CN109439175A - A kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating and preparation method thereof - Google Patents
A kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating and preparation method thereof Download PDFInfo
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- CN109439175A CN109439175A CN201811297265.7A CN201811297265A CN109439175A CN 109439175 A CN109439175 A CN 109439175A CN 201811297265 A CN201811297265 A CN 201811297265A CN 109439175 A CN109439175 A CN 109439175A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
A kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating and preparation method thereof; packing material is added in polycaprolactone; then stannous octoate is added; 130-140 DEG C of reaction 24-36h; solvent, crosslinking agent and dibutyl tin dilaurate is added; 60-80 DEG C of stirring 5-10h under nitrogen protection is then coated in metal surface, solidification.Optical-thermal conversion material is introduced polymer network using polycaprolactone as substrate, by situ aggregation method by the present invention, and introduces catalyst and crosslinking agent, is formed polymer network by crosslinked action, is prepared the shape memory polyurethane coating for capableing of selfreparing.Under Infrared irradiation, coat inside is set to be rapidly heated to 130-140 DEG C by photothermal conversion, high temperature stimulation shape memory is replied, become to making wound surface contact, simultaneously, polymer segment strenuous exercise, across damage interface and along with the fracture and reconstruct of ammonia ester bond, to realize the self-repair function of coating.
Description
Technical field
The present invention relates to metal anti-corrosive paint fields, and in particular to a kind of photoresponse selfreparing shape memory polyurethane anti-corrosion
Coating and preparation method thereof.
Background technique
Metal erosion is the problem of not can avoid, to show according to related data, the whole world every year due to metal erosion caused by
Direct economic loss is up to 700,000,000,000 dollars, China because caused by metal erosion economic loss account for about the 3% of gross national product.
It therefore, is always hot spot concerned by people for the anti-corrosion research of metal material.In recent years, people mainly utilize organic coating to apply
In metal surface, exclusion of water, air and corrosivity particle prevent corrosion of metal, but organic coating is difficult to resist extraneous evil summary
Coating damage caused by environment, aggressivity particle immerse metal surface by breakage, lead to metal erosion, make coating failure.
In view of the above problems, self-healing coatings come into being, self-healing coatings i.e. when coating surface generates damaged, itself
Response can be generated to outside stimulus, damaged part be repaired by certain mode, self-heal realizes coating to matrix gold again
The effect of the protection of category.People are classified as independently repairing and repair with non-autonomous according to necessity of the self-repair material to outside stimulus
It is multiple, according to whether there are consolidants to be divided into inherent repair and external reparation.The appearance of self-healing coatings improves metal material
Reliability, durability and service life.
In fact, the coating of filling consolidant is limited when repairing surface damage by release consolidant volume, only
When lesion volume is less than the consolidant volume of release, damage could repair completely.When the healing of material is independent of consolidant
When discharging, but depending on the exchange of reversible key or polymer chain diffusion, heal the local route repair being only limitted in reversible key range, when
When damage location is excessive, key bridge can not be formed between gap, also resulting in wound can not heal.Rodriguez et al. proposes one
The concept of kind shape memory auxiliary selfreparing (shape-memory assisted healing), for example, in polycaprolactone
(PCL) in cross-linked network, the linear PCL chain of half penetration type is once heated can be terminated and repair damage location.Thermal energy is first
It activates damage location shape memory to reply, and restores mechanical energy by generating new keys between linear chain.The repair process is complete
It does not need to apply any external force entirely.But tradition makes the reply for driving shape memory and the selfreparing of inside by thermostimulation,
Operating there is limitations, in contrast, infrared light stimulus reparation is physically easier to perform, heat up rapider, and can be with
The long-range accurate control in part.Therefore, it designs one kind and is capable of the self-healing coatings of infrared optical response shape memory auxiliary for preventing
The damage of coating large area is very necessary.
Summary of the invention
It is an object of that present invention to provide a kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating and preparation method thereof,
The coating has good self-healing properties and shape-memory properties under Infrared irradiation, without applying any external force, is easy to
Operation, there is good application prospect in terms of anti-corrosive metal coating.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating, comprising the following steps:
1) packing material is added in the container equipped with polycaprolactone, ultrasonic disperse makes packing material be uniformly dispersed, so
Afterwards under nitrogen protection, stannous octoate is added, 130-140 DEG C of reaction 24-36h obtains graft polymers；
2) solvent, crosslinking agent and dibutyl tin dilaurate are added into graft polymers, under nitrogen protection 60-80
5-10h is stirred at DEG C, obtains solution, solution is coated on metal surface, solidification obtains the poly- ammonia of photoresponse selfreparing shape memory
Ester corrosion-inhibiting coating.
