CN105693962B - The preparation method of gold nanorods and polymer hybrid material with self-healing properties - Google Patents

The preparation method of gold nanorods and polymer hybrid material with self-healing properties Download PDF

Info

Publication number
CN105693962B
CN105693962B CN201610090116.8A CN201610090116A CN105693962B CN 105693962 B CN105693962 B CN 105693962B CN 201610090116 A CN201610090116 A CN 201610090116A CN 105693962 B CN105693962 B CN 105693962B
Authority
CN
China
Prior art keywords
gold nanorods
self
hybrid material
preparation
healing properties
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610090116.8A
Other languages
Chinese (zh)
Other versions
CN105693962A (en
Inventor
袁丛辉
武彤
戴李宗
毛杰
刘诚
许婷
许一婷
曾碧榕
罗伟昂
陈国荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN201610090116.8A priority Critical patent/CN105693962B/en
Publication of CN105693962A publication Critical patent/CN105693962A/en
Application granted granted Critical
Publication of CN105693962B publication Critical patent/CN105693962B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Medicinal Preparation (AREA)

Abstract

The preparation method of gold nanorods and polymer hybrid material with self-healing properties, is related to organic/inorganic hybrid nano-material.The nanometer gold bar surface for first to prepare using ligand exchange method has reactive amino, Invertible ideal method is recycled to prepare the adjustable P of segment ratio (MMA co AAEM) b POEGMA copolymers, most gold nanorods are doped into polymer at last, by the imine linkage and hydrogen bond action formed between amino and polymer, the fine dispersion of gold nanorods in the polymer is realized, obtains hybrid material.The effective photothermal conversion performance of gold nanorods so that the hybrid material can carry out defect selfreparing in the presence of near infrared light.

