CN109021725A - A kind of oil pipeline wear-resistance and anti-corrosion conductive coating and preparation method thereof - Google Patents

A kind of oil pipeline wear-resistance and anti-corrosion conductive coating and preparation method thereof Download PDF

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CN109021725A
CN109021725A CN201810765925.3A CN201810765925A CN109021725A CN 109021725 A CN109021725 A CN 109021725A CN 201810765925 A CN201810765925 A CN 201810765925A CN 109021725 A CN109021725 A CN 109021725A
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parts
component
conductive coating
resistance
oil pipeline
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陈群
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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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • 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
    • C09D5/24—Electrically-conducting 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
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

Abstract

The present invention provides a kind of oil pipeline wear-resistance and anti-corrosion conductive coating and preparation method thereof, it is related to coating technology field, including component A and B component, the weight ratio of the component A and B component is 10-14:1, the component A includes the constituent of following parts by weight: 60-80 parts of PVDF resin, 40-50 parts of acrylic resin, 2, 20-30 parts of 4- toluene di-isocyanate(TDI), it is single-walled carbon nanotube 10-20 parts modified, 5-10 parts of DY-20, 5-20 parts of aluminum oxide colloidal sol, 1-10 parts of dispersing agent, 1-10 parts of defoaming agent, 200-250 parts of butyl acetate, 50-100 parts of ethyl alcohol, the B component is curing agent HX-90B, conductive coating items excellent in mechanical performance of the present invention, and wear-resistance and anti-corrosion, it is a kind of outstanding Oil pipeline wear-resistance and anti-corrosion conductive coating.

Description

A kind of oil pipeline wear-resistance and anti-corrosion conductive coating and preparation method thereof
Technical field
The present invention relates to coating technology fields, and in particular to a kind of oil pipeline wear-resistance and anti-corrosion conductive coating and its preparation Method.
Background technique
Oil-gas pipeline is either laid on underground or underwater, and pipeline outer wall is subjected to outside air, soil, water etc. Corrosion, corrosion of the inner wall of the pipe by pumped (conveying) medium.Especially when containing the pernicious gases such as sulfur dioxide, hydrogen sulfide in air, Chemical attack will be generated.In addition, underground can also generate chemical attack, underground stray electrical current can also generate electrochemical corrosion. Oil pipeline, which corrodes bring, mainly influences harmful ground installation and pipeline, causes production disruption, and bleed runs oil, base oil, leakage The safety accidents such as burning, explosion even occur for oil, can not only bring huge economic loss, but also can endanger personal safety, dirt Contaminate environment.
In addition, oil pipeline coating not only needs have extremely strong corrosion resisting property, but also there is preferable electric conductivity, and it is existing Coating can be dissolved mostly by the swelling of petroleum media, the conducting medium inside coating mostly uses greatly metal powder or metal to aoxidize Object, the protective performance and electric conductivity of this coating are all poor.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of oil pipeline wear-resistance and anti-corrosion conductive coating and its preparations Method.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component, the weight of the component A and B component Amount is than being 10-14:1, and the component A includes the constituent of following parts by weight: 60-80 parts of PVDF resin, acrylic resin 40-50 parts, 20-30 parts of 2,4 toluene diisocyanate, single-walled carbon nanotube 10-20 parts modified, 5-10 parts of DY-20, three oxidations Two 5-20 parts of Aluminum sols, 1-10 parts of dispersing agent, 1-10 parts of defoaming agent, 200-250 parts of butyl acetate, 50-100 parts of ethyl alcohol, the B Group is divided into curing agent HX-90B.
Preferably, including component A and B component, the weight ratio of the component A and B component is 10:1, and the component A includes The constituent of following parts by weight: 70 parts of PVDF resin, 25 parts of 2,4 toluene diisocyanate, changes 45 parts of acrylic resin Property 13 parts of single-walled carbon nanotube, 8 parts of DY-20,10 parts of aluminum oxide colloidal sol, 5 parts of dispersing agent, 5 parts of defoaming agent, butyl acetate 240 parts, 60 parts of ethyl alcohol, the B component are curing agent HX-90B.
Preferably, the production method of the modified multiwalled carbon nanotube are as follows: be added to trimethyl cetyl ammonium bromide In distilled water, metallic SWNTs are added after stirring and dissolving, 30-50 DEG C of ultrasonic disperse 5-10h naturally cools to room It is filtered after temperature, ethanol rinse after washing, 80 DEG C of drying.