A further improvement of the present invention lies in that packing material is graphene oxide, poly-dopamine or multi-walled carbon nanotube.
A further improvement of the present invention lies in that the quality of packing material is packing material and polycaprolactone gross mass
0.1%-5%.
A further improvement of the present invention lies in that the ratio 1g of packing material and polycaprolactone gross mass and stannous octoate:
(0.001-0.005)μL。
A further improvement of the present invention lies in that ultrasonic power is 400W, time 1-4h.
A further improvement of the present invention lies in that solvent DMSO, DMF or THF；The ratio of graft polymers and solvent is 1:
(10-20)mL。
A further improvement of the present invention lies in that crosslinking agent 4,4`- methyl diphenylene diisocyanate, toluene diisocynate
Ester, 1,6- hexamethylene diisocyanate or benzene dimethylene diisocyanate；The additional amount of crosslinking agent is graft polymers
The 13%-23% of quality.
A further improvement of the present invention lies in that the additional amount of dibutyl tin dilaurate is graft polymers and crosslinking agent
The 0-1% of gross mass.
A further improvement of the present invention lies in that cured temperature is 60-80 DEG C, time 12h.
A kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating obtained according to above-mentioned preparation method.
Compared with existing self-healing coatings, selfreparing shape memory polyurethane coating designed by the present invention has following excellent
Point:
Optical-thermal conversion material is introduced polymer network using polycaprolactone as substrate, by situ aggregation method by the present invention,
And catalyst and crosslinking agent are introduced, polymer network is formed by crosslinked action, prepares a kind of shape note for capableing of selfreparing
Recall polyurethane coating.Under Infrared irradiation, coat inside is set to be rapidly heated to 130 DEG C or so by photothermal conversion, high temperature pierces
Swash shape memory reply, becoming makes wound surface contact, meanwhile, polymer segment strenuous exercise, across damage interface and along with
The fracture and reconstruct of ammonia ester bond, to realize the self-repair function of coating.The present invention assists its selfreparing, nothing by shape memory
External force need to be applied, the coating damage of large area can be repaired.Optical-thermal conversion material is dispersed in polymer network by the present invention,
Therefore light source can be used as stimulus, coating damage position is made to carry out selfreparing, it is easy to operate, it is flexible in application, it can long distance
From and local accurate control.Coating after the present invention is repaired can still keep good mechanical performance, can reach former painting
80% or more of layer mechanical strength.Energy effective protection metal, prevents from corroding, and extends metal service life.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides；
Fig. 2 is the nuclear magnetic resonance spectroscopy for the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides；
Fig. 3 is the transmission electricity of the graphene oxide that the embodiment of the present invention 1 provides and selfreparing shape memory polyurethane coating
Mirror figure；Wherein, (a) is the TEM of graphene oxide, (b) is the TEM of selfreparing shape memory polyurethane coating.
Fig. 4 is the petrographic microscope that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides repairs front and back
Comparison diagram；Wherein, petrographic microscope when (a) is coating damage irradiates figure, (b) shines for the petrographic microscope after coating selfreparing
Penetrate figure.
Fig. 5 is the petrographic microscope that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 4 provides repairs front and back
Comparison diagram；Wherein, petrographic microscope when (a) is coating damage irradiates figure, (b) shines for the petrographic microscope after coating selfreparing
Penetrate figure.
Fig. 6 is the petrographic microscope that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 6 provides repairs front and back
Comparison diagram；Wherein, petrographic microscope when (a) is coating damage irradiates figure, (b) shines for the petrographic microscope after coating selfreparing
Penetrate figure.
Fig. 7 is the petrographic microscope that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 7 provides repairs front and back
Comparison diagram；Wherein, petrographic microscope when (a) is coating damage irradiates figure, (b) shines for the petrographic microscope after coating selfreparing
Penetrate figure.
