic zinc rich paint of water-tolerant and prepared by skill to environmental protection coating material
Art field has positive effect.
Invention content
Present invention mainly solves the technical issues of, at low ambient temperatures for current inorganic zinc rich paint, curing of coatings speed
It is very slow, construction period, and the defect that enamelled coating water proofing property is poor are seriously affected, it is anti-to provide a kind of porous silica Si modification
The preparation method of water inorganic zinc rich paint.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint, it is characterised in that specifically preparation process is：
（1）Into four-hole boiling flask, be added 50~60mL soybean oils, 10~12mL formic acid solutions, 20~25mL hydrogen peroxide and 30~
40mL sulfuric acid solutions start blender, are stirred with the rotating speed of 200~220r/min, and heat temperature raising, insulation reaction is subsequently moved within
In separatory funnel, washing discards water phase, obtains oil phase, in 400~500mL sodium hydroxide solutions and oil phase, then uses distilled water
Washing 2~3 times, obtains epoxidized soybean oil；
（2）Ethylene glycol monobutyl ether and n-butanol are mixed to get cosolvent, 180~200g bisphenol A type epoxy resins are placed in band
Have in the four-hole boiling flask of constant pressure funnel, oil bath heating heating is then added 300~350mL cosolvent, waits for bisphenol-A type ring
Oxygen resin all after dissolving, under nitrogen protection, continues oil bath heating heating, obtains pre-reaction liquid；
（3）Count in parts by weight, take 20~30 parts of methacrylic acids, 30~40 parts of butyl acrylates, 10~15 parts of styrene,
0.5~1.0 part of benzoyl peroxide mixing, obtains aqueous premix, 200~220mL aqueous premix is passed through constant pressure addition
Aqueous premix is added dropwise into above-mentioned four-hole boiling flask for funnel in pre-reaction liquid, modified milk glue is obtained after insulation reaction；
（4）80~85g phenol, 85~90mL formalins and 1~3g hydrogen-oxygens are added into the three-necked flask with agitating device
To change sodium, 14~16g atoleines, 20~25g brightness molybdenum mountain flours are added into three-necked flask, heat temperature raising starts blender, with
200~300r/min rotating speeds stir, insulation reaction, then by three-necked flask vacuum distillation dehydration, continue insulation reaction, Dang Sankou
Product starts after there is gel in flask, waits for that temperature is cooled to room temperature, and discharging obtains waterproof duct protective agent；
（5）4~5g polyethyleneimines and 7~8g tetraethylenepentamine are dissolved in the beaker equipped with 40~50mL absolute methanols, added
Heat heating, until polyethyleneimine is completely dissolved, addition 30~40g porous silica silicon materials into beaker are impregnated, are obtained for stirring
To aminated porous silica, then by waterproof duct protective agent heat temperature raising, the hole of aminated porous silica is flowed into
It in gap, is put into blast drier, closes the temperature power supply of blast drier, be naturally cooling to room temperature and obtain the porous dioxy of waterproof
SiClx；
（6）Ammonium hydroxide is added to modified milk glue, obtains the aqueous solvent of doping epoxy resin, counts in parts by weight, weigh 10~
15 parts of epoxidized soybean oils, 40~50 parts of aqueous solvents, 10~12 parts of diethylenetriamines, 20~30 parts of waterproofs for adulterating epoxy resin
Porous silica, 20~22 parts of zinc powders, 15~18 parts of maleic anhydrides, 30~35 parts of bentonites are placed in high speed dispersor and disperse
Afterwards, porous silica Si modification waterproof inorganic zinc rich paint is obtained.
Step（1）The mass fraction of the formic acid solution is 15%, and the mass fraction of hydrogen peroxide is 20%, sulfuric acid solution
Mass fraction is 75%, and temperature is 90~95 DEG C after four-hole boiling flask heat temperature raising, and the insulation reaction time is 2.0~2.5h, hydroxide
The mass fraction of sodium solution is 30%.
