CN101508870A - Electrostatic conductive anticorrosion paint and method of preparing the same - Google Patents

Electrostatic conductive anticorrosion paint and method of preparing the same Download PDF

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Publication number
CN101508870A
CN101508870A CNA2009100612187A CN200910061218A CN101508870A CN 101508870 A CN101508870 A CN 101508870A CN A2009100612187 A CNA2009100612187 A CN A2009100612187A CN 200910061218 A CN200910061218 A CN 200910061218A CN 101508870 A CN101508870 A CN 101508870A
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butyronitrile
epoxy
electrostatic
agent
resins
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CN101508870B (en
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施铭德
曾福生
周春爱
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Hubei Tieshen New Materials Co., Ltd.
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Wuhan Tieshen Chemical Co Ltd
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Abstract

An electrostatic conducted anti-corrosive paint comprises 45-66wt% of waterborne polyurethane- nitrile epoxy composite dispersed emulsion, 15-20wt% of composite conductive filler, 1-5wt% of inhibiter, 5-18wt% of ferrotitanium powder, 0.3-0.6wt% of dispersant, 0.4-0.8wt% of wetting agent, 0.2-0.5wt% of defoaming agent, 0.3-0.6wt% of flatting agent, 4-6wt% of film forming additive and 2-14wt% of titanium pigment. The invention also provides a method for preparing the electrostatic conducted anti-corrosive paint, comprising: the dispersant, the wetting agent, the titanium pigment and the ferrotitanium powder are mixed together, ground by sand to be dispersed into 60mum of fineness, and added with the composite conductive filler to be evenly stirred; after that, the waterborne polyurethane- nitrile epoxy composite dispersed emulsion, the defoaming agent, the flatting agent, the inhibiter and the film forming additive are added in to the mixture to be evenly stirred; finally, the electrostatic conducted anti-corrosive paint is obtained. The electrostatic conducted anti-corrosive paint has excellent chemical resistance and corrosion resistance, large superficial area of granule, is easy to disperse in resin and contact with each other, and can gain good and lasting electrostatic conducted property.

Description

A kind of electrostatic conductive anticorrosion paint and preparation method thereof
Technical field:
The present invention relates to a kind of electrostatic conductive anticorrosion paint and preparation method thereof.
Background technology:
The steel storage tank is the transportation of petroleum and petrochemical sector oil product, storage and the requisite facility of safe operation.Various storage tank play an important role in national economy and military field, and usage quantity is increasing many more, often suffer corrosion and static inside and outside, surrounding medium to bring hidden danger but be in operation.Here anticorrosion and lead the electrostatic problem with regard to existing storage tank.China Association of Coatings Industry organized and initiated to have worked out CNCIA-HG/T0001-2006 " application of petroleum storage tank electrostatic conductive anticorrosion paint and acceptance specification " in concert with " the oil tank static conductive coating detects standard " national standard management group in 2005, for paint spraying has been formulated compulsory standard and correlation technique standard, this is just for guaranteeing oil tank safety, guarantee that oil quality lays a good foundation, the regulation standard.Storage tank anticorrosion and lead electrostatic problem, the simplest terms of settlement is used anticorrosion static conductive coating exactly.Metal tank contacts with product media such as starting material for a long time with atmosphere, production, and chemistry and electrochemical action can take place, and produce chemistry and galvanic corrosion; And oil product impacts through continuous friction such as pump, valve, pipeline in the processing transportation, shears to produce static, and static gathers the generation high pressure and forms accident potential on its surface, and fire very easily sets off an explosion.
The solvent-borne type carbon black graphite that initial static conductive coating is used is led the static starting material, carbon black dissolving in oil easily, easily migration, and poor corrosion resistance influences oil quality, and regulation is not as conducting electrostatic materials at present.And adopt the conducting metal oxide material preparation lead electrostatic coating at (1%H 2SO 4+ 1%NaCl) under the ambient condition, just electrostatic conductive performance all has decline in the heavy crude oil of sulfur-bearing, and the protection life-span is restricted, because conducting metal oxide and resin are subjected to structural destruction under acidic conditions.The corrosive environment that the coating of therefore leading the preparation of static metal oxide materials is used for Bottom Plate of Crude Oil Storage is unaccommodated.