Preferably, trimethyl cetyl ammonium bromide, metallic SWNTs, distilled water weight ratio be 1:10: 50。
Preferably, the mass content of bismuth is 18-21% in DY-20.
Preferably, the dispersing agent be BYK-163, BYK-162, BYK-161, UNIQJET 9510, UNIQJET 9315, At least one of UNIQJET 9370.
Preferably, the defoaming agent is at least one of B113, B108, E334, E305.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, comprising the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete It after dissolution, after 2,4- toluene di-isocyanate(TDI), DY-20 are diluted to a certain concentration with butyl acetate respectively while instilling, is added dropwise Time is 30-40min, and control reaction temperature is 40-60 DEG C, reacts 5-10h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersing agent, defoaming agent, butyl acetate, ethyl alcohol mixing 40-60min is dispersed with stirring with the speed of 200r/min while sonic oscillation processing, obtains mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 30-40min, grinding distribution 2-4h；
Preferably, 2, the 4- toluene di-isocyanate(TDI) mass concentration after being diluted with butyl acetate is 10-15%, with acetic acid fourth DY-20 mass concentration after ester dilution is 2-5%.
Preferably, ultrasound intensity is 20-30W/cm when sonic oscillation is handled2。
(3) beneficial effect
The present invention provides a kind of oil pipeline wear-resistance and anti-corrosion conductive coating and preparation method thereof, have below beneficial to effect Fruit:
Modified single-walled carbon nanotube is added in the compound resin of PVDF resin, acrylic resin in the present invention, it is made The resistivity of the conductive coating obtained is minimum up to 2.24 × 102, electric conductivity fully meets oil pipeline to the conduction of conductive coating Property require；And modified single-walled carbon nanotube can reduce Coating Surface Roughness compared to metallic SWNTs, mention High-wear resistance, probably due to being that chain alkyl in trimethyl cetyl ammonium bromide passes through on Van der Waals force and carbon nanotube C-C, C=C combine, improve the dispersion performance of carbon nanotube, reduce reuniting effect, can be with visual verification from CLSM figure This guess；Contain a large amount of C-F key in this body structure of PVDF resin, C-F key bond energy is extremely strong, and C-C key main chain surrounding is by a system It arranges electronegative F atom to surround, forms highdensity bulk shield, ensure that the stabilization of coating, make it have fabulous corrosion resistant The adhesive force of PVDF resin and substrate can be improved in corrosion energy, the addition of acrylic resin, improves the consistency of coating, reduces Gap；On the other hand the addition of 2,4- toluene di-isocyanate(TDI) can be further improved the Corrosion Protection of conductive coating, may Be in 2,4- toluene di-isocyanate(TDI)-NCO group, penetrate between PVDF resin, acrylic resin, part and acrylic acid Carboxylic hydroxyl reaction on resin, partially forms with internal a small amount of moisture and applies with the stronger urea bond of metallic matrix adsorption capacity, raising The consistency and adsorption capacity of layer, to improve corrosion resistance；Conductive coating items excellent in mechanical performance of the present invention is a kind of excellent Elegant oil pipeline wear-resistance and anti-corrosion conductive coating.
Detailed description of the invention
Fig. 1 is progress CLSM figure after the made conductive coating brushing of comparative example 1；
Fig. 2 is progress CLSM figure after the made conductive coating brushing of embodiment 1.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention, Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component, the weight ratio of component A and B component For 10-14:1, component A includes the constituent of following parts by weight: 60-80 parts of PVDF resin, 40-50 parts of acrylic resin, 20-30 parts of 2,4 toluene diisocyanate, modified single-walled carbon nanotube 10-20 parts, 5-10 parts of DY-20, aluminum oxide colloidal sol 5-20 parts, 1-10 parts of dispersing agent, 1-10 parts of defoaming agent, 200-250 parts of butyl acetate, 50-100 parts of ethyl alcohol, B component is curing agent HX-90B。
PVDF resin, Guangzhou pine and cypress Chemical Co., Ltd. of producer；Acrylic resin, the triumphant mattress chemical industry in producer Shanghai；2,4- first Phenylene diisocyanate, ShouGuang Luyuan Salt Chemical Co., Ltd. of producer；Metallic SWNTs diameter 2nm, producer Xuzhou are prompt Innovative material Science and Technology Ltd.；DY-20, Shanghai De Yin Chemical Co., Ltd. of producer；Aluminum oxide colloidal sol, it is solidifying using solution The self-control of glue method；Butyl acetate, producer Jiangsu Suo Pu；Ethyl alcohol, Shanghai Lv Shi Chemical Co., Ltd. of producer；Curing agent HX-90B, factory Sen Baoli Chemical Co., Ltd. of Shunde District of Foshan City of family.