Step（2）The ethylene glycol monobutyl ether is 3 ︰ 2 with n-butanol mixed volume ratio, and temperature is after oil bath heating heating
70~78 DEG C, temperature is 140~150 DEG C after continuing oil bath heating heating.
Step（3）The drop rate of the constant pressure funnel is 5~8mL/min, and the insulation reaction time is 2~3h.
Step（4）The mass fraction of the formalin is 37%, and temperature is 100~110 after three-necked flask heat temperature raising
DEG C, the insulation reaction time is 40~50min.
Step（5）Temperature is 70~80 DEG C after the heat temperature raising, and soaking time is 10~12h, temperature after heat temperature raising
Degree is 140~150 DEG C, and blast drier set temperature is 120~130 DEG C.
Step（6）The mass fraction of the ammonium hydroxide is 30%, be added after ammonium hydroxide liquid pH in four-hole boiling flask be 6.8~
7.0, high speed dispersion rotating speed is 4000~4200r/min, and jitter time is 10~13min.
The beneficial effects of the invention are as follows：
（1）Although aqueous solvent of the epoxidized soybean oil dosage than modified doping epoxy resin in inorganic zinc rich paint in the present invention
Dosage is few, but epoxidized soybean oil is stronger in the reactivity of maleic anhydride epoxide epoxy group group, and epoxidized soybean oil is sent out with maleic anhydride
Raw double bond crosslinking, forms oligomer, so that the compatibility of epoxy resin and inorganic matter is obviously improved, and make unit volume inorganic zinc-rich
The curing activation energy of paint epoxy resin is reduced, and maleic anhydride can be cured crosslinking in low temperature with epoxy resin,
Make inorganic zinc rich paint that can cure under cryogenic, and waterproof duct protective agent is prepared by product of phenolic resin, first leads to
Cross the porous SiO of dipping of polyethyleneimine and tetraethylenepentamine2Keep its aminated, then the heating inflow of waterproof duct protective agent is more
Hole SiO2Hole in, slow cooling prepares the porous silica of internal pore surface waterproof under the conditions of air blast, makes porous two
Aqueous solvent inside silica quickly volatilizees, and accelerates the solidification rate of inorganic zinc rich paint, while waterproof inorganic zinc rich paint cures
Afterwards, fine and close convex-concave surface can be formed in metallic substrate surface, liquefying the droplet to be formed in coating surface in humid air can be fast
Speed air-dries, to achieve the purpose that enamelled coating waterproof；
（2）The protective agent in waterproof duct is phenol-formaldehyde resin modified in porous silica in the present invention, is added in the protective agent of duct
Brightness molybdenum mountain flour and atoleine, a large amount of element sulphurs are contained in brightness molybdenum stone, and sulfur-containing compound can be such that atoleine is generated with phenolic resin
Crosslinked action makes the compactness of the protectant surface protection film paraffin layer in duct be improved, the protectant primary raw material in duct
Phenolic resin is difficult to absorb water through fine and close protective film, and the silicone hydroxyl that silica generates is influenced to take off by the electronegativity of lye
Water condensation reaction reduces the content of surface hydrophilicity hydroxyl, improves duct protective agent water resistance, and use infusion process,
With polyethyleneimine and tetraethylenepentamine for amino modified dose, pass through porous SiO2The functional amido of material make silica with
Phenolic resin can dehydrating condensation, bonding is integral, and the internal hydrogen bond for having combination improves duct protective agent and silica
Binding force, prepare the porous silica being modified for inorganic zinc rich paint, improved by inner hydrophobic porous silica
The solvent volatilization efficiency of inorganic zinc rich paint, and zinc powder is enable to be uniformly distributed in enamelled coating, enamelled coating intensity is improved, is had persistently
Water resistance and electrochemical anti-corrosive performance, have a extensive future.
