CN105693962A - Preparation method of gold nanorod and polymer hybrid material with self-healing performance - Google Patents

Preparation method of gold nanorod and polymer hybrid material with self-healing performance Download PDF

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CN105693962A
CN105693962A CN201610090116.8A CN201610090116A CN105693962A CN 105693962 A CN105693962 A CN 105693962A CN 201610090116 A CN201610090116 A CN 201610090116A CN 105693962 A CN105693962 A CN 105693962A
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gold nanorods
self
hybrid material
preparation
aaem
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CN105693962B (en
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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
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Xiamen University
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    • 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
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    • 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
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Abstract

The invention discloses a preparation method of a gold nanorod and polymer hybrid material with a self-healing performance and relates to organic/inorganic hybrid nano materials.The preparation method includes enabling the surfaces of prepared gold nanorods to be provided with reactive aminos by a ligand exchange method, preparing P(MMA-co-AAEM)-b-POEGMA copolymers with proportion-adjustable chain segments by a reversible addition-fragmentation chain transfer polymerization method, and doping the gold nanorods into polymers to achieve good dispersion of the gold nanorods in the polymers under the action of imine bonds and hydrogen bonds formed between the aminos and the polymers so as to obtain the hybrid material.By the aid of effective light-heat conversion performance of the gold nanorods, the hybrid material can be subjected to defect self-healing under the action of near-infrared light.

Description

There is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material
Technical field
The present invention relates to hybrid field of nanometer material technology, the preparation method particularly relating to a kind of gold nanorods with self-healing properties and polymer hybrid material。
Background technology
In use procedure, owing to being subject to the impact of the factors such as environment's heat, mechanism and chemistry, the inside of macromolecular material can produce microfissure even crackle, thus affecting its normal mechanical property and service life。Microfissure is as the blasting fuse damaging material property, and it will eventually cause the macroscopic view cracking of material in the expansion of extending of material internal, and therefore, how the internal injury of repair composite material becomes the study hotspot of scientist。For the macroscopic macroscopic cracking of material surface or layering, it is possible to repaired by suitable manual operations, but once material internal occurs in that microfissure, it is difficult to locking damaged zone and repairs in time。If the microfissure of composite inner is not repaired, not only will affect the service life of material, and can grow in intensity, finally be expanded into macroscopic cracking so that material loses normal function, cause economic loss。Therefore, the self-healing properties studying composite suffers 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 metalchelated catechol functionalized macromolecular network utilizing mussel to inspire out。B.Kollbe group (B.KollbeAhn, DongWoogLee, etal.Surface-initiatedself-healingofpolymersinaqueousmed ia, NATUREMATERIALS, DOI:10.1038/NMAT4037) the surface-functionalized polyacrylate of catechol and polymethyl methacrylate is utilized to carry out selfreparing in metal-free water, they are found that these materials can first pass through and are connected by interface hydrogen bond under the effect of catechol, and what recycle that follow-up intermolecular force carries out repairing subsequently consolidates thus being finally reached the effect of selfreparing。B.Wang group (B.Wang, Y.S.Jeon, etal.Mussel-mimeticself-healingpolyaspartamidederivative gelviaboron-catecholinteractions, eXPRESSPolymerLetters, Vol.9, No.9 (2015) 799 808) utilize a kind of dopamine hydrochloride polymer with ethanolamine to form a kind of boron and the cross-linked gel of catechol coordination generation with acid reaction, this gel also exists the coordination mechanism being brought out guiding by pH, controlling thus reaching reversible gelling to complete self-repair procedure pH can be passed through under given conditions。