Fig. 8 is the scanning electron microscope pair that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides repairs front and back
Than figure；Wherein, SEM when (a) is coating damage is (b) SEM after coating selfreparing.
Fig. 9 is that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides shows coated on the anti-corrosion after blade
It is intended to.Wherein, (a) is the photo that pure blade is corroded, (b) photograph to be corroded after the blade damage of coating polyurethane coating
Piece, (c) photo to be corroded after the blade damage and selfreparing of coating polyurethane coating.
Figure 10 is that the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides is aobvious coated on the polarisation after blade
Micro mirror comparison diagram.Wherein, (a) is that pure blade is corroded the petrographic microscope photo of rear surface, is (b) coating polyurethane coating
The petrographic microscope photo on the surface being corroded after blade damage is (c) the blade damage and selfreparing of coating polyurethane coating
The petrographic microscope photo for the sample surfaces being corroded afterwards.
Specific embodiment
The present invention is prepared for a kind of shape memory polyurethane coating that can repair mass lesions.It is with reference to the accompanying drawing and real
Applying example, the present invention is described in further detail.Described herein the specific embodiments are only for explaining the present invention, rather than right
Restriction of the invention.
Optical-thermal conversion material is introduced polymer network using polycaprolactone as substrate, by situ aggregation method by the present invention,
And a certain amount of catalyst and crosslinking agent are introduced, polymer network is formed by crosslinked action, preparing one kind being capable of selfreparing
Shape memory polyurethane coating.Under Infrared irradiation, coat inside is set to be rapidly heated to 130 DEG C of left sides by photothermal conversion
The right side, high temperature stimulation shape memory are replied, and becoming makes wound surface contact, meanwhile, polymer segment strenuous exercise, across damage interface
And along with the fracture and reconstruct of ammonia ester bond, to realize the self-repair function of coating.
Photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating of the invention specific the preparation method is as follows:
1) packing material is weighed to be added in the container equipped with polycaprolactone, ultrasonic disperse makes packing material be uniformly dispersed,
Then under nitrogen protection, stannous octoate is added, 130-140 DEG C of reaction 24-36h obtains graft polymers；
Wherein, packing material is graphene oxide (GO), poly-dopamine particle or multi-walled carbon nanotube.
The quality of packing material is the 0.1%-5% of packing material and polycaprolactone gross mass.
The power of ultrasound is 400W, time 1-4h.
2) solvent, crosslinking agent and dibutyl tin dilaurate are added into graft polymers, under nitrogen protection 60-80
5-10h is stirred at DEG C, obtains solution, and solution is coated on metal surface, is solidified at 60-80 DEG C, is obtained photoresponse and review one's lessons by oneself complex
Shape memory polyurethane corrosion-inhibiting coating.
Wherein, solvent DMSO, DMF or THF；The ratio of graft polymers and solvent is 1:10-20mL；
Crosslinking agent is 4,4`- methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), 1,6- hexa-methylene diisocyanate
Ester or benzene dimethylene diisocyanate；The additional amount of crosslinking agent is the 13%-23% of the quality of graft polymers.
The additional amount of dibutyl tin dilaurate is the 0-1% of the gross mass of graft polymers and crosslinking agent.
Crosslinking agent is 4,4`- methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), 1,6- hexa-methylene diisocyanate
Ester or benzene dimethylene diisocyanate；The additional amount of crosslinking agent is the 13%-23% of the quality of graft polymers.
The additional amount of dibutyl tin dilaurate is the 0-1% of the gross mass of graft polymers and crosslinking agent.
Embodiment 1
It weighs 0.025g graphene oxide (GO) to be added in the flask containing 24.975g polycaprolactone, 400W ultrasound point
60mins is dissipated, finely dispersed material is obtained.Heating stirring in 130 DEG C of oil bath pans is put under nitrogen protection, 20 microlitres of instillation is pungent
Sour stannous, reaction for 24 hours, obtain GO-PCL-0.1% graft polymers.
Weigh 2.000gGO-PCL-0.1% graft polymers, be added 20mL n,N dimethylformamide (DMF) and
0.400g4,4`- methyl diphenylene diisocyanate (MDI), 0.240g mass concentration are 2% dibutyl tin dilaurate
(DBTDL) DMF solution of catalyst, 80 DEG C of stirring 5h, obtain solution under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape note containing GO-SMP-0.1%
Recall coatings.