Specific implementation mode
Into four-hole boiling flask, 50~60mL soybean oils are added, the formic acid solution that 10~12mL mass fractions are 15%, 20~
The sulfuric acid solution that the hydrogen peroxide and 30~40mL mass fractions that 25mL mass fractions are 20% are 75% starts blender, with 200~
The rotating speed of 220r/min stirs, and 90~95 DEG C of heat temperature raising, 2.0~2.5h of insulation reaction is subsequently moved in separatory funnel, water
It washes, discards water phase, obtain oil phase, be in 30% sodium hydroxide solution and oil phase with 400~500mL mass fractions, then use distilled water
Washing 2~3 times, obtains epoxidized soybean oil；It is that 3 ︰ 2 are mixed to get cosolvent by volume by ethylene glycol monobutyl ether and n-butanol,
180~200g bisphenol A type epoxy resins are placed in the four-hole boiling flask with constant pressure funnel, oil bath heating is warming up to 70~
78 DEG C, 300~350mL cosolvent is then added, after bisphenol A type epoxy resin all dissolving, under nitrogen protection, continues oil
Bath is heated to 140~150 DEG C, obtains pre-reaction liquid；It counts in parts by weight, takes 20~30 parts of methacrylic acids, 30~40
Part butyl acrylate, 10~15 parts of styrene, 0.5~1.0 part of benzoyl peroxide mixing, obtain aqueous premix, by 200~
220mL aqueous premix by constant pressure funnel with the drop rate of 5~8mL/min, the pre-reaction into above-mentioned four-hole boiling flask
Aqueous premix is added dropwise in liquid, modified milk glue is obtained after 2~3h of insulation reaction；Add into the three-necked flask with agitating device
Enter the formalin and 1~3g sodium hydroxides of 80~85g phenol, 85~90mL mass fractions for 37%, is added into three-necked flask
14~16g atoleines, 20~25g brightness molybdenum mountain flours are heated to 100~110 DEG C, start blender, with 200~300r/
Min rotating speeds stir, 40~50min of insulation reaction, and then by three-necked flask 30~45min of vacuum distillation dehydration, it is anti-to continue heat preservation
It answers, after product starts to occur gel in three-necked flask, waits for that temperature is cooled to room temperature, discharging obtains waterproof duct protective agent；By 4
~5g polyethyleneimines and 7~8g tetraethylenepentamine are dissolved in the beaker equipped with 40~50mL absolute methanols, are heated to 70
~80 DEG C, until polyethyleneimine is completely dissolved, addition 30~40g porous silica silicon materials into beaker impregnate 10 for stirring
~12h obtains aminated porous silica, and waterproof duct protective agent is then heated to 140~150 DEG C, flows into amine
In the hole of base porous silica, it is put into the blast drier that set temperature is 120~130 DEG C, closes forced air drying
The temperature power supply of machine is naturally cooling to room temperature and obtains waterproof porous silica；It is 30% that mass fraction, which is added, to modified milk glue
Ammonium hydroxide, until four-hole boiling flask in liquid pH be 6.8~7.0, obtain doping epoxy resin aqueous solvent, in parts by weight
Meter, weigh 10~15 parts of epoxidized soybean oils, 40~50 parts of doping aqueous solvents of epoxy resin, 10~12 parts of diethylenetriamines,
20~30 parts of waterproof porous silicas, 20~22 parts of zinc powders, 15~18 parts of maleic anhydrides, 30~35 parts of bentonites are placed in high speed
It is inorganic to be obtained after disperseing 10~13min with the rotating speed of 4000~4200r/min for porous silica Si modification waterproof in dispersion machine
Zinc rich paint.