Description

The preparation method of gold nanorods and polymer hybrid material with self-healing properties
Technical field
The present invention relates to hybrid field of nanometer material technology, more particularly to a kind of gold with self-healing properties The preparation method of nanometer rods and polymer hybrid material.
Background technology
During use, due to being influenceed by factors such as environment's heat, mechanism and chemistry, high polymer material it is interior Portion can produce microfissure even crackle, so as to influence its normal mechanical property and service life.Microfissure is as breaking-up material The blasting fuse of performance, it will eventually cause the macroscopic view cracking of material, therefore, how to repair multiple in the extension expansion of material internal The internal injury of condensation material becomes the study hotspot of scientific worker.For the macroscopic macroscopic cracking of material surface or Layering, can be repaired by appropriate manual operations, once but there is microfissure in material internal, be difficult to lock Simultaneously repair in time damaged zone.If the microfissure of composite inner is not repaired, the service life of material will be not only influenceed, And can grow in intensity, finally it is expanded into macroscopic cracking so that material loses normal function, causes economic loss.Therefore, grind The self-healing properties for studying carefully composite suffer from extremely important meaning for structural composite material and emerging high-tech area.
In the research field of modern self-repair material, main flow remains the adjacent benzene two of the metal-chelating inspired out using mussel Phenol functionalized macromolecular network.B.Kollbe groups (B.Kollbe Ahn, DongWoog Lee, et al.Surface- initiated self-healing of polymers in aqueous media,NATURE MATERIALS,DOI: 10.1038/NMAT4037) the surface-functionalized polyacrylate of catechol and poly- methyl-prop are utilized in metal-free water E pioic acid methyl ester carry out selfreparing, they find these materials can first by the presence of catechol by interface hydrogen bond phase Connection, then recycles the consolidation that follow-up intermolecular force is repaired so as to be finally reached the effect of selfreparing. B.Wang groups (B.Wang, Y.S.Jeon, et al.Mussel-mimetic self-healing polyaspartamide derivative gel via boron-catechol interactions,eXPRESS Polymer Letters,Vol.9, No.9 (2015) 799-808) using the polymer of a kind of Dopamine hydrochloride and monoethanolamine and acid reaction formed a kind of boron with it is adjacent Cross-linked gel caused by benzenediol coordination, this gel under given conditions may be used there is the coordination mechanism that guiding is induced by pH Self-repair procedure is completed to reach reversible gelling by the control to pH.
In recent years, nanogold has rapidly become international focus, Er Qiejin with its special dimensional effect, skin effect The most noticeable property of nanometer rods is exactly local surface plasma resonance effect (LSPR).This is due to that gold nanorods outer layer has The electronics of high activity, when light is incided on gold nanorods of the particle diameter much smaller than its excitation wavelength, caused plasma Ripple is limited at the structure periphery of nanogold, if the frequency of incident light is suitable with the vibration frequency of electronics, gold nanorods can be right Incident light produces strong LSPR and absorbed, and the absorption of this energy can make the temperature on gold nanorods surface rise to hundreds of degrees Celsius Even thousands of degrees Celsius, illumination can be thus utilized to cause the melting of polymer, therefore it is contemplated that by this spy of nanogold Different property is applied in selfreparing field.Seminar in our prior be present and nanometer is applied in self-repair material Gold, such as in 2010, Chan groups (Chan Woo Park, Antoinette B.South, et al.Gold nanoparticles reinforce self-healing microgel multilayers Colloid,Polym Sci, (2011)289:583-590) golden nanometer particle of the doping citrate-stable into hydrogel/polyelectrolyte multilayer film is passed through To provide the resistance to stress lesion capability of film in the dry state, imitated though this method does not have using the LSPR of nanogold Should, selfreparing still relies on hydrogel, but the research of this form is found that