Referring to Fig. 1, the infrared spectrogram of shape memory selfreparing polyurethane coating provided in this embodiment is visible in figure
3327cm-1For the absorption peak of hydroxyl, 1700cm-1For the absorption peak of carbonyl, preliminary proof PCL is grafted successfully, 1597cm-1It is secondary
Amine stretching vibration peak shows that MDI successfully reacts to form urethano with PCL.
Referring to fig. 2, the hydrogen nuclear magnetic resonance spectrogram of shape memory selfreparing polyurethane coating provided in this embodiment, it is main
Peak has marked in figure；4.03(t,-CH2-O-),2.28(t,-CH2-CO-),1.63(m,-CH2-),1.36(m,-CH2),
It is the absorption peak of the methylene of linkage section hydroxyl on PCL at 3.65 in nuclear-magnetism figure, acquired results further prove graft polymers
GO-PCL is successfully prepared.
Referring to the transmission of Fig. 3, the embodiment of the present invention 1 graphene oxide provided and selfreparing shape memory polyurethane coating
Electron microscope, it can be seen that graphene oxide is in polymer network without significantly building up, it was demonstrated that it evenly dispersed.
Referring to fig. 4, the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides repairs the polarized light microscopy of front and back
Mirror comparison diagram, it was demonstrated that grafting GO-SMP polymer coating has good self-healing properties.
Referring to Fig. 7, the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides repairs the scanning electron microscope of front and back
Comparison diagram proves that grafting GO-SMP polymer coating has good self-healing properties from microcosmic angle.
Referring to Fig. 8 and Fig. 9, the selfreparing shape memory polyurethane coating that the embodiment of the present invention 1 provides wraps up the anti-of blade
Rotten schematic diagram and petrographic microscope comparison diagram, it was demonstrated that grafting GO-SMP polymer coating can effective anti-corrosion, and can repair
Coating after multiple mass lesions and selfreparing can also play good anti-corrosion effect.
Embodiment 2
The preparation of the coatings metal of GO-PCL-0.1% catalyst content 0.5%.
1) polymer of grafting GO-PCL-0.1% is synthesized according to embodiment 1.
2) weigh 2.000gGO-PCL-0.1% graft polymers, be added 20mL n,N dimethylformamide (DMF) and
0.400g4,4`- methyl diphenylene diisocyanate (MDI), 1.200g mass concentration are 2% dibutyl tin dilaurate
(DBTDL) DMF solution of catalyst, 80 DEG C of stirring 5h, obtain solution under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape note containing GO-SMP-0.5%
Recall coatings.
The shooting that front and back carries out petrographic microscope and scanning electron microscope is repaired to the polyurethane coating according to embodiment 1, it was demonstrated that
The coating can effective selfreparing.
Embodiment 3
The preparation of the coatings metal of GO-PCL-0.1% catalyst content 1%.
1) polymer of grafting GO-PCL-0.1% is synthesized according to embodiment 1.
2) weigh 2.000gGO-PCL-0.1% graft polymers, be added 20mL n,N dimethylformamide (DMF) and
0.400g4,4`- methyl diphenylene diisocyanate (MDI), 2.400g mass concentration are 2% dibutyl tin dilaurate
(DBTDL) DMF solution of catalyst, 80 DEG C of stirring 5h, obtain solution under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape memory containing GO-SMP-1%
Coatings.
The shooting that front and back carries out petrographic microscope and scanning electron microscope is repaired to the polyurethane coating according to embodiment 1, it was demonstrated that
The coating can effective selfreparing.
Embodiment 4
The preparation of coatings metal of the GO-PCL-0.1% without catalyst.
1) polymer of grafting GO-PCL-0.1% is synthesized according to embodiment 1.
2) weigh 2.000g grafting GO-PCL-0.1% polymer, be added 20mLN, N-dimethylformamide (DMF) and
0.400g toluene di-isocyanate(TDI) (MDI) stirs 5h at 80 DEG C under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape memory containing GO-SMP-0 certainly
Reparation.
The shooting that front and back carries out petrographic microscope and scanning electron microscope is repaired to the polyurethane coating according to embodiment 1, it was demonstrated that
The coating can effective selfreparing.