In recent years, nanometer gold has rapidly become international focus with its special dimensional effect, skin effect, and the most noticeable character of gold nanorods is exactly local surface plasma resonance effect (LSPR)。This is owing to gold nanorods outer layer has the electronics of high activity, when light to particle diameter is much smaller than time on the gold nanorods of its excitation wavelength, the plasma wave produced is limited at the structure periphery of nanometer gold, if the frequency of incident illumination is suitable with the frequency of vibration of electronics, incident illumination can be produced strong LSPR and absorb by gold nanorods, the absorption of this energy can make the temperature on gold nanorods surface rise to hundreds of degree Celsius even thousands of degrees Celsius, illumination thus can be utilized to cause the melted of polymer, therefore it is contemplated that this for nanometer gold special character is applied in selfreparing field。There is seminar's applying nano gold in self-repair material in our prior, such as in 2010, Chan group (ChanWooPark, AntoinetteB.South, etal.Goldnanoparticlesreinforceself-healingmicrogelmulti layersColloid, PolymSci, (2011) 289:583 590) by the golden nanometer particle of citrate-stable of adulterating in hydrogel/polyelectrolyte multilayer thin film to provide thin film resistance to stress lesion capability in the dry state, though this method does not utilize the LSPR effect of nanometer gold, selfreparing still relies on hydrogel, but the research of this form is found that nanometer gold can't disturb the self-repair procedure of hydrogel, but also the toughness of thin film is strengthened by doping vario-property。Chinese patent CN103113745A openly has preparation and the self-repair method of the carbon fiber/golden nanometer particle/Polyethersulfone Composites of interface self-healing properties, first electricity consumption deep pulse area method prepares carbon fiber/golden nanometer particle fiber, compressing with polyether sulfone pellet again, form the carbon fiber/golden nanometer particle/Polyethersulfone Composites with interface self-healing properties, this method is mainly used in interface and repairs, and solves traditional carbon fibre composite and is easily generated crackle thus reducing a difficult problem for material lifetime。
Summary of the invention
Present invention aim at the preparation method that a kind of gold nanorods with self-healing properties and polymer hybrid material are provided。
The present invention comprises the following steps:
1) gold nanorods of monodispersity is first prepared, use ethanol centrifuge washing, remove CTAB unnecessary in gold nanorods growth course, again with the alcoholic solution centrifuge washing containing amino ligands, the CTAB amino ligands of gold nanorods surface attachment is replaced, finally uses ethanol centrifuge washing, remove unnecessary amino ligands, with ethanol, the gold nanorods dispersion that obtains is processed, obtain the gold nanorods alcoholic solution of monodispersity；
2) MMA, AAEM, CDB and AIBN are dissolved in oxolane, after freeze thawing is degassed under argon shield polyreaction, the sudden cold rear stopped reaction of liquid nitrogen, after reaction solution precipitates in ether, vacuum drying obtains random copolymerization without pink solid；
3) by step 2) random copolymerization that obtains is dissolved in oxolane without pink solid with OEGMA and AIBN; after freeze thawing is degassed under argon shield polyreaction; the sudden cold rear stopped reaction of liquid nitrogen; after reaction solution precipitates in ether; vacuum drying; obtain block copolymer P (MMA-co-AAEM)-b-POEGMA, pinkiness solid；
4) by step 3) block copolymer P (the MMA-co-AAEM)-b-POEGMA that obtains is dissolved in solvent, after ultrasonic disperse, add step 1) the gold nanorods alcoholic solution of gained monodispersity, continue ultrasonic disperse, obtain navy blue clear solution, turning evaporation again, namely after vacuum drying, under infrared lamp, illumination is moulding obtains the gold nanorods and polymer hybrid material with self-healing properties, and this product is black solid；Described solvent is the mixed solution of ethanol and oxolane。
In step 1) in, the gold nanorods of described preparation monodispersity is referred to document: BabakNikoobakhtandMostafaA.El-Sayed, PreparationandGrowthMechanismofGoldNanorods (NRs) UsingSeed-MediatedGrowthMethod, Chem.Mater.2003,15,1957-1962；Described ethanol centrifuge washing can centrifuge washing twice；The described one being selected from containing amino ligands in ethylenediamine, cyclohexanediamine, polymine, polyacrylamide etc.；Described can centrifuge washing twice with the alcoholic solution centrifuge washing containing amino ligands；Described last ethanol centrifuge washing can centrifuge washing twice；In the gold nanorods alcoholic solution of obtained monodispersity, the weight/mass percentage composition of gold nanorods can be 0.5%。
In step 2) in, the consumption of described MMA, AAEM, CDB, AIBN and oxolane can be: MMA:0.50g, 5mmol, AAEM:1.07g, 5mmol, CDB:27.24mg, 0.1mmol, AIBN:3.28mg, 0.02mmol, oxolane: 2mL；The degassed number of times of described freeze thawing can be 3～5 times；The temperature of described polyreaction can be 65 DEG C；After the sudden cold stopped reaction of liquid nitrogen, dynamics research can be carried out, often cross the interval sampling set and do GPC and NMR test。
In step 3) in, described random copolymerization without the consumption of pink solid, OEGMA, AIBN and oxolane can be: random copolymerization is without pink solid: 1.57g, 0.1mmol, OEGMA:0.24g, 0.5mmol, AIBN:3.28mg, 0.02mmol, oxolane: 2mL；The degassed number of times of described freeze thawing can be 3～5 times；The temperature of described polyreaction can be 65 DEG C；After the sudden cold stopped reaction of liquid nitrogen, dynamics research can be carried out, often cross the interval sampling set and do GPC and NMR test。
In step 4) in, the proportioning of described block copolymer P (MMA-co-AAEM)-b-POEGMA and solvent can be 0.5g: 6mL, and wherein, block copolymer P (MMA-co-AAEM)-b-POEGMA calculates in mass, and solvent is calculated by volume；The composition of the mixed solution of described ethanol and oxolane can be 1: 1 by volume；The time of described ultrasonic disperse can be 10min；Described continuation ultrasonic time can be 30min。
In the present invention, synthesized P (MMA-co-AAEM)-b-POEGMA polymer comprises the low POEGMA of the high PMMA of glass transition temperature, glass transition temperature and has the PAAEM that can react and be formed hydrogen bond action with amino。After the cetyl trimethylammonium bromide (CTAB) of the ligand-displacement gold rod surface attachment utilized containing amino, by the gold nanorods obtained and P (MMA-co-AAEM)-b-POEGMA polyblend, form organic/inorganic nano-hybrid materials。Imine linkage or hydrogen bond action can be formed between amino and the polymeric matrix on golden nanometer particle surface, promote gold nanorods stable and uniform dispersion in polymeric matrix。Now under near infrared light, there is strong LSPR effect in gold nanorods, the temperature on induction gold rod surface steeply rises, polymer is transferred heat to centered by gold rod, accelerate polymer when ambient temperature is far below the glass transition temperature of polymer and occur melted so that the hybrid material selfreparing being damaged。
Hybrid material prepared by the present invention has a characteristic that
(1) a kind of self-repair method is established, it is possible to accomplish section selfreparing accurately, it is adaptable to repair various difform section。
(2) hybrid material has efficient near-infrared absorption ability, and luminous energy can be transformed into heat energy, its selfreparing principle is in that gold nanorods absorbs infrared light under Infrared irradiation and produces big calorimetric and make ambient polymer reach viscous state, thus under external force filled opening, section to be to reach selfreparing effect。
(3) generalization of the present invention is strong, it is adaptable to multiple polymers, as long as active force can be utilized to make gold rod effectively mix with polymer can give polymer self-reparing capability。
(4) present invention is applicable to repeatedly repair。
(5) temperature-rise period of gold nanorods is driven by illumination, and the restriction therefore suffering from environment is less。
Accompanying drawing explanation
Fig. 1 be P (MMA-co-AAEM) polymer in embodiment 1 proton nmr spectra (1HNMR) result。As shown in the figure: PMMA:[δ=3.60 (3H, COOCH 3)]；PAAEM:[δ=4.37 (2H, COOCH 2CH2OCOCH2COCH3), 4.19 (2H, COOCH2CH 2OCOCH2COCH3), 3.60 (2H, COOCH2CH2OCOCH 2COCH3)]。Nuclear-magnetism peak integral area ratio is it can be seen that P (MMAx-co-AAEMy) x: y be 0.95: 1。
Fig. 2 be P (MMA-co-AAEM)-b-POEGMA polymer in embodiment 1 proton nmr spectra (1HNMR) result。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)]。Nuclear-magnetism peak integral area ratio is it can be seen that P (MMAx-co-AAEMy)m-b-POEGMAnM: n be 21.3: 1。
Fig. 3 is the optical microscope photograph after gold nanorods in embodiment 1-polymer hybrid material is repaired。In figure 3, a is for repairing 0min；B is for repairing 5min；C is for repairing 10min；D is for repairing 15min。
Detailed description of the invention
The present invention is not limited only to specific embodiments set forth below, also can combine arbitrarily according to real needs。
Embodiment is as follows:
One, surface has the gold nanorods of response type amino and prepares:
(1) the gold nanorods preparation method list of references of monodispersity: BabakNikoobakhtandMostafaA.El-Sayed, PreparationandGrowthMechanismofGoldNanorods (NRs) UsingSeed-MediatedGrowthMethod, Chem.Mater.2003,15,1957-1962。
(2) by CTAB unnecessary in twice removal gold rod growth course of gold nanorods ethanol centrifuge washing of preparing in step (1), replace by twice CTAB amino ligands by gold rod surface attachment of the alcoholic solution centrifuge washing containing amino ligands more afterwards, finally remove unnecessary amino ligands for twice with ethanol centrifuge washing again。
(3) with 10mL ethanol, preparation gold rod is carried out dispersion process, obtain the gold nanorods alcoholic solution of monodispersity。
In described step (2) can be ethylenediamine, cyclohexanediamine, polyacrylamide, polymine etc. containing amino ligands。
Two, the preparation of P (MMA-co-AAEM)-b-POEGMA polymer:
1) MMA, AAEM, CDB and AIBN are dissolved in oxolane, after degassed 3～5 times of continuous freeze thawing under argon shield after 65 DEG C of polymerizations, reaction set time the sudden cold stopped reaction of liquid nitrogen。Dynamics research is then often crossed the interval sampling set and is done GPC and NMR test。After reaction solution precipitates in ether, vacuum drying obtains random copolymerization without pink solid。According to polymer difference chain length P (MMA in experimentx-co-AAEMy) feed intake, wherein, x, y are the molar content (x, y span 0.9～0.1) of repetitive MMA and repetitive AAEM。
Note:
(1) in experiment, the content of CDB feeds intake according to the 1mol% of MMA and AAEM monomer total amount；
(2) in experiment, the content of AIBN feeds intake according to the 20mol% of CDB；
(3) embodiment 1～9 all uses polymine that CTAB is replaced。
Repetitive MMA and the molar content x of repetitive AAEM, y span are 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) by step 1) in gained pink solid, OEGMA and AIBN is dissolved in oxolane, after degassed 3～5 times of continuous freeze thawing under argon shield after 65 DEG C of polymerizations, reaction set time the sudden cold stopped reaction of liquid nitrogen。Dynamics research is then often crossed the interval sampling set and is done GPC and NMR test。After reaction solution precipitates in ether, vacuum drying obtains block copolymer pink solid。According to polymer different polymerization degree P (MMA in experimentx-co-AAEMy)m-b-POEGMAn, m, n are P (MMAx-co-AAEMy) and the degree of polymerization (m, n span is 90～10) of POEGMA。
Note:
(1) amount of AIBN is according to first paragraph P (MMAx-co-AAEMy) 20mol% of copolymer feeds 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 the degree of polymerization m of POEGMA, 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
Three, the preparation of gold nanorods-polymer hybrid material
(1) take in the mixed solution that P (MMA-co-AAEM)-b-POEGMA polymer is dissolved in ethanol and oxolane, ultrasonic 10min is uniformly dispersed, add the nanometer gold bar alcoholic solution of gained 0.5wt% in described step one, continue ultrasonic 30min to be uniformly dispersed, obtain navy blue clear solution。
(2) gained clear solution in described step (1) being rotated evaporation, after vacuum drying, under infrared lamp, illumination is moulding then can obtain black solid hybrid material。
Note:
1) P (MMA in embodiment 19～27x-co-AAEMy)m-b-POEGMAnX and y be 0.5, m and n is 50；
2) in list, nanometer gold bar content refers to the mass fraction (wt%) accounting for P (MMA-co-AAEM)-b-POEGMA polymer, namely by the nanometer gold bar alcoholic solution conversion gained of 0.5wt%。
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-(Methylacrylic acid polyethylene glycol single armor ether ester) hybrid material of poly-(methyl methacrylate-co-AAEM)-b-(to be called for short: preparation method Aurod/P (MMA-co-AAEM)-b-POEGMA) and self-healing properties thereof。Ligand exchange method is first adopted to make the nanometer gold bar surface of preparation have reactive amino, recycling reversible addion-fragmentation chain transfer polymerization prepares segment ratio adjustable P (MMA-co-AAEM)-b-POEGMA copolymer, gold nanorods is doped in polymer the most at last, by the imine linkage formed between amino and polymer and hydrogen bond action, realize gold nanorods fine dispersion in the polymer, it is thus achieved that hybrid material。The effective optical and thermal conversion performance of gold nanorods so that this hybrid material can carry out defect selfreparing under the effect of near infrared light。

Claims (10)

1. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material, it is characterised in that comprise the following steps:
1) gold nanorods of monodispersity is first prepared, use ethanol centrifuge washing, remove CTAB unnecessary in gold nanorods growth course, again with the alcoholic solution centrifuge washing containing amino ligands, the CTAB amino ligands of gold nanorods surface attachment is replaced, finally uses ethanol centrifuge washing, remove unnecessary amino ligands, with ethanol, the gold nanorods dispersion that obtains is processed, obtain the gold nanorods alcoholic solution of monodispersity；
2) MMA, AAEM, CDB and AIBN are dissolved in oxolane, after freeze thawing is degassed under argon shield polyreaction, the sudden cold rear stopped reaction of liquid nitrogen, after reaction solution precipitates in ether, vacuum drying obtains random copolymerization without pink solid；
3) by step 2) random copolymerization that obtains is dissolved in oxolane without pink solid with OEGMA and AIBN; after freeze thawing is degassed under argon shield polyreaction; the sudden cold rear stopped reaction of liquid nitrogen; after reaction solution precipitates in ether; vacuum drying; obtain block copolymer P (MMA-co-AAEM)-b-POEGMA, pinkiness solid；
4) by step 3) block copolymer P (the MMA-co-AAEM)-b-POEGMA that obtains is dissolved in solvent, after ultrasonic disperse, add step 1) the gold nanorods alcoholic solution of gained monodispersity, continue ultrasonic disperse, obtain navy blue clear solution, turning evaporation again, namely after vacuum drying, under infrared lamp, illumination is moulding obtains the gold nanorods and polymer hybrid material with self-healing properties, and this product is black solid；Described solvent is the mixed solution of ethanol and oxolane。
2. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterised in that in step 1) in, described ethanol centrifuge washing is centrifuge washing twice；Described it is centrifuge washing twice with the alcoholic solution centrifuge washing containing amino ligands；Described finally it is centrifuge washing twice with ethanol centrifuge washing。
3. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterised in that in step 1) in, the described one containing amino ligands in ethylenediamine, cyclohexanediamine, polymine, polyacrylamide。
4. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterized in that in step 2) in, the consumption of described MMA, AAEM, CDB, AIBN and oxolane is: MMA:0.50g, 5mmol, AAEM:1.07g, 5mmol, CDB:27.24mg, 0.1mmol, AIBN:3.28mg, 0.02mmol, oxolane: 2mL。
5. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterised in that in step 2) in, the degassed number of times of described freeze thawing is 3～5 times。
6. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterised in that in step 2) in, the temperature of described polyreaction is 65 DEG C。
7. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterized in that in step 3) in, described random copolymerization without the consumption of pink solid, OEGMA, AIBN and oxolane is: random copolymerization is without pink solid: 1.57g, 0.1mmol, OEGMA:0.24g, 0.5mmol, AIBN:3.28mg, 0.02mmol, oxolane: 2mL。
8. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterised in that in step 3) in, the degassed number of times of described freeze thawing is 3～5 times；The temperature of described polyreaction can be 65 DEG C。
9. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterized in that in step 4) in, the proportioning of described block copolymer P (MMA-co-AAEM)-b-POEGMA and solvent is 0.5g: 6mL, wherein, block copolymer P (MMA-co-AAEM)-b-POEGMA calculates in mass, and solvent is calculated by volume；The composition of the mixed solution of described ethanol and oxolane can be 1: 1 by volume。
10. there is the gold nanorods of self-healing properties and the preparation method of polymer hybrid material as claimed in claim 1, it is characterised in that in step 4) in, the time of described ultrasonic disperse is 10min；Described continuation ultrasonic time is 30min。
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