nanogold can't disturb reviewing one's lessons by oneself for hydrogel Multiple process, but also strengthen by doping vario-property the toughness of film.Chinese patent CN103113745A is disclosed with interface certainly The preparation of carbon fiber/golden nanometer particle/Polyethersulfone Composites of repairing performance and self-repair method, first electricity consumption deeptensepulse area method system It is standby go out carbon fiber/golden nanometer particle fiber, it is then compressing with polyether sulfone pellet, it is fine to form the carbon with interface self-healing properties Dimension/golden nanometer particle/Polyethersulfone Composites, this method are mainly used in interface reparation, it is compound to solve traditional carbon fiber Material is also easy to produce crackle so as to reduce the problem of material lifetime.
The content of the invention
Present invention aims at provide a kind of preparation of gold nanorods and polymer hybrid material with self-healing properties Method.
The present invention comprises the following steps：
1) gold nanorods of monodispersity are first prepared, with ethanol centrifuge washing, it is unnecessary in gold nanorods growth course to remove CTAB, then with the ethanol solution centrifuge washing containing amino ligands, the CTAB of gold nanorods surface attachment is entered with amino ligands Row is replaced, and finally with ethanol centrifuge washing, removes unnecessary amino ligands, with ethanol to obtained gold nanorods decentralized processing, Obtain the gold nanorods ethanol solution of monodispersity；
2) MMA, AAEM, CDB and AIBN are dissolved in tetrahydrofuran, polymerize instead under argon gas protection after freeze thawing deaerates Should, liquid nitrogen it is sudden it is cold after stop reaction, after reaction solution precipitate in ether, vacuum drying obtain random copolymerization without pink admittedly Body；
3) random copolymerization that step 2) obtains is dissolved in tetrahydrofuran without pink solid and OEGMA and AIBN, through freezing Melt degassing after argon gas protection under polymerisation, liquid nitrogen it is sudden it is cold after stop reaction, after reaction solution precipitates in ether, vacuum is done It is dry, produce block copolymer P (MMA-co-AAEM)-b-POEGMA, pinkiness solid；
4) block copolymer P (MMA-co-AAEM)-b-POEGMA that step 3) obtains is dissolved in solvent, ultrasonic disperse Afterwards, the gold nanorods ethanol solution of monodispersity obtained by step 1) is added, continues ultrasonic disperse, obtains navy blue clear solution, then Turn evaporation, after vacuum drying under infrared lamp the moulding gold nanorods produced with self-healing properties of illumination and polymer hybrid material Material, the product is in black solid；The solvent is the mixed solution of ethanol and tetrahydrofuran.
In step 1), the gold nanorods for preparing monodispersity refer to document：Babak Nikoobakht and Mostafa A.El-Sayed,Preparation and Growth Mechanism of Gold Nanorods(NRs) Using Seed-Mediated Growth Method,Chem.Mater.2003,15,1957-1962；It is described to be centrifuged with ethanol Washing can centrifuge washing twice；It is described to may be selected from ethylenediamine, cyclohexanediamine, polyethyleneimine, polyacrylamide containing amino ligands One kind in；It is described with the ethanol solution centrifuge washing containing amino ligands can centrifuge washing twice；It is described finally with ethanol from The heart washing can centrifuge washing twice；The quality percentage of gold nanorods contains in the gold nanorods ethanol solution of obtained monodispersity Amount can be 0.5%.
In step 2), described MMA, AAEM, CDB, AIBN and tetrahydrofuran dosage can be：MMA：0.50g, 5mmol, AAEM：1.07g, 5mmol, CDB：27.24mg, 0.1mmol, AIBN：3.28mg, 0.02mmol, tetrahydrofuran：2mL；The jelly The number for melting degassing can be 3~5 times；The temperature of the polymerisation can be 65 DEG C；After the sudden cold stopping reaction of liquid nitrogen, action can be entered Mechanics study, often cross the time interval sampling set and do GPC and NMR tests.
In step 3), dosage of the random copolymerization without pink solid, OEGMA, AIBN and tetrahydrofuran can be：Nothing Rule copolymerization is without pink solid：1.57g, 0.1mmol, OEGMA：0.24g, 0.5mmol, AIBN：3.28mg, 0.02mmol, four Hydrogen furans：2mL；The number of the freeze thawing degassing can be 3~5 times；The temperature of the polymerisation can be 65 DEG C；Liquid nitrogen is sudden cold to stop After only reacting, dynamics research can be carried out, the time interval sampling set is often crossed and does GPC and NMR tests.
