CN107057326A - Composite of photoresponse shape memory selfreparing and preparation method thereof, restorative procedure and application - Google Patents
Composite of photoresponse shape memory selfreparing and preparation method thereof, restorative procedure and application Download PDFInfo
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- CN107057326A CN107057326A CN201710083543.8A CN201710083543A CN107057326A CN 107057326 A CN107057326 A CN 107057326A CN 201710083543 A CN201710083543 A CN 201710083543A CN 107057326 A CN107057326 A CN 107057326A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
- C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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Abstract
The present invention relates to composite of photoresponse shape memory selfreparing and preparation method thereof, restorative procedure and application, belong to functional high polymer material field.Poly-dopamine is compounded in the polymeric material matrix with shape memory self-healing properties, available for protective coating, selfreparing device, CD-ROM driver, the field such as the hot physiotherapy of photo-thermal.Specific method is that poly-dopamine has excellent photo-thermal effect, near-infrared can effectively be absorbed to the light of visible light wave range, minimal amount of poly-dopamine is introduced with regard to that polymeric matrix can be made to be rapidly heated, so as to reach the characteristic temperature of shape memory, or the reversible transition temperature of dynamic key, so as to which the reparation for material provides a kind of easy and effective, and the energy supply of site-directed quantitative.
Description
Technical field
The present invention relates to composite of photoresponse shape memory selfreparing and preparation method thereof, restorative procedure and application,
Belong to functional high polymer material field.
Background technology
Material is during processing and use easily by some extraneous factors (machinery, chemistry, heat, ultraviolet radioactive etc.)
Destruction, inside produce be difficult or can not from external detection to fine crack, or compared with the damage of large deformation, the performance of material is big
Big reduction, service life shortens.But common self-healing polymers material generally requires the mode of external heat to be repaiied
It is multiple, whole material or period heating when typically, it is impossible to accomplish Local treatment, inconvenience is caused to practical application.Therefore, make
It is standby it is a kind of can local simple process can be achieved with the polymer for the property reviewed one's lessons by oneself to solving to be unable to localized heat reparation in practical application
The problem of be highly desirable to.
The content of the invention
A kind of photoresponse shape memory selfreparing that the purpose of the present invention is in view of the shortcomings of the prior art and developed is poly- more
The preparation and application of bar amine/polymer composites.
Concrete technical scheme is：
The composite of photoresponse shape memory selfreparing, by following components by weight：
99.99~95 parts of polymer with shape memory or self-repair function；
0.01~5 part of poly-dopamine.
Wherein, the described polymer with shape memory or self-repair function, including one kind or many in following material
Plant mixture：Polyurethane, polysiloxanes, PLA, polyvinyl alcohol, and its hydrogel of above material polymerization.
The preparation method of the composite of the photoresponse shape memory selfreparing, comprises the following steps：
(1) a certain amount of ammoniacal liquor is added into the mixed solution of water and ethanol, salt is added after adjusting pH value, stirring 30min
Sour aqueous dopamine solution, gentle agitation；
(2) after reaction 24h, high speed centrifugation washing, freeze-drying, according to the difference of pH value, obtains particle diameter and arrived for 50nm
1000nm poly-dopamines；
(3) poly-dopamine and the mixed with polymers with shape memory or self-repair function, including solution blending, melt are common
It is mixed, mechanical blending, in-situ polymerization.
The restorative procedure of the composite of the photoresponse shape memory selfreparing, realizes reparation by way of illumination.Its
The crackle or damage that product is produced in use can realize reparation by way of illumination, meanwhile, if there is big shape
The broken words become can be that failure mechanics contact with each other and repaired by shape memory function.Needed for reparation and shape memory function
Temperature can all be realized by the introducing of poly-dopamine, the photo-thermal effect of generation.
Wherein, illumination light source during reparation is light source of the visible ray near infrared light wave band.
The application of the composite of the photoresponse shape memory selfreparing, for preparing protective coating, selfreparing device, light
Driver, photo-thermal physical therapy equipment.
Poly-dopamine has excellent photo-thermal effect, can effectively absorb near-infrared to the light of visible light wave range, minimal amount
Poly-dopamine introduce and can just polymeric matrix is rapidly heated, so as to reach the characteristic temperature of shape memory, or dynamic key
Reversible transition temperature.So as to be that the shape memory of material or selfreparing provide a kind of easy and effective, and the energy of site-directed quantitative
Supply.