The a large amount of employings of existing anticorrosion static conductive coating membrane-forming agent are solvent type, are easy to generate " dodging quick-fried " at the dead front type storage tank and cause personnel and property damage.Its temperature tolerance does not reach " standard " requirement.
Summary of the invention:
The present invention provides a kind of electrostatic conductive anticorrosion paint and preparation method thereof at the problems referred to above exactly, the not only every index of resulting electrostatic conductive anticorrosion paint can reach CNCIA-HG/0001-2006 index request, and has good antirust, anticorrosion, conductivity.
Technical scheme provided by the invention is: a kind of electrostatic conductive anticorrosion paint comprises 45~66% aqueous polyurethanes-butyronitrile epoxy composite dispersion emulsion; 15~20% complex conductive fillerses, 1~5% inhibiter, 5~18% ferrotitanium powder, 0.3~0.6% dispersion agent, 0.4~0.8% wetting agent, 0.2~0.5% defoamer, 0.3~0.6% flow agent, 4~6% film coalescence aid and 2~14% color stuffings; Described complex conductive fillers is made by laxative remedy: get 60%~80% and lead quiet mica powder, 10%~30% polyaniline, 5%~10% stannic oxide, with polytetrafluoroethylene (PTFE) emulsion mixing and stirring, under 500~1000 ℃ of temperature, roasting, ball milling becomes 5~10 μ m powder then, and the consumption of ptfe emulsion is 20~40% of conductive mica powder, polyaniline and a stannic oxide amount of the mixture; Above per-cent is weight percentage.
Above-mentioned aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion is obtained by laxative remedy: under nitrogen protection; with the total mol ratio of NCO/OH is that the polyether Glycols of 1.4~1.7 tolylene diisocyanate and dehydration is at 80 ℃; reaction 1~3h; the linking agent TriMethylolPropane(TMP) that adds the polyether Glycols mixture total weight amount 2~10% of tolylene diisocyanate and dehydration; 1~5% chainextender dimethylol propionic acid and 20~50% butyronitrile Resins, epoxy; reaction 2-5h; be cooled to room temperature; add triethylamine and be neutralized to neutrality, the emulsifying water that adds the polyether Glycols mixture total weight amount 20-25% of tolylene diisocyanate and dehydration under 1000-1500 rev/mins high speed shear power obtains aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion.
Above-mentioned butyronitrile Resins, epoxy is prepared by laxative remedy: in the presence of catalyzer Diisopropyl azodicarboxylate or methylimidazole, and 10~30wt% paracril and 70~90wt% Resins, epoxy, 80~120 ℃ of reacting by heating of temperature of reaction obtain butyronitrile Resins, epoxy.
The polyether Glycols of above-mentioned dehydration is obtained by laxative remedy: with polyether Glycols (Mn=1500~2000) at 90~110 ℃ of following decompression dehydration 4~6h.
Above-mentioned inhibiter is SER-ADFA179, and dispersion agent is W6038, and wetting agent is W203, and defoamer is W4002, and flow agent is W3018, and film coalescence aid is Texonol, and color stuffing is barium sulfate or titanium dioxide.
The present invention also provides the preparation method of above-mentioned electrostatic conductive anticorrosion paint: dispersion agent, wetting agent, titanium dioxide and ferrotitanium powder are mixed, sand milling is dispersed to fineness less than 60 μ m under 1000-1500 rev/mins shearing force, adding the composite conductive powder filler again stirs, add aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion, defoamer, flow agent, inhibiter and film coalescence aid then and stir, obtain electrostatic conductive anticorrosion paint.
The present invention adopts ternary system conducting electrostatic materials (conductive mica powder, polyaniline, stannic oxide), resin adopts aqueous polyurethane-acrylonitrile butadiene rubber modified epoxy resin latex, form electrostatic conductive anticorrosion paint, every index all reaches CNCIA-HG/0001-2006 index request.