In step 4), the proportioning of block copolymer P (the MMA-co-AAEM)-b-POEGMA and solvent can be 0.5g: 6mL, wherein, block copolymer P (MMA-co-AAEM)-b-POEGMA is calculated by mass, and solvent is in terms of volume；The ethanol Composition with the mixed solution of tetrahydrofuran can be 1: 1 by volume；The time of the ultrasonic disperse can be 10min；It is described after The time for continuing ultrasound can be 30min.
It is high to include glass transition temperature for synthesized P (MMA-co-AAEM)-b-POEGMA polymer in the present invention The low POEGMA of PMMA, glass transition temperature and with can with amino react and formed hydrogen bond action PAAEM.Utilizing After part containing amino replaces the cetyl trimethylammonium bromide (CTAB) of golden rod surface attachment, by the gold nanorods of acquisition with P (MMA-co-AAEM)-b-POEGMA polymer is blended, and forms organic/inorganic nano-hybrid materials.Golden nanometer particle surface Imine linkage or hydrogen bond action can be formed between amino and polymeric matrix, promotes gold nanorods stable and uniform in polymeric matrix It is scattered.Now under near infrared light, strong LSPR effects occur for gold nanorods, induce the temperature on golden rod surface drastically on Rise, polymer is transferred heat to centered on golden rod, accelerate when environment temperature is far below the glass transition temperature of polymer Polymer melts so that the hybrid material selfreparing being damaged.
Hybrid material prepared by the present invention has following features：
(1) a kind of self-repair method is established, accurate section selfreparing can be accomplished, suitable for repairing various not similar shapes The section of shape.
(2) hybrid material has efficient near-infrared absorption ability, and luminous energy can be transformed into heat energy, and it reviews one's lessons by oneself recovery Reason is that gold nanorods absorb infrared light under Infrared irradiation and produce big calorimetric so that ambient polymer reaches viscous state, so that Filled opening, section are to reach selfreparing effect under external force.
(3) generalization of the present invention is strong, suitable for multiple polymers, as long as using active force golden rod and polymer can be caused to have Effect mixing can assign polymer self-reparing capability.
(4) present invention is applied to repeatedly repair.
(5) temperature-rise period of gold nanorods is driven by illumination, therefore is limited by environment smaller.
Brief description of the drawings
Fig. 1 be embodiment 1 in P (MMA-co-AAEM) polymer proton nmr spectra (1H NMR) result.As schemed Show：PMMA：[δ=3.60 (3H, COOCH 3)]；PAAEM：[δ=4.37 (2H, COOCH 2CH2OCOCH2COCH3), 4.19 (2H, COOCH2CH 2OCOCH2COCH3), 3.60 (2H, COOCH2CH2OCOCH 2COCH3)].Knowable to nuclear-magnetism peak integral area ratio, P (MMAx-co-AAEMy) x: y 0.95: 1.
Fig. 2 be embodiment 1 in P (MMA-co-AAEM)-b-POEGMA polymer proton nmr spectra (1H NMR) knot Fruit.As shown in the figure：PMMA：[δ=3.61 (3H, COOCH 3)]；PAAEM：[δ=4.37 (2H, COOCH 2CH2OCOCH2COCH3), 4.19 (2H, COOCH2CH 2OCOCH2COCH3), 3.61 (2H, COOCH2CH2OCOCH 2COCH3)]；POEGMA：[δ=3.39 (3H, COO(CH2CH2O)8CH 3)].Knowable to nuclear-magnetism peak integral area ratio, P (MMAx-co-AAEMy)m-b-POEGMAnM: n 21.3: 1。
Fig. 3 is the optical microscope photograph after gold nanorods in embodiment 1-polymer hybrid material reparation.In figure 3, a To repair 0min；B is reparation 5min；C is reparation 10min；D is reparation 15min.
Embodiment
The present invention is not limited only to specific embodiment set forth below, can also arbitrarily be combined according to real needs.
Embodiment is as follows：
First, prepared by the gold nanorods that surface has response type amino：
(1) the gold nanorods preparation method bibliography of monodispersity：Babak Nikoobakht and Mostafa A.El-Sayed,Preparation and Growth Mechanism of Gold Nanorods(NRs)Using Seed- Mediated Growth Method,Chem.Mater.2003,15,1957-1962。
(2) gold nanorods prepared in step (1) are removed twice with ethanol centrifuge washing more in golden rod growth course Remaining CTAB, the CTAB of golden rod surface attachment is matched somebody with somebody with amino twice with the ethanol solution centrifuge washing containing amino ligands again afterwards Body is replaced, and finally removes unnecessary amino ligands twice with ethanol centrifuge washing again.