Preferably, including component A and B component, the weight ratio of component A and B component is 10:1, and component A includes following weight The constituent of number: 70 parts of PVDF resin, 45 parts of acrylic resin, 25 parts of 2,4 toluene diisocyanate, modified single wall carbon 13 parts of nanotube, 8 parts of DY-20,10 parts of aluminum oxide colloidal sol, 5 parts of dispersing agent, 5 parts of defoaming agent, 240 parts of butyl acetate, second 60 parts of alcohol, B component is curing agent HX-90B.
Preferably, the production method of modified multiwalled carbon nanotube are as follows: trimethyl cetyl ammonium bromide is added to distillation In water, metallic SWNTs are added after stirring and dissolving, 30-50 DEG C of ultrasonic disperse 5-10h, after cooled to room temperature It filters, ethanol rinse after washing, 80 DEG C of drying.
Preferably, trimethyl cetyl ammonium bromide, metallic SWNTs, distilled water weight ratio be 1:10: 50。
Preferably, the mass content of bismuth is 18-21% in DY-20.
Preferably, dispersing agent BYK-163, BYK-162, BYK-161, UNIQJET 9510, UNIQJET 9315, At least one of UNIQJET 9370.
Dispersant B YK-163, BYK-162, BYK-161 are purchased from Dongguan City Zhong Dimei fine chemistry industry Import and Export Co., Ltd., Place of production Germany；UNIQJET 9510, UNIQJET 9315, UNIQJET 9370, the easy Chemical Co., Ltd. of sea light in producer.
Preferably, at least one of defoaming agent B113, B108, E334, E305.
Defoaming agent is B113, B108, E334, E305, Nanjing Lei Pu Chemical Co., Ltd. of producer.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, comprising the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete It after dissolution, after 2,4- toluene di-isocyanate(TDI), DY-20 are diluted to a certain concentration with butyl acetate respectively while instilling, is added dropwise Time is 30-40min, and control reaction temperature is 40-60 DEG C, reacts 5-10h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersing agent, defoaming agent, butyl acetate, ethyl alcohol mixing 40-60min is dispersed with stirring with the speed of 200r/min while sonic oscillation processing, obtains mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 30-40min, grinding distribution 2-4h；
Preferably, 2, the 4- toluene di-isocyanate(TDI) mass concentration after being diluted with butyl acetate is 10-15%, with acetic acid fourth DY-20 mass concentration after ester dilution is 2-5%.
Preferably, ultrasound intensity is 20-30W/cm when sonic oscillation is handled2。
Embodiment 1:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 10:1, and component A includes the constituent of following parts by weight: PVDF resin 70 Part, 45 parts of acrylic resin, 25 parts of 2,4 toluene diisocyanate, modified 8 parts of 13 parts of single-walled carbon nanotube, DY-20 (DY-20 The mass content of middle bismuth be 18.5%), 10 parts of aluminum oxide colloidal sol, 5 parts of dispersant B YK-163,5 parts of defoaming agent B113, 240 parts of butyl acetate, 60 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube are as follows: trimethyl cetyl ammonium bromide is added in distilled water, is stirred Metallic SWNTs (trimethyl cetyl ammonium bromide, metallic SWNTs, distillation are added after mixing dissolution The weight ratio of water is 1:10:50), 40 DEG C of ultrasonic disperse 8h are filtered after cooled to room temperature, ethanol rinse after washing, 80 DEG C Drying.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, which comprises the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete After dissolution, it is 12%, mass concentration that 2,4- toluene di-isocyanate(TDI), DY-20, which are diluted to mass concentration with butyl acetate respectively, It is 4%, then instills simultaneously, time for adding 35min, control reaction temperature is 50 DEG C, reacts 7h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersant B YK-163, defoaming agent B113, acetic acid fourth Ester, ethyl alcohol mixing sonic oscillation processing while with the speed of 200r/min be dispersed with stirring 50min (sonic oscillation processing when ultrasound Intensity is 25W/cm2), obtain mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 35min, grinding distribution 3h.
Embodiment 2:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 11:1, and component A includes the constituent of following parts by weight: PVDF resin 65 Part, 43 parts of acrylic resin, 22 parts of 2,4 toluene diisocyanate, modified 7 parts of 16 parts of single-walled carbon nanotube, DY-20 (DY-20 The mass content of middle bismuth be 20%), 15 parts of aluminum oxide colloidal sol, 6 parts of dispersant B YK-162,2 parts of defoaming agent B108, second 220 parts of acid butyl ester, 70 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube are as follows: trimethyl cetyl ammonium bromide is added in distilled water, is stirred Metallic SWNTs (trimethyl cetyl ammonium bromide, metallic SWNTs, distillation are added after mixing dissolution The weight ratio of water is 1:10:50), 35 DEG C of ultrasonic disperse 7h are filtered after cooled to room temperature, ethanol rinse after washing, 80 DEG C Drying.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, which comprises the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete After dissolution, it is 13%, mass concentration that 2,4- toluene di-isocyanate(TDI), DY-20, which are diluted to mass concentration with butyl acetate respectively, It is 3%, then instills simultaneously, time for adding 32min, control reaction temperature is 45 DEG C, reacts 5.5h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersant B YK-162, defoaming agent B108, acetic acid fourth Ester, ethyl alcohol mixing sonic oscillation processing while with the speed of 200r/min be dispersed with stirring 55min (sonic oscillation processing when ultrasound Intensity is 30W/cm2), obtain mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 40min, grinding distribution 2.5h.
Embodiment 3:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 10:1, and component A includes the constituent of following parts by weight: PVDF resin 60 Part, 40 parts of acrylic resin, 20 parts of 2,4 toluene diisocyanate, modified 5 parts of 10 parts of single-walled carbon nanotube, DY-20 (DY-20 The mass content of middle bismuth be 18%), 5 parts of aluminum oxide colloidal sol, 1 part of dispersant B YK-161,1 part of defoaming agent E334, acetic acid 200 parts of butyl ester, 50 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube are as follows: trimethyl cetyl ammonium bromide is added in distilled water, is stirred Metallic SWNTs (trimethyl cetyl ammonium bromide, metallic SWNTs, distillation are added after mixing dissolution The weight ratio of water is 1:10:50), 30 DEG C of ultrasonic disperse 5h are filtered after cooled to room temperature, ethanol rinse after washing, 80 DEG C Drying.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, which comprises the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete After dissolution, it is 10%, mass concentration that 2,4- toluene di-isocyanate(TDI), DY-20, which are diluted to mass concentration with butyl acetate respectively, It is 2%, then instills simultaneously, time for adding 30min, control reaction temperature is 40 DEG C, reacts 5h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersant B YK-161, defoaming agent E334, acetic acid fourth Ester, ethyl alcohol mixing sonic oscillation processing while with the speed of 200r/min be dispersed with stirring 40min (sonic oscillation processing when ultrasound Intensity is 20W/cm2), obtain mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 30min, grinding distribution 2h.
Embodiment 4:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 14:1, and component A includes the constituent of following parts by weight: PVDF resin 80 Part, 50 parts of acrylic resin, 30 parts of 2,4 toluene diisocyanate, modified 10 parts of 20 parts of single-walled carbon nanotube, DY-20 (DY- In 20 the mass content of bismuth be 21%), 20 parts of aluminum oxide colloidal sol, 9,510 10 parts of dispersing agent UNIQJET, defoaming agent E305 10 parts, 250 parts of butyl acetate, 100 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube are as follows: trimethyl cetyl ammonium bromide is added in distilled water, is stirred Metallic SWNTs (trimethyl cetyl ammonium bromide, metallic SWNTs, distillation are added after mixing dissolution The weight ratio of water is 1:10:50), 50 DEG C of ultrasonic disperse 10h are filtered after cooled to room temperature, ethanol rinse after washing, 80 DEG C Drying.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, which comprises the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete After dissolution, it is 15%, mass concentration that 2,4- toluene di-isocyanate(TDI), DY-20, which are diluted to mass concentration with butyl acetate respectively, It is 5%, then instills simultaneously, time for adding 40min, control reaction temperature is 60 DEG C, reacts 10h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersing agent UNIQJET9510, defoaming agent E305, second 60min is dispersed with stirring (when sonic oscillation processing with the speed of 200r/min while acid butyl ester, the processing of ethyl alcohol mixing sonic oscillation Ultrasound intensity is 30W/cm2), obtain mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 40min, grinding distribution 4h.
Embodiment 5:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 10:1, and component A includes the constituent of following parts by weight: PVDF resin 60 Part, 44 parts of acrylic resin, 26 parts of 2,4 toluene diisocyanate, modified 10 parts of 10 parts of single-walled carbon nanotube, DY-20 (DY- In 20 the mass content of bismuth be 21%), 8 parts of aluminum oxide colloidal sol, 9,315 1 parts of dispersing agent UNIQJET, defoaming agent B113, 10 parts of B108 (weight ratio of B113, B108 are 1:1), 220 parts of butyl acetate, 60 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube are as follows: trimethyl cetyl ammonium bromide is added in distilled water, is stirred Metallic SWNTs (trimethyl cetyl ammonium bromide, metallic SWNTs, distillation are added after mixing dissolution The weight ratio of water is 1:10:50), 32 DEG C of ultrasonic disperse 6.5h are filtered after cooled to room temperature, ethanol rinse after washing, 80 DEG C drying.
The preparation method of above-mentioned oil pipeline wear-resistance and anti-corrosion conductive coating, which comprises the following steps:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, several melted paraxylenes are added dropwise, stirs to complete After dissolution, it is that 12.5%, quality is dense that 2,4- toluene di-isocyanate(TDI), DY-20, which are diluted to mass concentration with butyl acetate respectively, Degree is 4%, is then instilled simultaneously, time for adding 30min, and control reaction temperature is 45 DEG C, reacts 5.5h, obtains mixed material A；
(2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersing agent UNIQJET9315, defoaming agent B113, 60min (ultrasound vibration is dispersed with stirring with the speed of 200r/min while B108, butyl acetate, the processing of ethyl alcohol mixing sonic oscillation Ultrasound intensity is 25W/cm when swinging processing2), obtain mixed material B；
(3) mixed material B is transferred into grinder, is slowly added to mixed material A in grinding, control is added the time and is 38min, grinding distribution 2.5h.
Embodiment 6:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 10:1, and component A includes the constituent of following parts by weight: PVDF resin 80 Part, 40 parts of acrylic resin, 30 parts of 2,4 toluene diisocyanate, modified 10 parts of 10 parts of single-walled carbon nanotube, DY-20 (DY- In 20 the mass content of bismuth be 18%), 20 parts of aluminum oxide colloidal sol, 9,370 1 parts of dispersing agent UNIQJET, defoaming agent E334, 10 parts of E305 (weight ratio of E334, E305 are 2:1), 200 parts of butyl acetate, 100 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube is identical with embodiment 1.
The preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating is substantially the same manner as Example 1, and difference is, dispersing agent For UNIQJET 9370, defoaming agent E334, E305.
Embodiment 7:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 14:1, and component A includes the constituent of following parts by weight: PVDF resin 60 Part, 50 parts of acrylic resin, 20 parts of 2,4 toluene diisocyanate, modified 5 parts of 20 parts of single-walled carbon nanotube, DY-20 (DY-20 The mass content of middle bismuth be 21%), 5 parts of aluminum oxide colloidal sol, 10 parts of dispersant B YK-163, BYK-162 (BYK-163, The weight ratio of BYK-162 is 5:1), 10 parts of defoaming agent B108,200 parts of butyl acetate, 100 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube is identical with embodiment 1.
The preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating is substantially the same manner as Example 1, and difference is, dispersing agent For BYK-163, BYK-162, defoaming agent B108.
Embodiment 8:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 11.5:1, and component A includes the constituent of following parts by weight: PVDF resin 60 parts, 40 parts of acrylic resin, 20 parts of 2,4 toluene diisocyanate, modified 5 parts of 10 parts of single-walled carbon nanotube, DY-20 (DY- In 20 the mass content of bismuth be 18%), 5 parts of aluminum oxide colloidal sol, 1 part of dispersant B YK-163,1 part of defoaming agent B113, second 200 parts of acid butyl ester, 50 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube is identical with embodiment 1.
The preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating is identical with embodiment 1.
Embodiment 9:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 11.5:1, and component A includes the constituent of following parts by weight: PVDF resin 76 parts, 44 parts of acrylic resin, 26 parts of 2,4 toluene diisocyanate, modified 5 parts of 10 parts of single-walled carbon nanotube, DY-20 (DY- In 20 the mass content of bismuth be 20.5%), 15 parts of aluminum oxide colloidal sol, 5.5 parts of dispersant B YK-163, defoaming agent B1135.5 parts, 240 parts of butyl acetate, 60 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube is identical with embodiment 1.
The preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating is identical with embodiment 1.
Embodiment 10:
A kind of oil pipeline wear-resistance and anti-corrosion conductive coating, including component A and B component；
The weight ratio of component A and B component is 14:1, and component A includes the constituent of following parts by weight: PVDF resin 80 Part, 50 parts of acrylic resin, 30 parts of 2,4 toluene diisocyanate, modified 10 parts of 20 parts of single-walled carbon nanotube, DY-20 (DY- In 20 the mass content of bismuth be 21%), 20 parts of aluminum oxide colloidal sol, 1 part of dispersant B YK-163,1 part of defoaming agent B113, 200 parts of butyl acetate, 50 parts of ethyl alcohol；
B component is curing agent HX-90B.
The production method of modified multiwalled carbon nanotube is identical with embodiment 1.
The preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating is identical with embodiment 1.
Comparative example 1:
Substantially the same manner as Example 1, difference is, modified single-walled carbon nanotube is replaced with metal single-wall carbon nanometer Pipe.
Comparative example 2:
Substantially the same manner as Example 1, difference is, is added without modified single-walled carbon nanotube.
Comparative example 3:
Substantially the same manner as Example 1, difference is, is added without 2,4- toluene di-isocyanate(TDI).
The test of conductive coating surface roughness:
In order to study whether metallic SWNTs are modified influence to conductive coating roughness, by 1 He of embodiment Laser confocal scanning microscope (CLSM) morphologic observation is carried out after the made conductive coating brushing of comparative example 1, observation result is as schemed 1, shown in Fig. 2, roughness test result is as shown in lower section table 1:
Table 1:
As seen from the above table, it is thick compared to metallic SWNTs can to reduce coating surface for modified single-walled carbon nanotube Rugosity improves wear-resisting property, it may be possible to which the chain alkyl in trimethyl cetyl ammonium bromide passes through Van der Waals force and carbon nanometer C-C, C=C on pipe are combined, and are improved the dispersion performance of carbon nanotube, are reduced reuniting effect.
The test of conductive coating surface resistivity:
By GB/T 1410-2006 " solid insulating material volume resistivity and surface resistivity test method " regulation into Row test, the pretreatment condition of test specimen is (23 ± 2) DEG C, 4h, electrochemical time 1min, test voltage 10V under RH (50 ± 3) %, Test result is as follows shown in square table 2:
Table 2:
As seen from the above table, the conductive coating of modified single-walled carbon nanotube is added compared to addition metallic SWNTs Conductive coating its surface resistivity difference it is little, but do not add the coating of modified single-walled carbon nanotube, surface resistivity Reach 4.56 × 1011, do not have electric conductivity, so the present invention adds modified single-walled carbon nanotube, coating can be substantially reduced Surface resistivity, improve conductive effect.
The test of conductive coating salt spray resistance:
This test is carried out referring to GB/T6458-1986 " metal cladding neutral salt spray test (NSS test) ", the testing time For for 24 hours, 96h, 240h and 480h, test result is as follows shown in table 3:
Table 3:
As seen from the above table, conductive coating of the present invention has outstanding Corrosion Protection, on the one hand, this body structure of PVDF resin In contain a large amount of C-F key, C-F key bond energy is extremely strong, and C-C key main chain surrounding is surrounded by a series of electronegative F atoms, is formed high The bulk shield of density ensure that the stabilization of coating, make it have fabulous corrosion resistance, the addition of acrylic resin can To improve the adhesive force of PVDF resin and substrate, the consistency of coating is improved, reduces gap；Another aspect 2,4- toluene diisocyanate The addition of acid esters can be further improved the Corrosion Protection of conductive coating, it may be possible to-the NCO in 2,4- toluene di-isocyanate(TDI)s Group penetrates between PVDF resin, acrylic resin, partially reacts with the carboxylic hydroxyl on acrylic resin, partially with it is interior A small amount of moisture in portion is formed and the stronger urea bond of metallic matrix adsorption capacity, the consistency and adsorption capacity of coating is improved, to improve Corrosion resistance.
Conductive coating Mechanics Performance Testing:
1-5 conductive coating Mechanics Performance Testing comparing result of the embodiment of the present invention is as shown in table 4 below:
Table 4:
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that There is also other identical elements in process, method, article or equipment including the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.

Claims (10)

1. a kind of oil pipeline wear-resistance and anti-corrosion conductive coating, which is characterized in that including component A and B component, the component A and B The weight ratio of component is 10-14:1, and the component A includes the constituent of following parts by weight: 60-80 parts of PVDF resin, third 40-50 parts of olefin(e) acid resin, 20-30 parts of 2,4 toluene diisocyanate, modified single-walled carbon nanotube 10-20 parts, DY-205-10 Part, 5-20 parts of aluminum oxide colloidal sol, 1-10 parts of dispersing agent, 1-10 parts of defoaming agent, 200-250 parts of butyl acetate, ethyl alcohol 50- 100 parts, the B component is curing agent HX-90B.
2. oil pipeline wear-resistance and anti-corrosion conductive coating as described in claim 1, which is characterized in that including component A and B group Point, the weight ratio of the component A and B component is 10:1, and the component A includes the constituent of following parts by weight: PVDF tree 70 parts of rouge, 45 parts of acrylic resin, 25 parts of 2,4 toluene diisocyanate, modified 13 parts of single-walled carbon nanotube, DY-208 parts, three 10 parts of Al 2 O colloidal sol, 5 parts of dispersing agent, 5 parts of defoaming agent, 240 parts of butyl acetate, 60 parts of ethyl alcohol, the B component are curing agent HX-90B。
3. oil pipeline wear-resistance and anti-corrosion conductive coating as described in claim 1, which is characterized in that the modified multi wall carbon is received The production method of mitron are as follows: trimethyl cetyl ammonium bromide is added in distilled water, metal mold is added after stirring and dissolving Single-walled carbon nanotube, 30-50 DEG C of ultrasonic disperse 5-10h are filtered after cooled to room temperature, ethanol rinse after washing, 80 DEG C of bakings It is dry.
4. oil pipeline wear-resistance and anti-corrosion conductive coating as claimed in claim 3, which is characterized in that trimethyl hexadecane bromide Change ammonium, metallic SWNTs, distilled water weight ratio be 1:10:50.
5. oil pipeline wear-resistance and anti-corrosion conductive coating as described in claim 1, which is characterized in that the quality of bismuth in DY-20 Content is 18-21%.
6. oil pipeline wear-resistance and anti-corrosion conductive coating as described in claim 1, which is characterized in that the dispersing agent is BYK- 163, at least one of BYK-162, BYK-161, UNIQJET 9510, UNIQJET 9315, UNIQJET 9370.
7. oil pipeline wear-resistance and anti-corrosion conductive coating as described in claim 1, which is characterized in that the defoaming agent is At least one of B113, B108, E334, E305.
8. the preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating as described in claim 1, which is characterized in that including with Lower step:
(1) appropriate butyl acetate is added into PVDF resin, acrylic resin, is added dropwise several melted paraxylenes, stirring is to being completely dissolved Afterwards, it after 2,4- toluene di-isocyanate(TDI), DY-20 being diluted to a certain concentration with butyl acetate respectively while instilling, time for adding For 30-40min, controlling reaction temperature is 40-60 DEG C, reacts 5-10h, obtains mixed material A；
It (2) will modified single-walled carbon nanotube, aluminum oxide colloidal sol, dispersing agent, defoaming agent, butyl acetate, ethyl alcohol mixing ultrasound 40-60min is dispersed with stirring with the speed of 200r/min while oscillation treatment, obtains mixed material B；
(3) mixed material B is transferred into grinder, mixed material A is slowly added in grinding, the time is added as 30- in control 40min, grinding distribution 2-4h.
9. the preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating as claimed in claim 8, which is characterized in that use acetic acid 2,4- toluene di-isocyanate(TDI) mass concentration after butyl ester dilution is 10-15%, and the DY-20 mass after being diluted with butyl acetate is dense Degree is 2-5%.
10. the preparation method of oil pipeline wear-resistance and anti-corrosion conductive coating as claimed in claim 8, which is characterized in that ultrasound Ultrasound intensity is 20-30W/cm when oscillation treatment2。
CN201810765925.3A 2018-07-12 2018-07-12 A kind of oil pipeline wear-resistance and anti-corrosion conductive coating and preparation method thereof Pending CN109021725A (en)

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Application publication date: 20181218