Poly-dopamine is a kind of Melanoidins material, and its synthetic method is simple and environment-friendly.Poly-dopamine is not only good
Good adhesion, as filler addition, interface compatibility is good in polymer matrix body, and with prominent absorbing properties,
Visible ray can be absorbed to the light of near infrared light wave band, photo-thermal effect is produced in the base, material is locally fast and effectively risen
Temperature.The photo-thermal effect for poly-dopamine being compounded in poly-dopamine being utilized in polymeric matrix is had not yet to see, to material damage
Part local light, which shines, can quickly realize the report of reparation.
Shape-memory material is received significant attention in every field, in application process, energy input form and selfreparing
The problem of function has similar can also be realized by introducing poly-dopamine using its photo-thermal effect.In addition, occurring big shape in material
When becoming damage, shape memory auxiliary self-repair function can be played.
The composite for the photoresponse shape memory selfreparing that the present invention is provided, is imitated using the excellent photo-thermal of poly-dopamine
Should, near-infrared is effectively absorbed to the light of visible light wave range, and minimal amount of poly-dopamine is introduced with regard to polymeric matrix can be made quickly to rise
Temperature, so as to reach the characteristic temperature of shape memory, or dynamic key reversible transition temperature.So as to provide one for the reparation of material
Plant easy and effective, and the energy supply of site-directed quantitative.
Brief description of the drawings
Fig. 1 is obtained poly-dopamine scanning electron microscope (SEM) photograph in embodiment；
Fig. 2 is the profile scanning electron microscope of the composite of photoresponse shape memory selfreparing obtained by embodiment, poly- DOPA
Amine content is 0.1%.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to which this is pointed out that the present embodiment is served only for again
To further illustrating that the present invention is carried out, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations according to the content of foregoing invention.
Poly-dopamine is prepared first：
(1) a certain amount of ammoniacal liquor is added into the mixed solution of water and ethanol, salt is added after adjusting pH value, stirring 30min
Sour aqueous dopamine solution, gentle agitation；
(2) after reaction 24h, high speed centrifugation washing, freeze-drying, according to the difference of pH value, obtains particle diameter and arrived for 50nm
1000nm poly-dopamines.
Obtained poly-dopamine scanning electron microscope (SEM) photograph such as Fig. 1.
Embodiment 1
0.1g particle diameters are dispersed in the solution containing 100g shape memory polyurethanes for 50nm poly-dopamine particle, machine
Tool removes solvent after being uniformly mixed, and obtains shape memory poly-dopamine/compound polyurethane material of photoresponse.
Embodiment 2
0.05g particle diameters are dispersed in the solution containing 100g selfreparing polyurethane for 100nm poly-dopamine particle, machine
Tool removes solvent after being uniformly mixed, and obtains selfreparing poly-dopamine/compound polyurethane material of photoresponse.
Embodiment 3
3.6g particle diameters are dispersed in containing the molten of 100g shape memory selfreparing polyurethane for 330nm poly-dopamine particle
In liquid, solvent is removed after mechanical agitation is well mixed, selfreparing poly-dopamine/compound polyurethane material of photoresponse is obtained.
Embodiment 4
0.01g particle diameters are dispersed in for 280nm poly-dopamine particle molten containing 100g selfreparing polysiloxanes presomas
In liquid, solvent is removed after mechanical agitation is well mixed, solidification obtains selfreparing poly-dopamine/polysiloxanes composite wood of photoresponse
Material.
Embodiment 5
5g particle diameters are dispersed in containing the poly- silica of 100g selfreparing polyurethane shape memories for 180nm poly-dopamine particle
In the precursor solution of alkane, solvent is removed after mechanical agitation is well mixed, solidification obtains the selfreparing poly-dopamine of photoresponse/poly-
Silicone composite material.
Embodiment 6
0.55g particle diameters are dispersed in the solution containing 100g selfreparing polyvinyl alcohol for 780nm poly-dopamine particle,
Freeze-thaw circulation obtains selfreparing poly-dopamine/polyvinyl alcohol composite material of photoresponse after mechanical agitation is well mixed.
Embodiment 7
4g particle diameters are dispersed in the solution containing 100g shape memory polyvinyl alcohol for 100nm poly-dopamine particle,
Solvent is removed after mechanical agitation is well mixed, selfreparing poly-dopamine/polyvinyl alcohol composite material of photoresponse is obtained.
Embodiment 8
0.05g particle diameters are dispersed in containing 100g selfreparing polyvinyl alcohol water solutions for 1000nm poly-dopamine particle
In, freeze-thaw circulation after mechanical agitation is well mixed, the selfreparing poly-dopamine/polyvinyl alcohol hydrogel for obtaining photoresponse is multiple
Condensation material.
Embodiment 9
2.2g particle diameters are dispersed in containing in 100g polyvinyl alcohol water solutions for 400nm poly-dopamine particle, machinery is stirred
Well mixed rear freeze-thaw circulation is mixed, shape memory selfreparing poly-dopamine/polyvinyl alcohol hydrogel of photoresponse is obtained
Composite.
Embodiment 10
1.8g particle diameters are gathered for 600nm poly-dopamine particle by mechanical melt blended be dispersed in containing 100g selfreparings
In the solution of urethane, solvent is removed after mechanical agitation is well mixed, the selfreparing poly-dopamine/polyurethane for obtaining photoresponse is combined
Material.
Embodiment 11
The poly-dopamine particle that 1.5g particle diameters are 550nm is dispersed in the presoma containing 100g selfreparing polysiloxanes molten
In liquid, solvent is removed after mechanical agitation is well mixed, selfreparing poly-dopamine/polysiloxanes composite of photoresponse is obtained.
Embodiment 12
1g particle diameters are dispersed in the solution containing 100g shape memory selfreparing polyurethane for 440nm poly-dopamine particle
In, solvent is removed after mechanical agitation is well mixed, selfreparing poly-dopamine/compound polyurethane material of photoresponse is obtained.
Embodiment 13
0.8g particle diameters are dispersed in the solution containing 100g selfreparing polyvinyl alcohol for 800nm poly-dopamine particle,
Solvent is removed after mechanical agitation is well mixed, selfreparing poly-dopamine/polyvinyl alcohol composite material of photoresponse is obtained.
Embodiment 14
Dopamine hydrochloride is dispersed in water/alcohol mixed solution containing 100g selfreparing polyvinyl alcohol hydrogels, is added
Ammoniacal liquor adjusts pH value, and Dopamine hydrochloride aggregates into poly-dopamine in the hydrogel matrix situ being swelled, and then compound obtains light
Selfreparing poly-dopamine/polyvinyl alcohol hydrogel composite of response.
Embodiment 15
By 0.3g particle diameters for the 380nm method that is blended by screw extrusion machinery of poly-dopamine particle be dispersed in containing
In the solution of 100g selfreparing polyurethane, selfreparing poly-dopamine/compound polyurethane material of photoresponse is obtained.
Fig. 2 is the profile scanning for the composite that poly-dopamine content is 0.1% gained photoresponse shape memory selfreparing
Electron microscope.
Claims (6)
1. the composite of photoresponse shape memory selfreparing, it is characterised in that by following components by weight：
99.99~95 parts of polymer with shape memory or self-repair function；
0.01~5 part of poly-dopamine.
2. the composite of photoresponse shape memory selfreparing according to claim 1, it is characterised in that described has
One or more mixtures in the polymer of shape memory or self-repair function, including following material：Polyurethane, poly- silica
Alkane, PLA, polyvinyl alcohol, and its hydrogel of above material polymerization.
3. the preparation method of the composite of photoresponse shape memory selfreparing according to claim 1 or 2, its feature exists
In comprising the following steps：
(1) a certain amount of ammoniacal liquor is added into the mixed solution of water and ethanol, addition hydrochloric acid after pH value, stirring 30min is adjusted many
Bar amine aqueous solution, gentle agitation；
(2) after reaction 24h, high speed centrifugation washing, freeze-drying, according to the difference of pH value, obtains particle diameter for 50nm to 1000nm
Poly-dopamine；
(3) poly-dopamine and the mixed with polymers with shape memory or self-repair function, including solution blending, melt blended,
Mechanical blending, in-situ polymerization.
4. the restorative procedure of the composite of photoresponse shape memory selfreparing according to claim 1 or 2, its feature exists
In realizing reparation by way of illumination.
5. the restorative procedure of the composite of photoresponse shape memory selfreparing according to claim 4, it is characterised in that
Illumination light source during reparation is light source of the visible ray near infrared light wave band.
6. the application of the composite of photoresponse shape memory selfreparing according to claim 1 or 2, it is characterised in that
For preparing protective coating, selfreparing device, CD-ROM driver, photo-thermal physical therapy equipment.
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Cited By (17)
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| CN107915826A (en) * | 2017-11-06 | 2018-04-17 | 四川大学 | A kind of preparation method of the self-repair type shape memory polyurethane containing double selenium keys |
| CN108003527A (en) * | 2017-12-07 | 2018-05-08 | 深圳大学 | Composite material of shape memory that water and near infrared light double-bang firecracker are answered and preparation method thereof |
| CN108504057A (en) * | 2018-03-29 | 2018-09-07 | 北京大学深圳研究生院 | A kind of composite material of shape memory and preparation method thereof |
| CN108912657A (en) * | 2018-08-21 | 2018-11-30 | 成都市水泷头化工科技有限公司 | A kind of selfreparing polyurethane cable cover(ing) and preparation method |
| CN108962438A (en) * | 2018-07-26 | 2018-12-07 | 深圳市华星光电技术有限公司 | A kind of conducting sphere and preparation method thereof, liquid crystal display device |
| CN109439175A (en) * | 2018-11-01 | 2019-03-08 | 西安交通大学 | A kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating and preparation method thereof |
| CN110483813A (en) * | 2019-09-09 | 2019-11-22 | 南昌航空大学 | A kind of preparation method of room temperature photo-thermal selfreparing hydrogel |
| CN110819096A (en) * | 2019-12-10 | 2020-02-21 | 四川大学 | Polyurea composite material capable of repairing macroscopic scratches and preparation method and application thereof |
| CN110922766A (en) * | 2019-12-09 | 2020-03-27 | 四川大学 | Silicone rubber material capable of repairing macroscopic scratches as well as preparation method and application thereof |
| CN111138952A (en) * | 2020-01-22 | 2020-05-12 | 江苏金陵特种涂料有限公司 | Preparation method of water-based self-repairing coating material |
| CN112472818A (en) * | 2020-11-16 | 2021-03-12 | 安徽农业大学 | Nano material using modified natural melanin as carrier, and preparation method and application thereof |
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| CN113249025A (en) * | 2021-06-16 | 2021-08-13 | 四川大学 | Near-infrared quick response accurate self-repairing anticorrosive coating and preparation method thereof |
| CN113372527A (en) * | 2021-06-07 | 2021-09-10 | 中国人民解放军陆军工程大学 | Preparation method of bionic room-temperature self-repairing polyurethane material |
| CN114752165A (en) * | 2022-04-22 | 2022-07-15 | 大连理工大学 | Preparation method of non-covalent bond type self-repairing polymer material |
| CN116102771A (en) * | 2022-11-16 | 2023-05-12 | 上海海事大学 | Preparation method of efficient gel for sea water desalination |
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Cited By (22)
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| CN107915826A (en) * | 2017-11-06 | 2018-04-17 | 四川大学 | A kind of preparation method of the self-repair type shape memory polyurethane containing double selenium keys |
| CN108003527A (en) * | 2017-12-07 | 2018-05-08 | 深圳大学 | Composite material of shape memory that water and near infrared light double-bang firecracker are answered and preparation method thereof |
| CN108504057B (en) * | 2018-03-29 | 2020-07-17 | 北京大学深圳研究生院 | Shape memory composite material and preparation method thereof |
| CN108504057A (en) * | 2018-03-29 | 2018-09-07 | 北京大学深圳研究生院 | A kind of composite material of shape memory and preparation method thereof |
| CN108962438A (en) * | 2018-07-26 | 2018-12-07 | 深圳市华星光电技术有限公司 | A kind of conducting sphere and preparation method thereof, liquid crystal display device |
| CN108912657A (en) * | 2018-08-21 | 2018-11-30 | 成都市水泷头化工科技有限公司 | A kind of selfreparing polyurethane cable cover(ing) and preparation method |
| CN109439175A (en) * | 2018-11-01 | 2019-03-08 | 西安交通大学 | A kind of photoresponse selfreparing shape memory polyurethane corrosion-inhibiting coating and preparation method thereof |
| CN110483813A (en) * | 2019-09-09 | 2019-11-22 | 南昌航空大学 | A kind of preparation method of room temperature photo-thermal selfreparing hydrogel |
| CN110922766A (en) * | 2019-12-09 | 2020-03-27 | 四川大学 | Silicone rubber material capable of repairing macroscopic scratches as well as preparation method and application thereof |
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