(3) decentralized processing is carried out to preparing golden rod with 10mL ethanol, obtains the gold nanorods ethanol solution of monodispersity.
In the step (2) can be ethylenediamine, cyclohexanediamine, polyacrylamide, polyethyleneimine containing amino ligands Deng.
2nd, the preparation of P (MMA-co-AAEM)-b-POEGMA polymer：
1) MMA, AAEM, CDB and AIBN are dissolved in tetrahydrofuran, protected after continuous freeze thawing deaerates 3~5 times in argon gas Under 65 DEG C polymerization, react the set time after liquid nitrogen it is sudden it is cold stop reaction.Dynamics research then often crosses the time interval set GPC and NMR tests are done in sampling.After reaction solution precipitates in ether, vacuum drying obtains random copolymerization without pink solid.It is real Test middle according to polymer difference chain length P (MMAx-co-AAEMy) fed intake, wherein, x, y are repeat unit MMA and repetition Unit AAEM molar content (x, y span 0.9~0.1).
Note：
(1) CDB content is fed intake according to the 1mol% of MMA and AAEM monomer total amounts in testing；
(2) AIBN content is fed intake according to CDB 20mol% in testing；
(3) embodiment 1~9 is replaced using polyethyleneimine to CTAB.
Repeat unit MMA and repeat unit AAEM molar content x, y span is referring to table 1.
Table 1
Embodiment 1 2 3 4 5 6 7 8 9
x 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
y 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
2) gained pink solid, OEGMA and AIBN in step 1) are dissolved in tetrahydrofuran, through continuous freeze thawing degassing 3 After~5 times the sudden cold stopping reaction of liquid nitrogen after the set time is reacted under argon gas protection in 65 DEG C of polymerizations.Dynamics research then every mistake GPC and NMR tests are done in the time interval sampling set.After reaction solution precipitates in ether, vacuum drying obtains block and is total to Polymers pink solid.According to polymer different polymerization degree P (MMA in experimentx-co-AAEMy)m-b-POEGMAn, m, n P (MMAx-co-AAEMy) and POEGMA the degree of polymerization (m, n span be 90~10).
Note：
(1) AIBN amount is according to first paragraph P (MMAx-co-AAEMy) 20mol% of copolymer fed intake；
(2) P (MMA in embodiment 10~18x-co-AAEMy) x and y be 0.5.
P (MMA in embodiment 10~18x-co-AAEMy) and POEGMA degree of polymerization m, n span referring to table 2.
Table 2
Embodiment 10 11 12 13 14 15 16 17 18
m 10 20 30 40 50 60 70 80 90
n 90 80 70 60 50 40 30 20 10
3rd, the preparation of gold nanorods-polymer hybrid material
(1) P (MMA-co-AAEM)-b-POEGMA polymer is taken to be dissolved in the mixed solution of ethanol and tetrahydrofuran, ultrasound 10min is uniformly dispersed, and adds the nanometer gold bar ethanol solution of gained 0.5wt% in the step 1, continues ultrasonic 30min and disperse Uniformly, navy blue clear solution is obtained.
(2) gained clear solution in the step (1) is subjected to rotary evaporation, after being then dried in vacuo under infrared lamp light Black solid hybrid material is can obtain according to moulding.
Note：
1) P (MMA in embodiment 19~27x-co-AAEMy)m-b-POEGMAnX and y be that 0.5, m and n is 50；
2) nanometer gold bar content refers to the mass fraction for accounting for P (MMA-co-AAEM)-b-POEGMA polymer in list (wt%), i.e., by 0.5wt% nanometer gold bar ethanol solution conversion gained.
Nanometer gold bar content in embodiment 19~27 is referring to table 3.
Table 3
The present invention provides a kind of gold nanorods/poly- (methyl methacrylate-co- acetoacetate methacrylic acid second Ester) poly- (Methylacrylic acid polyethylene glycol single armor ether ester) hybrid materials of-b- are (referred to as：Au rod/P(MMA-co-AAEM)-b- POEGMA preparation method) and its self-healing properties.The nanometer gold bar surface for first to prepare using ligand exchange method has anti- Answering property amino, reversible addion-fragmentation chain transfer polymerization is recycled to prepare segment ratio adjustable P (MMA-co-AAEM)-b- POEGMA copolymers, most gold nanorods are doped into polymer at last, by the imine linkage formed between amino and polymer and Hydrogen bond action, the fine dispersion of gold nanorods in the polymer is realized, obtain hybrid material.The effective optical and thermal of gold nanorods turns Change performance so that the hybrid material can carry out defect selfreparing in the presence of near infrared light.