Embodiment 5
1) polymer of grafting GO-PCL-0.1% is synthesized according to embodiment 1.
2) weigh 2.000g grafting GO-PCL-0.1% polymer, be added 20mLN, N-dimethylformamide (DMF) and
0.400g toluene di-isocyanate(TDI) (TDI), 0.2400g mass concentration are 2% dibutyl tin dilaurate (DBTDL) catalyst
DMF solution, 80 DEG C of stirring 5h, obtain solution under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape note containing GO-SMP-0.1%
Recall coatings.
The shooting that front and back carries out petrographic microscope and scanning electron microscope is repaired to the polyurethane coating according to embodiment 1, it was demonstrated that
The coating can effective selfreparing.
Embodiment 6
1) it weighs 1.250g multi-walled carbon nanotube (MWCNT) to be added in the flask containing 23.750g polycaprolactone, 400W
Ultrasonic disperse 2h obtains finely dispersed material.Heating stirring in 130 DEG C of oil bath pans is put under nitrogen protection, 20 microlitres of instillation is pungent
Sour stannous, reaction is for 24 hours.Obtain MWCNT-PCL-5% graft polymers.
2) polymer of 2.000gMWCNT-PCL-5% is weighed, 20mLN, N-dimethylformamide (DMF), 0.500g is added
Toluene di-isocyanate(TDI) (MDI) and 0.240g mass concentration are that the DMF of 2% dibutyl tin dilaurate (DBTDL) catalyst is molten
Liquid, 80 DEG C of stirring 5h, obtain solution under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape memory containing MWCNT-SMP
Coatings.
It is that the polarisation for the selfreparing shape memory polyurethane coating reparation front and back that the embodiment of the present invention 6 provides is aobvious referring to Fig. 5
Micro mirror comparison diagram, it was demonstrated that grafting MWCNT-SMP coating has good self-healing properties.
Embodiment 7
1) it weighs 0.250g poly-dopamine (PDA) to be added in the flask containing 24.750g caprolactone, 400W ultrasonic disperse
4h obtains finely dispersed material.It is put into heating stirring in 130 DEG C of oil bath pans under nitrogen protection, instills 20 microlitres of stannous octoates,
Reaction for 24 hours, obtains PDA-PCL-1% graft polymers.
2) polymer of 2.000gPDA-PCL-1% is weighed, 20mLN, N-dimethylformamide (DMF) and 0.400g is added
Toluene di-isocyanate(TDI) (MDI), 0.240g mass concentration are that the DMF of 2% dibutyl tin dilaurate (DBTDL) catalyst is molten
Liquid, 80 DEG C of stirring 5h, obtain solution under nitrogen protection.
Acquired solution is coated on metal surface, and in 80 DEG C of solidification 12h, obtains the shape memory containing PDA-SMP certainly
Reparation.
It is that the polarisation for the selfreparing shape memory polyurethane coating reparation front and back that the embodiment of the present invention 7 provides is aobvious referring to Fig. 6
Micro mirror comparison diagram, it was demonstrated that grafting PDA-SMP polymer coating has good self-healing properties.
Embodiment 8
A kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating, comprising the following steps:
1) it weighs packing material to be added in the container equipped with polycaprolactone, ultrasonic disperse 1h makes packing material point under 400W
It dissipates uniformly, then under nitrogen protection, stannous octoate is added, 140 DEG C of reactions for 24 hours, obtain graft polymers；Wherein, material is filled
Material is graphene oxide, and the quality of packing material is the 2% of packing material and polycaprolactone gross mass.
2) addition solvent, crosslinking agent and dibutyl tin dilaurate into graft polymers, 70 DEG C under nitrogen protection
Lower stirring 7h, obtains solution, and solution is coated on metal surface, solidifies 12h at 70 DEG C, obtains photoresponse selfreparing shape memory
Polyurethane anticorrosion coating.Wherein, the ratio 1g:0.003 μ L of packing material and polycaprolactone gross mass and stannous octoate；Solvent is
DMSO, DMF or THF；The ratio of graft polymers and solvent is 1:10mL；Crosslinking agent is 4,4`- methyl diphenylene diisocyanate；
The additional amount of crosslinking agent is the 23% of the quality of graft polymers；The additional amount of dibutyl tin dilaurate be graft polymers with
The 0.5% of the gross mass of crosslinking agent.
Embodiment 9
1) it weighs packing material to be added in the container equipped with polycaprolactone, ultrasonic disperse 2h makes packing material point under 400W
It dissipates uniformly, then under nitrogen protection, stannous octoate is added, 135 DEG C of reaction 30h obtain graft polymers；Wherein, material is filled
Material is poly-dopamine, and the quality of packing material is the 5% of packing material and polycaprolactone gross mass.
2) addition solvent, crosslinking agent and dibutyl tin dilaurate into graft polymers, 80 DEG C under nitrogen protection
Lower stirring 5h, obtains solution, and solution is coated on metal surface, solidifies 12h at 60 DEG C, obtains photoresponse selfreparing shape memory
Polyurethane anticorrosion coating.Wherein, the ratio 1g:0.005 μ L of packing material and polycaprolactone gross mass and stannous octoate；Solvent is
DMSO, DMF or THF；The ratio of graft polymers and solvent is 1:20mL；Crosslinking agent is 1,6- hexamethylene diisocyanate；It hands over
The additional amount of connection agent is the 17% of the quality of graft polymers；The additional amount of dibutyl tin dilaurate is graft polymers and hands over
Join the 1% of the gross mass of agent.
Embodiment 10
1) it weighs packing material to be added in the container equipped with polycaprolactone, ultrasonic disperse 1h makes packing material point under 400W
It dissipates uniformly, then under nitrogen protection, stannous octoate is added, 130 DEG C of reaction 36h obtain graft polymers；Wherein, material is filled
Material is multi-walled carbon nanotube, and the quality of packing material is the 0.1% of packing material and polycaprolactone gross mass.
2) addition solvent, crosslinking agent and dibutyl tin dilaurate into graft polymers, 60 DEG C under nitrogen protection
Lower stirring 10h, obtains solution, and solution is coated on metal surface, solidifies 12h at 80 DEG C, obtains photoresponse selfreparing shape note
Recall polyurethane anticorrosion coating.Wherein, the ratio 1g:0.001 μ L of packing material and polycaprolactone gross mass and stannous octoate；Solvent is
DMSO, DMF or THF；The ratio of graft polymers and solvent is 1:15mL；Crosslinking agent is benzene dimethylene diisocyanate；Crosslinking
The additional amount of agent is the 13% of the quality of graft polymers；The additional amount of dibutyl tin dilaurate is graft polymers and crosslinking
The 0.1% of the gross mass of agent.
Claims (10)
1. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating, which is characterized in that including following step
It is rapid:
1) packing material is added in the container equipped with polycaprolactone, ultrasonic disperse makes packing material be uniformly dispersed, and then exists
Under nitrogen protection, stannous octoate is added, 130-140 DEG C of reaction 24-36h obtains graft polymers；
2) solvent, crosslinking agent and dibutyl tin dilaurate are added into graft polymers, under nitrogen protection at 60-80 DEG C
5-10h is stirred, solution is obtained, solution is coated on metal surface, it is anti-to obtain photoresponse selfreparing shape memory polyurethane for solidification
Rotten coating.
2. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, packing material is graphene oxide, poly-dopamine or multi-walled carbon nanotube.
3. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, the quality of packing material is the 0.1%-5% of packing material and polycaprolactone gross mass.
4. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 3,
It is characterized in that, the ratio 1g:(0.001-0.005 of packing material and polycaprolactone gross mass and stannous octoate) μ L.
5. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, ultrasonic power is 400W, time 1-4h.
6. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, solvent DMSO, DMF or THF；The ratio of graft polymers and solvent is 1:(10-20) mL.
7. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, crosslinking agent 4,4`- methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), 1,6- hexa-methylene, two isocyanide
Acid esters or benzene dimethylene diisocyanate；The additional amount of crosslinking agent is the 13%-23% of the quality of graft polymers.
8. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, the additional amount of dibutyl tin dilaurate is the 0-1% of the gross mass of graft polymers and crosslinking agent.
9. a kind of preparation method of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating according to claim 1,
It is characterized in that, cured temperature is 60-80 DEG C, time 12h.
10. a kind of photoresponse selfreparing shape memory polyurethane obtained based on any one of claim 1-9 preparation method
Corrosion-inhibiting coating.
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