Into four-hole boiling flask, 50mL soybean oils are added, the formic acid solution that 10mL mass fractions are 15%, 20mL mass fractions
The sulfuric acid solution that hydrogen peroxide and 30mL mass fractions for 20% are 75% starts blender, is stirred, is added with the rotating speed of 200r/min
90 DEG C of heat heating, insulation reaction 2.0h is subsequently moved in separatory funnel, and washing discards water phase, obtains oil phase, with 400mL mass
Score is in 30% sodium hydroxide solution and oil phase, then is washed 2 times with distilled water, obtains epoxidized soybean oil；By ethylene glycol monobutyl ether
It is that 3 ︰ 2 are mixed to get cosolvent by volume with n-butanol, 180g bisphenol A type epoxy resins is placed in constant pressure funnel
Four-hole boiling flask in, oil bath heating is warming up to 70 DEG C, then be added 300mL cosolvent, wait for bisphenol A type epoxy resin all dissolve
Afterwards, under nitrogen protection, continue oil bath heating and be warming up to 140 DEG C, obtain pre-reaction liquid；It counts in parts by weight, takes 20 parts of methyl
Acrylic acid, 30 parts of butyl acrylates, 10 parts of styrene, 0.5 part of benzoyl peroxide mixing, obtain aqueous premix, by 200mL
Aqueous premix, with the drop rate of 5mL/min, is added dropwise into above-mentioned four-hole boiling flask in pre-reaction liquid by constant pressure funnel
Aqueous premix obtains modified milk glue after insulation reaction 2h；Be added into the three-necked flask with agitating device 80g phenol,
The formalin and 1g sodium hydroxides that 85mL mass fractions are 37%, 14g atoleines, 20g brightness molybdenum stones are added into three-necked flask
Powder is heated to 100 DEG C, starts blender, is stirred with 200r/min rotating speeds, insulation reaction 40min, then by three-necked flask
Vacuum distillation dehydration 30min continues insulation reaction and waits for that temperature is down to room temperature after product starts to occur gel in three-necked flask
Afterwards, discharging obtains waterproof duct protective agent；4g polyethyleneimines and 7g tetraethylenepentamine are dissolved in equipped with 40mL absolute methanols
In beaker, 70 DEG C are heated to, stirring is completely dissolved up to polyethyleneimine, and 30g porous silicas are added into beaker
Material impregnates 10h, obtains aminated porous silica, and waterproof duct protective agent is then heated to 140 DEG C, flows into
In the hole of aminated porous silica, it is put into the blast drier that set temperature is 120 DEG C, closes blast drier
Temperature power supply is naturally cooling to room temperature and obtains waterproof porous silica；The ammonia that mass fraction is 30% is added to modified milk glue
Water obtains the aqueous solvent of doping epoxy resin, counts in parts by weight, weigh 10 parts until liquid pH is 6.8 in four-hole boiling flask
Epoxidized soybean oil, 40 parts of aqueous solvents, 10 parts of diethylenetriamines, 20 parts of waterproof porous silicas, 20 for adulterating epoxy resin
Part zinc powder, 15 parts of maleic anhydrides, 30 parts of bentonites are placed in the rotating speed in high speed dispersor with 4000r/min, after disperseing 10min,
Obtain porous silica Si modification waterproof inorganic zinc rich paint.
Into four-hole boiling flask, 55mL soybean oils are added, the formic acid solution that 11mL mass fractions are 15%, 22mL mass fractions
The sulfuric acid solution that hydrogen peroxide and 35mL mass fractions for 20% are 75% starts blender, is stirred, is added with the rotating speed of 210r/min
92 DEG C of heat heating, insulation reaction 2.2h is subsequently moved in separatory funnel, and washing discards water phase, obtains oil phase, with 450mL mass
Score is in 30% sodium hydroxide solution and oil phase, then is washed 2 times with distilled water, obtains epoxidized soybean oil；By ethylene glycol monobutyl ether
It is that 3 ︰ 2 are mixed to get cosolvent by volume with n-butanol, 190g bisphenol A type epoxy resins is placed in constant pressure funnel
Four-hole boiling flask in, oil bath heating is warming up to 74 DEG C, then be added 320mL cosolvent, wait for bisphenol A type epoxy resin all dissolve
Afterwards, under nitrogen protection, continue oil bath heating and be warming up to 145 DEG C, obtain pre-reaction liquid；It counts in parts by weight, takes 25 parts of methyl
Acrylic acid, 35 parts of butyl acrylates, 12 parts of styrene, 0.7 part of benzoyl peroxide mixing, obtain aqueous premix, by 210mL
Aqueous premix, with the drop rate of 7mL/min, is added dropwise into above-mentioned four-hole boiling flask in pre-reaction liquid by constant pressure funnel
Aqueous premix obtains modified milk glue after insulation reaction 2.5h；82g benzene is added into the three-necked flask with agitating device
Phenol, the formalin that 87mL mass fractions are 37% and 2g sodium hydroxides, 15g atoleines, 22g brightness are added into three-necked flask
Molybdenum mountain flour is heated to 105 DEG C, starts blender, is stirred with 250r/min rotating speeds, insulation reaction 45min, then by three mouthfuls
Flask vacuum distillation dehydration 32min continues insulation reaction and waits for that temperature is down to after product starts to occur gel in three-necked flask
After room temperature, discharging obtains waterproof duct protective agent；4g polyethyleneimines and 7g tetraethylenepentamine are dissolved in equipped with 45mL without water beetle
In the beaker of alcohol, 75 DEG C are heated to, stirring is completely dissolved up to polyethyleneimine, and the porous dioxies of 35g are added into beaker
Silicon nitride material impregnates 11h, obtains aminated porous silica, waterproof duct protective agent is then heated to 145 DEG C,
It flows into the hole of aminated porous silica, is put into the blast drier that set temperature is 125 DEG C, closes forced air drying
The temperature power supply of machine is naturally cooling to room temperature and obtains waterproof porous silica；It is 30% that mass fraction, which is added, to modified milk glue
Ammonium hydroxide, until four-hole boiling flask in liquid pH be 6.9, obtain doping epoxy resin aqueous solvent, count, weigh in parts by weight
12 parts of epoxidized soybean oils, 45 parts of aqueous solvent, 11 parts of diethylenetriamines, 25 parts of waterproof porous silicas for adulterating epoxy resin
Silicon, 21 parts of zinc powders, 17 parts of maleic anhydrides, 32 parts of bentonites are placed in the rotating speed in high speed dispersor with 4100r/min, dispersion
After 11min, porous silica Si modification waterproof inorganic zinc rich paint is obtained.
Into four-hole boiling flask, 60mL soybean oils are added, the formic acid solution that 12mL mass fractions are 15%, 25mL mass fractions
The sulfuric acid solution that hydrogen peroxide and 40mL mass fractions for 20% are 75% starts blender, is stirred, is added with the rotating speed of 220r/min
95 DEG C of heat heating, insulation reaction 2.5h is subsequently moved in separatory funnel, and washing discards water phase, obtains oil phase, with 500mL mass
Score is in 30% sodium hydroxide solution and oil phase, then is washed 3 times with distilled water, obtains epoxidized soybean oil；By ethylene glycol monobutyl ether
It is that 3 ︰ 2 are mixed to get cosolvent by volume with n-butanol, 200g bisphenol A type epoxy resins is placed in constant pressure funnel
Four-hole boiling flask in, oil bath heating is warming up to 78 DEG C, then be added 350mL cosolvent, wait for bisphenol A type epoxy resin all dissolve
Afterwards, under nitrogen protection, continue oil bath heating and be warming up to 150 DEG C, obtain pre-reaction liquid；It counts in parts by weight, takes 30 parts of methyl
Acrylic acid, 40 parts of butyl acrylates, 15 parts of styrene, 1.0 parts of benzoyl peroxide mixing, obtain aqueous premix, by 220mL
Aqueous premix, with the drop rate of 8mL/min, is added dropwise into above-mentioned four-hole boiling flask in pre-reaction liquid by constant pressure funnel
Aqueous premix obtains modified milk glue after insulation reaction 3h；Be added into the three-necked flask with agitating device 85g phenol,
The formalin and 3g sodium hydroxides that 90mL mass fractions are 37%, 16g atoleines, 25g brightness molybdenum stones are added into three-necked flask
Powder is heated to 110 DEG C, starts blender, is stirred with 300r/min rotating speeds, insulation reaction 50min, then by three-necked flask
Vacuum distillation dehydration 45min continues insulation reaction and waits for that temperature is down to room temperature after product starts to occur gel in three-necked flask
Afterwards, discharging obtains waterproof duct protective agent；5g polyethyleneimines and 8g tetraethylenepentamine are dissolved in equipped with 50mL absolute methanols
In beaker, 80 DEG C are heated to, stirring is completely dissolved up to polyethyleneimine, and 40g porous silicas are added into beaker
Material impregnates 12h, obtains aminated porous silica, and waterproof duct protective agent is then heated to 150 DEG C, flows into
In the hole of aminated porous silica, it is put into the blast drier that set temperature is 130 DEG C, closes blast drier
Temperature power supply is naturally cooling to room temperature and obtains waterproof porous silica；The ammonia that mass fraction is 30% is added to modified milk glue
Water obtains the aqueous solvent of doping epoxy resin, counts in parts by weight, weigh 15 parts until liquid pH is 7.0 in four-hole boiling flask
Epoxidized soybean oil, 50 parts of doping aqueous solvents of epoxy resin, 12 parts of diethylenetriamines, 0 part of waterproof porous silica, 22 parts
Zinc powder, 18 parts of maleic anhydrides, 35 parts of bentonites are placed in the rotating speed in high speed dispersor with 4200r/min, after disperseing 13min, obtain
To porous silica Si modification waterproof inorganic zinc rich paint.
The porous silica Si modification waterproof inorganic zinc rich paint that comparative example is produced with Company in Chongqing is as a comparison case to this
Porous silica Si modification waterproof in invention porous silica Si modification waterproof inorganic zinc rich paint and comparative example obtained is inorganic
Zinc rich paint carries out performance detection, and testing result is as shown in table 1：
Test method：
Low-temperature setting time test is cured at low ambient temperatures, measures hardening time.
Water resistance test is detected by the standard of GB/T1733, and measures the adhesive force after Water Resistance Test.
1 inorganic zinc rich paint performance measurement result of table
It is fast according to the porous silica Si modification waterproof inorganic zinc rich paint low-temperature setting speed of the above-mentioned detection data present invention,
Hardening time is short, water-tolerant, and the adhesive force grade after Water Resistance Test reaches 0 grade, has broad application prospects.
Claims (7)
1. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint, it is characterised in that specifically preparation process is：
（1）Into four-hole boiling flask, be added 50~60mL soybean oils, 10~12mL formic acid solutions, 20~25mL hydrogen peroxide and 30~
40mL sulfuric acid solutions start blender, are stirred with the rotating speed of 200~220r/min, and heat temperature raising, insulation reaction is subsequently moved within
In separatory funnel, washing discards water phase, obtains oil phase, in 400~500mL sodium hydroxide solutions and oil phase, then uses distilled water
Washing 2~3 times, obtains epoxidized soybean oil；
（2）Ethylene glycol monobutyl ether and n-butanol are mixed to get cosolvent, 180~200g bisphenol A type epoxy resins are placed in band
Have in the four-hole boiling flask of constant pressure funnel, oil bath heating heating is then added 300~350mL cosolvent, waits for bisphenol-A type ring
Oxygen resin all after dissolving, under nitrogen protection, continues oil bath heating heating, obtains pre-reaction liquid；
（3）Count in parts by weight, take 20~30 parts of methacrylic acids, 30~40 parts of butyl acrylates, 10~15 parts of styrene,
0.5~1.0 part of benzoyl peroxide mixing, obtains aqueous premix, 200~220mL aqueous premix is passed through constant pressure addition
Aqueous premix is added dropwise into above-mentioned four-hole boiling flask for funnel in pre-reaction liquid, modified milk glue is obtained after insulation reaction；
（4）80~85g phenol, 85~90mL formalins and 1~3g hydrogen-oxygens are added into the three-necked flask with agitating device
To change sodium, 14~16g atoleines, 20~25g brightness molybdenum mountain flours are added into three-necked flask, heat temperature raising starts blender, with
200~300r/min rotating speeds stir, insulation reaction, then by three-necked flask vacuum distillation dehydration, continue insulation reaction, Dang Sankou
Product starts after there is gel in flask, waits for that temperature is cooled to room temperature, and discharging obtains waterproof duct protective agent；
（5）4~5g polyethyleneimines and 7~8g tetraethylenepentamine are dissolved in the beaker equipped with 40~50mL absolute methanols, added
Heat heating, until polyethyleneimine is completely dissolved, addition 30~40g porous silica silicon materials into beaker are impregnated, are obtained for stirring
To aminated porous silica, then by waterproof duct protective agent heat temperature raising, the hole of aminated porous silica is flowed into
It in gap, is put into blast drier, closes the temperature power supply of blast drier, be naturally cooling to room temperature and obtain the porous dioxy of waterproof
SiClx；
（6）Ammonium hydroxide is added to modified milk glue, obtains the aqueous solvent of doping epoxy resin, counts in parts by weight, weigh 10~
15 parts of epoxidized soybean oils, 40~50 parts of aqueous solvents, 10~12 parts of diethylenetriamines, 20~30 parts of waterproofs for adulterating epoxy resin
Porous silica, 20~22 parts of zinc powders, 15~18 parts of maleic anhydrides, 30~35 parts of bentonites are placed in high speed dispersor and disperse
Afterwards, porous silica Si modification waterproof inorganic zinc rich paint is obtained.
2. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint according to claim 1, feature
It is：Step（1）The mass fraction of the formic acid solution is 15%, and the mass fraction of hydrogen peroxide is 20%, the matter of sulfuric acid solution
It is 75% to measure score, and temperature is 90~95 DEG C after four-hole boiling flask heat temperature raising, and the insulation reaction time is 2.0~2.5h, sodium hydroxide
The mass fraction of solution is 30%.
3. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint according to claim 1, feature
It is：Step（2）The ethylene glycol monobutyl ether is 3 ︰ 2 with n-butanol mixed volume ratio, and temperature is 70 after oil bath heating heating
~78 DEG C, temperature is 140~150 DEG C after continuing oil bath heating heating.
4. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint according to claim 1, feature
It is：Step（3）The drop rate of the constant pressure funnel is 5~8mL/min, and the insulation reaction time is 2~3h.
5. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint according to claim 1, feature
It is：Step（4）The mass fraction of the formalin is 37%, and temperature is 100~110 DEG C after three-necked flask heat temperature raising,
The insulation reaction time is 40~50min.
6. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint according to claim 1, feature
It is：Step（5）Temperature is 70~80 DEG C after the heat temperature raising, and soaking time is 10~12h, and temperature is after heat temperature raising
140~150 DEG C, blast drier set temperature is 120~130 DEG C.
7. a kind of preparation method of porous silica Si modification waterproof inorganic zinc rich paint according to claim 1, feature
It is：Step（6）The mass fraction of the ammonium hydroxide is 30%, and liquid pH is 6.8~7.0 in four-hole boiling flask after addition ammonium hydroxide, high
Speed dispersion rotating speed is 4000~4200r/min, and jitter time is 10~13min.
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| CN110408295A (en) * | 2019-06-21 | 2019-11-05 | 王玉琢 | A kind of preparation method of acidproof waterproof corrosion-resistant epoxy paint |
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Application publication date: 20181030 |