Claims (10)

1. the preparation method of gold nanorods and polymer hybrid material with self-healing properties, it is characterised in that including following step Suddenly：
1) gold nanorods of monodispersity are first prepared, with ethanol centrifuge washing, are removed unnecessary ten in gold nanorods growth course Six alkyl trimethyl ammonium bromides, then with the ethanol solution centrifuge washing containing amino ligands, by the 16 of gold nanorods surface attachment Alkyl trimethyl ammonium bromide is replaced with amino ligands, finally with ethanol centrifuge washing, is removed unnecessary amino ligands, is used second Alcohol obtains the gold nanorods ethanol solution of monodispersity to obtained gold nanorods decentralized processing；
2) by methyl methacrylate, AAEM, the withered ester of dithiobenzoic acid and the isobutyl of azo two Nitrile is dissolved in tetrahydrofuran, and polymerisation, the sudden cold rear stopping of liquid nitrogen are reacted under argon gas protection after freeze thawing deaerates, reaction solution After being precipitated in ether, vacuum drying obtains random copolymerization without pink solid；
3) by the random copolymerization that step 2) obtains without pink solid and Methylacrylic acid polyethylene glycol single armor ether ester and azo two Isobutyronitrile is dissolved in tetrahydrofuran, polymerisation, the sudden cold rear stopping reaction of liquid nitrogen, reaction under argon gas protection after freeze thawing deaerates After solution precipitates in ether, vacuum drying, block copolymer P (MMA-co-AAEM)-b-POEGMA is produced, pinkiness is solid Body；
4) block copolymer P (MMA-co-AAEM)-b-POEGMA that step 3) obtains is dissolved in solvent, after ultrasonic disperse, added Enter the gold nanorods ethanol solution of monodispersity obtained by step 1), continue ultrasonic disperse, obtain navy blue clear solution, then rotate steaming Hair, after vacuum drying under infrared lamp the moulding gold nanorods and polymer hybrid material produced with self-healing properties of illumination, The product is in black solid；The solvent is the mixed solution of ethanol and tetrahydrofuran.
2. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign be in step 1), it is described with ethanol centrifuge washing be centrifuge washing twice；The ethanol solution containing amino ligands Centrifuge washing be centrifuge washing twice；It is described finally with ethanol centrifuge washing be centrifuge washing twice.
3. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign be in step 1), it is described containing amino ligands in ethylenediamine, cyclohexanediamine, polyethyleneimine, polyacrylamide It is a kind of.
4. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 2) methyl methacrylate, AAEM, dithiobenzoic acid are withered The dosage of ester, azodiisobutyronitrile and tetrahydrofuran is：Methyl methacrylate：0.50g, 5mmol, acetoacetyl methyl-prop Olefin(e) acid ethyl ester：1.07g, 5mmol, the withered ester of dithiobenzoic acid：27.24mg, 0.1mmol, azodiisobutyronitrile：3.28mg 0.02mmol, tetrahydrofuran：2mL.
5. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 2) number of the freeze thawing degassing is 3~5 times.
6. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 2) temperature of the polymerisation is 65 DEG C.
7. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 3) random copolymerization is different without pink solid, Methylacrylic acid polyethylene glycol single armor ether ester, azo two The dosage of butyronitrile and tetrahydrofuran is：Random copolymerization is without pink solid：1.57g, 0.1mmol, metering system acid polyethylene glycol Monomethyl ether ester：0.24g, 0.5mmol, azodiisobutyronitrile：3.28mg, 0.02mmol, tetrahydrofuran：2mL.
8. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 3) number of the freeze thawing degassing is 3~5 times；The temperature of the polymerisation is 65 DEG C.
9. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 4) proportioning of block copolymer P (the MMA-co-AAEM)-b-POEGMA and solvent are 0.5g: 6mL, Wherein, block copolymer P (MMA-co-AAEM)-b-POEGMA is calculated by mass, and solvent is in terms of volume；The ethanol and four The composition of the mixed solution of hydrogen furans is 1: 1 by volume.
10. the preparation method of the gold nanorods with self-healing properties and polymer hybrid material as claimed in claim 1, it is special Sign is that in step 4) time of the ultrasonic disperse is 10min；The time for continuing ultrasound is 30min.
CN201610090116.8A 2016-02-18 2016-02-18 The preparation method of gold nanorods and polymer hybrid material with self-healing properties Active CN105693962B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610090116.8A CN105693962B (en) 2016-02-18 2016-02-18 The preparation method of gold nanorods and polymer hybrid material with self-healing properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610090116.8A CN105693962B (en) 2016-02-18 2016-02-18 The preparation method of gold nanorods and polymer hybrid material with self-healing properties