The present invention makes conducting electrostatic materials with conductive mica powder, and it has excellent anti-chemical and erosion resistance, and its granule surface area is big, is easy to disperse in resin and be in contact with one another, and can obtain good persistent electrostatic conductive performance.Metal oxide is good semiconductor material, and stable performance can be not oxidized, can play the dual function of conduction and anticorrosion (sacrificial anode).Polyaniline material have good antirust, anticorrosion, conduct electricity very well, their threes unite doping and can form stable conductive network, to oil-proofness, the preservative property of paint film, lead static good performance guarantee is provided.
Embodiment
Embodiment 1:
In the presence of the catalyzer Diisopropyl azodicarboxylate, 10wt% liquid acrylonitrile butadiene rubber-40 (Lanzhou Petrochemical Company product) and 90wt% Resins, epoxy (E51) are heated to 110 ℃ of reaction 1h, obtain butyronitrile Resins, epoxy.
Polyether Glycols (Mn=1500) is stand-by at 110 ℃ of following reduced vacuum (0.1MPa) dehydration 5h.In the four-hole bottle that thermometer, agitator, prolong are housed, at N 2The total mol ratio of adding NCO/OH is 1.6 tolylene diisocyanate under the gas shiled; the polyether Glycols of dehydration; be warmed up to 80 ℃ gradually; reaction 3h; sampling and measuring NCO base content; after reaching prescribed value; the linking agent TriMethylolPropane(TMP) that adds the polyether Glycols mixture total weight amount 8% of tolylene diisocyanate and dehydration; 3.5% chainextender dimethylol propionic acid and 22% butyronitrile Resins, epoxy; reaction 4h; be cooled to room temperature; add triethylamine and be neutralized to neutrality; under the high speed shear power of 1300r/min, the emulsifying water that adds the polyether Glycols mixture total weight amount 20% of tolylene diisocyanate and dehydration obtains aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion.
Get the 70wt% conductive mica powder, 23wt% conductive polyaniline (JGT-ES-1, Chongqing Jingute Chemical New Material Techn Co., Ltd.), the stannic oxide of 7wt% is with PTFE emulsion (consumption be quiet mica powder, polyaniline and stannic oxide mixture total weight amount 30%) mixing and stirring, put into chamber type electric resistance furnace under 800 ℃ of temperature, roasting 2~3h is cooled to room temperature, and it is stand-by that ball milling becomes 5~10 μ m powder (complex conductive fillers) then.
10 gram water are added aqueous dispersant (W6038, rise imperial chemical industry trade Co., Ltd) 0.5 gram stirs well, add wetting agent (W203 then, rise imperial chemical industry trade Co., Ltd) 0.6 gram, titanium dioxide (rutile-type) 2 grams, ferrotitanium powder 7 grams, sand milling disperses 30min under the 1300r/min shearing force, makes fineness less than 50 μ m, adds complex conductive fillers 18 grams again and stirs 30min, add aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion 55 grams then, defoamer (W4002 rises imperial chemical industry trade Co., Ltd) 0.3 gram, flow agent (W3018, rise imperial chemical industry trade Co., Ltd) 0.4 gram, inhibiter (SER-ADFA179, Shanghai auspicious group industry development company limited) 2 grams, film coalescence aid (Texonol, Changfeng Chemical Plant, Shanghai) 4 grams mix and obtain light water-based electrostatic conductive anticorrosion paint.
Embodiment 2:
In the presence of the catalyzer methylimidazole, 30wt% liquid acrylonitrile butadiene rubber-26 (Lanzhou Petrochemical Company product) and 70wt% Resins, epoxy (E51) are heated to 80 ℃ of reaction 1.5h, obtain butyronitrile Resins, epoxy.
Polyether Glycols (Mn=2000) is stand-by at 90 ℃ of following reduced vacuum (0.1MPa) dehydration 6h.In the four-hole bottle that thermometer, agitator, prolong are housed, at N 2The total mol ratio of adding NCO/OH is 1.4 tolylene diisocyanate under the gas shiled; the polyether Glycols of dehydration; be warmed up to 80 ℃ gradually; reaction 1.5h; sampling and measuring NCO base content; after reaching prescribed value; the linking agent TriMethylolPropane(TMP) that adds the polyether Glycols mixture total weight amount 4% of tolylene diisocyanate and dehydration; 5% chainextender dimethylol propionic acid and 40% butyronitrile Resins, epoxy; reaction 2h; be cooled to room temperature; add triethylamine and be neutralized to neutrality; under the high speed shear power of 1000r/min, the emulsifying water that adds the polyether Glycols mixture total weight amount 25% of tolylene diisocyanate and dehydration obtains aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion.
Get the 80wt% conductive mica powder, 12wt% polyaniline (ZP-ES1, Zhengji Science and Technology Development Co., Ltd., Jilin), the stannic oxide of 8wt% is with PTFE emulsion (consumption be conductive mica powder, polyaniline and stannic oxide mixture total weight amount 40%) mixing and stirring, put into chamber type electric resistance furnace under 600 ℃ of temperature, roasting 3h is cooled to room temperature, and it is stand-by that ball milling becomes 5~10 μ m powder (complex conductive fillers) then.
Dispersion agent (W6038) 0.3 gram is stirred well, add wetting agent (W203) 0.7 gram then, process white 12 grams, ferrotitanium powder 15 grams, sand milling disperses 20min under the 1500r/min shearing force, make fineness less than 60 μ m, add complex conductive fillers 16 grams again and stir 30min, add aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion 46 grams then, defoamer (W4002) 0.5 gram, flow agent (W3018) 0.5 gram, inhibiter (SER-ADFA179) 4 restrain, film coalescence aid (Texonol) 5 grams mix and obtain light water-based electrostatic conductive anticorrosion paint.
Coating detected result provided by the invention is except satisfying general index.Special index is as follows: 1. electrostatic conductive anticorrosion paint resistivity Ps is 10 6~10 8Ω/cm 22. the coating heatproof is at 150 ℃~180 ℃; 3. this product price is than fluorine carbon electrostatic conductive anticorrosion paint low 40~60%.
Adopt ternary system conducting electrostatic materials (conductive mica powder, polyaniline, stannic oxide) in this present invention, resin adopts aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion, form electrostatic conductive anticorrosion paint, every index all reaches CNCIA-HG/0001-2006 index request.
It has excellent anti-chemical and erosion resistance to make conducting electrostatic materials with conductive mica powder, and its granule surface area is big, is easy to disperse in resin and be in contact with one another, and can obtain good persistent electrostatic conductive performance.Metal oxide is good semiconductor material, and stable performance can be not oxidized, can play the dual function of conduction and anticorrosion (sacrificial anode).Polyaniline material have good antirust, anticorrosion, conduct electricity very well, their threes unite doping and can form stable conductive network, to oil-proofness, the preservative property of paint film, lead static good performance guarantee is provided.

Claims (6)

1. an electrostatic conductive anticorrosion paint comprises 45~66% aqueous polyurethanes-butyronitrile epoxy composite dispersion emulsion; 15~20% complex conductive fillerses, 1~5% inhibiter, 5~18% ferrotitanium powder, 0.3~0.6% dispersion agent, 0.4~0.8% wetting agent, 0.2~0.5% defoamer, 0.3~0.6% flow agent, 4~6% film coalescence aid and 2~14% color stuffings; Described complex conductive fillers is made by laxative remedy: get 60%~80% and lead quiet mica powder, 10%~30% polyaniline, 5%~10% stannic oxide, use the ptfe emulsion mixing and stirring, under 500~1000 ℃ of temperature, roasting, ball milling becomes 5~10 μ m powder then, and the consumption of ptfe emulsion is 20~40% of conductive mica powder, polyaniline and a stannic oxide amount of the mixture; Above per-cent is weight percentage.
2. electrostatic conductive anticorrosion paint according to claim 1; it is characterized in that aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion is obtained by laxative remedy: under nitrogen protection; with the total mol ratio of NCO/OH is that the polyether Glycols of 1.4~1.7 tolylene diisocyanate and dehydration is at 80 ℃; reaction 1~3h; the linking agent TriMethylolPropane(TMP) that adds the polyether Glycols mixture total weight amount 2~10% of tolylene diisocyanate and dehydration; 1~5% chainextender dimethylol propionic acid and 20~50% butyronitrile Resins, epoxy; reaction 2-5h; be cooled to room temperature; add triethylamine and be neutralized to neutrality, the emulsifying water that adds the polyether Glycols mixture total weight amount 20-25% of tolylene diisocyanate and dehydration under 1000-1500 rev/mins high speed shear power obtains aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion.
3. electrostatic conductive anticorrosion paint according to claim 2, it is characterized in that: butyronitrile Resins, epoxy is prepared by laxative remedy: in the presence of catalyzer Diisopropyl azodicarboxylate or methylimidazole, 10~30wt% paracril and 70~90wt% Resins, epoxy, 80~120 ℃ of reacting by heating of temperature of reaction obtain butyronitrile Resins, epoxy.
4. according to claim 2 or 3 described electrostatic conductive anticorrosion paints, it is characterized in that the polyether Glycols that dewaters is obtained by laxative remedy: with polyether Glycols at 90~110 ℃ of following decompression dehydration 4~6h.
5. according to claim 1 or 2 or 3 described electrostatic conductive anticorrosion paints, it is characterized in that: inhibiter is SER-ADFA179, dispersion agent is W6038, wetting agent is W203, defoamer is W4002, flow agent is W3018, and film coalescence aid is Texonol, and color stuffing is process white or rutile titanium dioxide.
6. the preparation method of the described electrostatic conductive anticorrosion paint of claim 1, dispersion agent, wetting agent, titanium dioxide and ferrotitanium powder are mixed, sand milling is dispersed to fineness less than 60 μ m under 1000-1500 rev/mins shearing force, adding the composite conductive powder filler again stirs, add aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion, defoamer, flow agent, inhibiter and film coalescence aid then and stir, obtain electrostatic conductive anticorrosion paint; Described aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion is obtained by laxative remedy: under nitrogen protection, with the total mol ratio of NCO/OH is that the polyether Glycols of 1.4~1.7 tolylene diisocyanate and dehydration is at 80 ℃, reaction 1~3h, the linking agent TriMethylolPropane(TMP) that adds the polyether Glycols mixture total weight amount 2~10% of tolylene diisocyanate and dehydration, chainextender dimethylol propionic acid 1~5% and butyronitrile Resins, epoxy 20~50%, reaction 2-5h, be cooled to room temperature, add triethylamine and be neutralized to neutrality, the emulsifying water that adds the polyether Glycols mixture total weight amount 20-25% of tolylene diisocyanate and dehydration under 1000-1500 rev/mins high speed shear power obtains aqueous polyurethane-butyronitrile epoxy composite dispersion emulsion; Described butyronitrile Resins, epoxy is prepared by laxative remedy: in the presence of catalyzer Diisopropyl azodicarboxylate or methylimidazole, and 10~30wt% paracril and 70~90wt% Resins, epoxy, 80~120 ℃ of reacting by heating of temperature of reaction obtain butyronitrile Resins, epoxy; Described complex conductive fillers is made by laxative remedy: gets 50~80wt% and leads quiet mica powder, and 10~30wt% polyaniline, 5~10wt% stannic oxide, with PTFE emulsion mixing and stirring, under 500~1000 ℃ of temperature, roasting, ball milling becomes 5~10 μ m powder then.
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CN102070960A (en) * 2010-12-15 2011-05-25 常州大学 Aqueous anticorrosive conductive coating containing conductive polymer and preparation method thereof
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CN105419620B (en) * 2015-12-10 2018-06-05 中山新隆昌化工有限公司 A kind of modified polyurethane resin coating and preparation method thereof
CN105969176A (en) * 2016-06-01 2016-09-28 许婷 Anticorrosive paint for electric system and preparing method thereof
CN106752141A (en) * 2016-12-14 2017-05-31 北京先研科技有限责任公司 Waterborne conductive anticorrosive paint
CN109259364A (en) * 2018-08-19 2019-01-25 宁波元元尚品服饰科技有限公司 A kind of garment material and its processing method with antibiotic property

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