Publications (2)

Publication Number Publication Date
CN105693962A CN105693962A (en) 2016-06-22
CN105693962B true CN105693962B (en) 2018-01-12

Family

ID=56223052

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610090116.8A Active CN105693962B (en) 2016-02-18 2016-02-18 The preparation method of gold nanorods and polymer hybrid material with self-healing properties

Country Status (1)

Country Link
CN (1) CN105693962B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021114057A1 (en) * 2019-12-09 2021-06-17 彩科(苏州)生物科技有限公司 Composite microsphere and preparation method and application thereof
CN112194959A (en) * 2020-09-30 2021-01-08 浙江中泓新材料科技有限公司 Epoxy anticorrosive primer and production process thereof
CN113363087A (en) * 2021-05-27 2021-09-07 上海应用技术大学 Low-temperature-resistant self-healing hydrogel electrolyte and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102492250A (en) * 2011-12-08 2012-06-13 天津工业大学 Temperature-sensitive polymer/gold nanoparticle hybrid microspheres and preparation method thereof
CN103113745A (en) * 2013-03-13 2013-05-22 哈尔滨工业大学 Preparation and self-repairing method of carbon fiber/gold nanoparticle/polyether sulfone composite material with interface self-repairing performance
WO2013079469A1 (en) * 2011-11-28 2013-06-06 Fundación Cidetec Self-healing material and method for the preparation thereof
CN103159969A (en) * 2013-03-13 2013-06-19 哈尔滨工业大学 Preparation method and self-repair method of self-repairable polymethylmethacrylate resin film
CN103756229A (en) * 2013-12-19 2014-04-30 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of thermosensitive composite gold nanoparticles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013079469A1 (en) * 2011-11-28 2013-06-06 Fundación Cidetec Self-healing material and method for the preparation thereof
CN102492250A (en) * 2011-12-08 2012-06-13 天津工业大学 Temperature-sensitive polymer/gold nanoparticle hybrid microspheres and preparation method thereof
CN103113745A (en) * 2013-03-13 2013-05-22 哈尔滨工业大学 Preparation and self-repairing method of carbon fiber/gold nanoparticle/polyether sulfone composite material with interface self-repairing performance
CN103159969A (en) * 2013-03-13 2013-06-19 哈尔滨工业大学 Preparation method and self-repair method of self-repairable polymethylmethacrylate resin film
CN103756229A (en) * 2013-12-19 2014-04-30 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of thermosensitive composite gold nanoparticles

Also Published As

Publication number Publication date
CN105693962A (en) 2016-06-22

Similar Documents

Publication Publication Date Title
CN105693962B (en) The preparation method of gold nanorods and polymer hybrid material with self-healing properties
Zhu et al. Microfluidics‐assisted assembly of injectable photonic hydrogels toward reflective cooling
Fang et al. Shape-memory polymer composites selectively triggered by near-infrared light of two certain wavelengths and their applications at macro-/microscale
CN101429436A (en) Composition and film for producing polymer dispersion liquid crystal, and producing method thereof
CN100497489C (en) Method for preparing nano pigment water-borne dispersion
CN104745055A (en) High-strength coating formed by virtue of photo-thermal dual-curing and preparation method thereof
Yang et al. Polydopamine Particle‐Filled Shape‐Memory Polyurethane Composites with Fast Near‐Infrared Light Responsibility
CN109503862B (en) Near-infrared response type nano composite supramolecular hydrogel and preparation method thereof
CN103130969A (en) Fluoropolymer microsphere
CN101942058B (en) Infrared photodeformable liquid crystal high-polymer nano composite material and preparation method thereof
WO2017164496A1 (en) Method for producing superabsorbent resin fiber
CN113480774B (en) Super-elastic solar interface evaporation cellulose aerogel and preparation method thereof
Wan et al. Synthesis and characterization of phase change materials microcapsules with paraffin core/cross-linked hybrid polymer shell for thermal energy storage
CN101735465B (en) Porous konjak high water absorbability colloidal particles and preparation method thereof
CN109825034A (en) It is a kind of to realize sulfydryl-epoxy deep layer photocuring method and combinations thereof
CN109250702A (en) Porous carbon materials and its preparation method and application
Zhou et al. Preparation of shape memory epoxy resin for asphalt mixtures and its influences on the main pavement performance
CN103772861B (en) A kind of responding microwave type shape memory polymer composite material and preparation method thereof
Xing et al. Strong, tough, fatigue-resistant and 3D-printable hydrogel composites reinforced by aramid nanofibers
CN107778416A (en) High-strength and high ductility mineralising hydrogel and its preparation method and application
KR102634904B1 (en) Super absorbent polymer and preparation method for the same
Kwon et al. Semi‐IPN superabsorbent polymer based on itaconic acid and polyvinyl alcohol with improved gel strength and salt resistance
Li et al. A route of polyethylene glycol-based phase change heat storage wood with AlN as the thermal conductive filler
CN104387710A (en) Method for preparing microwave driving type interpenetrating network shape memory polymer
CN103588931B (en) Two in-situ synthetic methods of temperature-responsive nano silver composite hydrogel

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant