CN105670285B - A kind of nanogold/polyimide composite film and preparation method thereof - Google Patents
A kind of nanogold/polyimide composite film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to field of compound material, and in particular to a kind of nanogold/polyimide composite film and preparation method thereof.The polyimides that the laminated film is blocked by the nano Au particle and anhydride group of Cysteamine-stabilized is combined by the amidation process between the amino of mercaptoethylmaine and the anhydride group of the polyimides, and the part by weight of the polyimides of nano Au particle and the anhydride group end-blocking of Cysteamine-stabilized is 0.065 0.327：100.The preparation method of the laminated film includes the nmp solution preparation of the nano Au particle of Cysteamine-stabilized, the preparation of polyimides of anhydride group end-blocking and three steps of preparation of nanogold/polyimide composite film.It is combined together between nano Au particle and polyimides by the effect of imide bond, the active force of chemical bond acts on much larger than physical blending, it is effectively reduced the reunion of nano Au particle, ensure the good catalytic efficiency of nanogold, while also enhance the mechanical performance of the polyimides as matrix material, heat resistance.
Description
Technical field
The invention belongs to field of compound material, and in particular to a kind of nanogold/polyimide composite film and its preparation side
Method.
Background technology
With the rapid development of modern science and technology, people put forward higher requirement to the species and performance of material.Receive
The one kind of meter Jin as nano material, it with small-size effect, surface-interface effect, quantum size effect etc. except typically receiving
Possessed by rice material outside property, also with good biocompatibility, inoxidizability and catalytic performance.In recent years, nitrobenzene
The pollution of phenol and nitrophenyl phenolic compounds to water body causes the extensive concern of people, and China, which is classified as in water, to be needed preferentially to control
One of pollution of system.Due to the excellent catalytic performance of nano gold catalysis material, it has become the one of catalysis reduction nitrophenol
Efficient, the quick and environment-friendly catalysis material of kind；Synthesize high degree of dispersion, size uniformity, stably, easily separated and recyclable repetition
The nano gold catalysis material utilized is the research emphasis in the field.Polyimides (PI) has good weatherability, acid and alkali-resistance, resistance to
High temperature, radiation hardness and good mechanical performance.Nanogold and polyimides are compounded in one by this experiment by chemical bond
Rise so that nanogold is uniformly disperseed in matrix material, inhibits the reunion of nano Au particle well, so not only can be with
Strengthen the heat resistance, mechanical strength etc. of polyimides, and greatly extend nanogold and use ring in catalytic applications
Border, the efficiency of nanogold reuse is improved very well.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of nanogold/polyimide composite film and its preparation side
Method, it can be very good the advantage of two kinds of materials of comprehensive prominent nanogold and polyimides and synergistic function is obvious, enhancing
The heat resistance and mechanical strength of polyimides, make nanogold preferably disperse, and catalytic efficiency, reuse ability, varying environment
In applicability etc. effectively strengthen.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：It is multiple that the present invention provides a kind of nanogold/polyimides
Film is closed, amino and institute of the polyimides blocked by the nano Au particle and anhydride group of Cysteamine-stabilized by mercaptoethylmaine
The amidation process stated between the anhydride group of polyimides is combined, the nano Au particle and acid anhydrides of the Cysteamine-stabilized
The part by weight of the polyimides of base end-blocking is 0.065-0.327：100.
Specifically, the particle diameter of the nano Au particle of the Cysteamine-stabilized is 30-60nm.
Specifically, the polyimides of anhydride group end-blocking is by 4,4- diaminodiphenyl ethers, Bisphenol A Type Diether Dianhydride and 4,
4- biphenyl ether dianhydrides are according to 2：1：It is the 4,4- biphenyl ether dianhydride 0.1-0.2 that 1 mol ratio, which is copolymerized, adds molal quantity afterwards,
Bisphenol A Type Diether Dianhydride again blocks, finally progress chemical imidization is made.
The present invention also provides a kind of method for preparing above-mentioned nanogold/polyimide composite film, comprises the following steps：
S1. prepared by the nmp solution of the nano Au particle of Cysteamine-stabilized：By appropriate NaBH4Ethanol solution, gold chloride
Ethanol solution and the ethanol solution of mercaptoethylmaine be stirred and fully react at normal temperatures, obtain the nanometer of Cysteamine-stabilized
The ethanol solution of gold particle, appropriate nmp solvent is added, be sufficiently stirred rear rotary evaporation and fall ethanol, obtain Cysteamine-stabilized
Nano Au particle nmp solution, the wherein concentration of nano Au particle is 0.55-1.25g/L, and the Cysteamine-stabilized is received
The particle diameter of rice gold particle is 30-60nm；
S2. the preparation of the polyimides of anhydride group end-blocking：The nmp solution of 4,4- diaminodiphenyl ethers is prepared, wherein 4,4-
Diaminodiphenyl ether concentration is 0.15-0.25mol/L, and molal quantity is added in the nmp solution of 4,4- diaminodiphenyl ethers and is
The Bisphenol A Type Diether Dianhydride and 4,4- biphenyl ether dianhydride solid powder, room temperature and nitrogen of 0.5 times of 4, the 4- diaminodiphenyl ethers
It is stirred under protection and fully reacts, continuously adds the bisphenol A-type that molal quantity is 0.1-0.2 times of 4, the 4- biphenyl ether dianhydride
Two ether dianhydrides carry out anhydride group end-blocking, obtain the polyamic acid solution of anhydride group end-blocking, add appropriate acetic anhydride and pyridine, institute
The molal quantity for stating acetic anhydride and pyridine is respectively 9-11 times and 5-7 times of 4, the 4- biphenyl ether dianhydride, is sufficiently stirred, adds at room temperature
Hot fully reaction carries out chemical imidization, obtains clear yellow viscous solution, absolute ethyl alcohol precipitating, filters and be fully dried to obtain acid anhydrides
The polyimides of base end-blocking；
S3. the preparation of nanogold/polyimide composite film：Prepare the polyimides of the anhydride group end-blocking prepared in S2
Nmp solution, its concentration are 75-100g/L, by the nmp solution and acid anhydrides of the nano Au particle of the Cysteamine-stabilized prepared in S1
The nmp solution of the polyimides of base end-blocking is according to 1-4：5 volume ratio mixing, is sufficiently stirred, the viscous fluid that will be obtained at room temperature
Body casting film-forming on glass plate or silica gel plate, respectively dried at a temperature of 80,100,150,180,220,250 and 280 DEG C afterwards
8th, 2,2,2,1,2/3 and 2/3 hours, nanogold/polyimide composite film is obtained.
Specifically, in S1 the ethanol solution of NaBH4 ethanol solution, the ethanol solution of gold chloride and mercaptoethylmaine concentration
It is followed successively by 2mol/L, 0.13-0.17g/L, 2mol/L.
Specifically, the NaBH4Ethanol solution, gold chloride ethanol solution and mercaptoethylmaine ethanol solution according to 1：
1：600 volume ratio mixing.
Specifically, the ethanol solution of the gold chloride by aqueous solution of chloraurate and absolute ethyl alcohol according to 1：600 volume ratio
It is mixed to prepare, the concentration of the aqueous solution of chloraurate is 80-100g/L.
Preferably, the process that fully reaction carries out chemical imidization is heated in S2 is, at a temperature of 60,80 and 100 DEG C
Each reaction 6,2 and 2 hours respectively.
Preferably, the mol ratio of acetic anhydride and pyridine is 2 in S2：1.
Preferably, the thickness of the nanogold/polyimide composite film obtained in S3 is 0.25-1mm.
The present invention has following features compared with prior art：
1) be all between most of nano Au particle and carrier by the method for physical blending at present and compound, it is and such a
Method often due to the small-size effect of blend and be easier to reunite, not only make the catalytic performance of nanogold reduce, and
Original performance of matrix material is set also to have declined；And it is in the present invention, between nano Au particle and polyimides to pass through acyl
The effect of imine linkage and be combined together, the active force of chemical bond is far longer than physical blending effect, and nano Au particle is not easy
Desorption, is so effectively reduced the reunion of nano Au particle, not only ensure that catalysis of the nano Au particle in catalytic applications
Efficiency and recycling number, also cause mechanical performance, heat resistance of the polyimides as matrix material etc. to strengthen.
2) polyimides has good weatherability, acid and alkali-resistance, high temperature resistant, radiation hardness and good mechanical performance, with
It can make nano Au particle be used for more catalytic environments as matrix material, i.e. its applicability strengthens.
3) golden nanometer particle is compound by chemical bond and matrix material polyimides, and Jenner's particle is in the laminated film
In be uniformly dispersed, the electric property of the laminated film can be adjusted with the change of golden nanometer particle content, and it is most probably
As a kind of semiconductor for having potential application and researching value or conductor material.
Brief description of the drawings
Fig. 1 is XRD spectrum, and wherein b is the XRD curves of nanogold/polyimide composite film prepared by the present invention, and a is
The XRD curves of the Kapton of non-composite nano-gold；
Fig. 2 is the Kapton of nanogold/polyimide composite film (AuNPs/PI) and non-composite nano-gold
(PI) thermal gravimetric analysis curve；
Fig. 3 is that nanogold/polyimide composite film is catalyzed the uv-spectrogram monitored during 2- nitroanilines；
The purple that Fig. 4 is monitored when being and being catalyzed 2- nitroanilines as control using the polyimide composite film of non-composite nano-gold
Outer collection of illustrative plates；
Fig. 5 is the syntheti c route of nanogold/polyimide composite film.
Embodiment
Below by specific embodiment, the invention will be further described, and following examples are descriptive, is not limit
Qualitatively, it is impossible to once limit protection scope of the present invention.
Method used in the present invention, it is conventional method unless otherwise required, reagent used in the present invention, such as
It is commercially available prod without particular provisions.
Embodiment 1
A kind of method for preparing above-mentioned nanogold/polyimide composite film, comprises the following steps：
S1. prepared by the nmp solution of the nano Au particle of Cysteamine-stabilized：500uL aqueous solution of chloraurate (93g/L) is added
Enter to 300mL ethanol solutions, then 1mmol mercaptoethylmaine is dissolved in 500uL ethanol solutions, is added to
State and 30min is sufficiently stirred in solution, 1mmol NaBH4It is dissolved in 500uL absolute ethyl alcohols and is added in mixed solution, it is molten
Liquid color moment is changed into claret from yellow, and constant speed stirs 1 hour, adds 50mLNMP solvents into above-mentioned mixed solution, after
Rotary evaporation falls ethanol and arrives the nmp solution to the nano Au particle of Cysteamine-stabilized, wherein nano-scale gold particle after continuous stirring 1h
The concentration of son is 0.93g/L, and the particle diameter of the nano Au particle of the Cysteamine-stabilized is 30-60nm；
S2. the preparation of the polyimides of anhydride group end-blocking：4mmol 4,4- diaminodiphenyl ethers (ODA) are dissolved in 20ml N-
The nmp solution of 4,4- diaminodiphenyl ethers is obtained in methyl pyrrolidone (NMP) solvent, its concentration is 0.2mol/L, by 2mmol
It is molten that Bisphenol A Type Diether Dianhydride (BPADA) and 2mmol 4,4- biphenyl ether dianhydride (ODPA) solid powder are added to above-mentioned NMP together
In liquid, at ambient temperature, 24h is stirred in nitrogen atmosphere, the BPADA powder for then adding a small amount of (0.2mmol) is used for acid anhydrides
Base blocks, and so as to obtain polyamic acid (PAA) solution of anhydride group end-blocking, then adds 2mL in PAA solution
(21.15mmol) acetic anhydride and 1mL (12.42mmol) pyridine, for by PAA imidizations, stirring 12 hours at ambient temperature,
Then obtained clear yellow viscous solution is sunk in absolute ethyl alcohol in each reaction of 60,80 and 100 DEG C of difference 6,2 and 2 hours again
Analysis, obtains lurid flocculent deposit, filters, and drying in 24 hours is dried in 100 DEG C of baking ovens, produces；
S3. the preparation of nanogold/polyimide composite film：The polyimides 0.4g for taking the anhydride group prepared in S2 to block
It is dissolved in 5mL NMP, obtains the nmp solution of the polyimides of anhydride group end-blocking, its concentration is 80g/L, takes what is prepared in S1
The nmp solution 5mL of the polyimides of the nmp solution 3mL of the nano Au particle of Cysteamine-stabilized and above-mentioned anhydride group end-blocking is mixed
Close, be sufficiently stirred at room temperature, by obtained thick liquid on glass plate or silica gel plate casting film-forming, afterwards 80,100,
150th, it is each at a temperature of 180,220,250 and 280 DEG C to dry 8,2,2,2,1,2/3 and 2/3 hours, obtain nanogold/polyimides
Laminated film.
Fig. 5 is the syntheti c route of nanogold/polyimide composite film.
The thickness of the nanogold/polyimide composite film is 0.55mm after testing, and the particle diameter of nano Au particle is thereon
The part by weight of 30-60nm, wherein nano Au particle and the polyimides of anhydride group end-blocking is 0.196：100.
The present invention has carried out XRD diffraction to above-mentioned nanogold/polyimide composite film and has tested and the diffracting spectrum is entered
Row analysis, Fig. 1 is XRD spectrum, and a is the XRD curves of polyimides that block of anhydride group of non-composite Nano gold particle in Fig. 1, b
For the XRD curves of nano Au particle/polyimide composite film, showing copolyimide part knot at 2 θ=17.5 °
Crystalline substance, corresponding (111) crystal face at 2 θ=38 °, the crystal plane structure for showing nano Au particle is still face-centred cubic structure, and this shows nanometer
Gold particle is successfully combined in polyimide matrix.
The present invention has carried out thermal performance test to above-mentioned nano gold/polyimide composite film, and Fig. 2 is thermogravimetric analysis
Curve, as can be seen from Fig. 2 with the introducing of nano Au particle, thermostabilization of the laminated film (AuNPs/PI) before 5% weightlessness
Property improve 70 DEG C (395.0 DEG C are increased to 466.7 DEG C), and be that (493.0 DEG C are increased to for the temperature raising of only having slightly when 10%
496.7℃).Because it is compound, the same nanometer of effect by chemical bond between nano Au particle and polyimides
Its ethamine of multiple mercaptos of gold particle connection can while act on the end anhydride group of a plurality of polyimides, so in certain temperature
In the range of, nanogold adds the active force of polyimide molecule interchain, so the thermal decomposition temperature of composite membrane can improve.But work as
When temperature exceedes certain limit, the S-Au keys between mercaptoethylmaine and nanogold can be broken, so the weightless temperature of the 10% of composite membrane
The raising of degree only slightly.
The present invention is tested to the mechanical performance of above-mentioned nanogold/polyimide composite film, is found after tested altogether
After golden nanometer particle being successfully introduced into poly- polyimides by the effect of chemical bond, before being not introduced into relatively, its tensile strength
It is significantly improved with elongation at break, tensile strength is lifted to 97.0MPa by 85.4MPa before, and elongation at break is by before
13.1% lifting to 20.8%.
Determined during the measuring mechanical property of film by CMT4014 types electronic tensile machine, rate of extension 5mm/
min.The preparation of batten is about 10cm, wide about 4mm size, and every group of style at least surveys 3 battens, and test result is averaged.
The present invention has also carried out catalytic performance test to above-mentioned nanogold/polyimide composite film：Pass through 2- nitrobenzene
Amine catalytic reduction reaction has detected the catalytic performance of laminated film, and monitors the progress of reaction by ultraviolet spectrometer.
Configuration concentration is 1g/L 2- nitroaniline storing solutions first, then prepares the film sample that length and width are respectively 1cm
Bar, experimentation are first to take 2- nitroaniline soiution 2ml, then add the NaBH that 2ml concentration is 0.1mol/L4The aqueous solution, connect
Since film sample bar is added into mixed solution, a ultraviolet spectra is surveyed at interval of 5min.
During using nanogold/polyimide composite film as catalyst, with the extension in reaction time, the 2- nitrobenzene of yellow
Amine aqueous solution color naked eyes are distinguishable to be gradually become shallower as, the spy of the 2- nitroanilines in ultraviolet spectrogram as shown in Figure 3 at 420nm
Sign absorption peak strength weakens rapidly, the intensity vanishing probably in 1500s；Without plus stating nanogold/polyimides THIN COMPOSITE
Film, and add the polyamides of the anhydride group end-blocking of phase homogenous quantities when carrying out amine film, test result is as shown in figure 4,2- nitre at 420nm
The characteristic absorption peak intensity of base aniline only slightly reduces as time went on.This shows above-mentioned nanogold/polyimides THIN COMPOSITE
Film has preferable catalytic performance；In addition, find, by same one piece of nanogold/polyimide composite film, to repeat through overtesting
Using ten parts of concentration of catalysis and the identical 2- nitroaniline soiutions of volume, the catalytic decomposition time completely used does not almost have
Decline, this shows that nanogold/polyimide composite film prepared by the present invention has good stability, reusable.
Embodiment 2
A kind of method for preparing above-mentioned nanogold/polyimide composite film, comprises the following steps：
S1. prepared by the nmp solution of the nano Au particle of Cysteamine-stabilized：By 500uL aqueous solution of chloraurate (80g/L)
300mL ethanol solutions are added to, then 1mmol mercaptoethylmaine is dissolved in 500uL ethanol solutions, is added to
30min, 1mmol NaBH are sufficiently stirred in above-mentioned solution4It is dissolved in 500uL absolute ethyl alcohols and is added in mixed solution,
Solution colour moment is changed into claret from yellow, and constant speed stirs 1 hour, adds 70mLNMP solvents into above-mentioned mixed solution,
Continue rotary evaporation after stirring 1h to fall ethanol and arrive the nmp solution to the nano Au particle of Cysteamine-stabilized, wherein nanogold
The concentration of particle is 0.57g/L, and the particle diameter of the nano Au particle of the Cysteamine-stabilized is 30-60nm；
S2. the preparation of the polyimides of anhydride group end-blocking：3mmol 4,4- diaminodiphenyl ethers (ODA) are dissolved in 15ml N-
The nmp solution of 4,4- diaminodiphenyl ethers is obtained in methyl pyrrolidone (NMP) solvent, its concentration is 0.2mol/L, will
1.5mmol Bisphenol A Type Diether Dianhydrides (BPADA) and 1.5mmol 4,4- biphenyl ether dianhydride (ODPA) solid powder are added to together
In above-mentioned nmp solution, at ambient temperature, 24h is stirred in nitrogen atmosphere, then add the BPADA powder of a small amount of (0.1mmol)
Blocked for anhydride group, so as to obtain polyamic acid (PAA) solution of anhydride group end-blocking, then add 1.5mL in PAA solution
(15.86mmol) acetic anhydride and 0.64mL (7.93mmol) pyridine, for by PAA imidizations, it is small to stir 12 at ambient temperature
When, then again 60,80 and 100 DEG C of difference it is each reaction 6,2 and 2 hours, by obtained clear yellow viscous solution in absolute ethyl alcohol
Precipitating, lurid flocculent deposit is obtained, filtered, and drying in 24 hours is dried in 100 DEG C of baking ovens, produced；
S3. the preparation of nanogold/polyimide composite film：The polyimides 0.5g for taking the anhydride group prepared in S2 to block
It is dissolved in 5mL NMP, obtains the nmp solution of the polyimides of anhydride group end-blocking, its concentration is 100g/L, takes in S1 and prepares
Cysteamine-stabilized nano Au particle nmp solution 1.5mL and above-mentioned anhydride group end-blocking polyimides nmp solution
5mL is mixed, and is sufficiently stirred at room temperature, by obtained thick liquid on glass plate or silica gel plate casting film-forming, afterwards 80,
100th, it is each at a temperature of 150,180,220,250 and 280 DEG C to dry 8,2,2,2,1,2/3 and 2/3 hours, obtain nanogold/polyamides
Imines laminated film, the thickness of the film is 0.25mm, and the particle diameter of nano Au particle is 30-60nm, wherein nano-scale gold particle thereon
The sub part by weight with the polyimides of anhydride group end-blocking is 0.065：100.
Embodiment 3
A kind of method for preparing above-mentioned nanogold/polyimide composite film, comprises the following steps：
S1. prepared by the nmp solution of the nano Au particle of Cysteamine-stabilized：By 500uL aqueous solution of chloraurate (100g/L)
300mL ethanol solutions are added to, then 1mmol mercaptoethylmaine is dissolved in 500uL ethanol solutions, is added to
30min, 1mmol NaBH are sufficiently stirred in above-mentioned solution4It is dissolved in 500uL absolute ethyl alcohols and is added in mixed solution,
Solution colour moment is changed into claret from yellow, and constant speed stirs 1 hour, adds 54mLNMP solvents into above-mentioned mixed solution,
Continue rotary evaporation after stirring 1h to fall ethanol and arrive the nmp solution to the nano Au particle of Cysteamine-stabilized, wherein nanogold
The concentration of particle is 1.25g/L, and the particle diameter of the nano Au particle of the Cysteamine-stabilized is 30-60nm；
S2. the preparation of the polyimides of anhydride group end-blocking：6mmol 4,4- diaminodiphenyl ethers (ODA) are dissolved in 30ml N-
The nmp solution of 4,4- diaminodiphenyl ethers is obtained in methyl pyrrolidone (NMP) solvent, its concentration is 0.2mol/L, by 3mmol
It is molten that Bisphenol A Type Diether Dianhydride (BPADA) and 3mmol 4,4- biphenyl ether dianhydride (ODPA) solid powder are added to above-mentioned NMP together
In liquid, at ambient temperature, 24h is stirred in nitrogen atmosphere, the BPADA powder for then adding a small amount of (0.6mmol) is used for acid anhydrides
Base blocks, and so as to obtain polyamic acid (PAA) solution of anhydride group end-blocking, then adds 5.1mL in PAA solution
(27.05mmol) acetic anhydride and 1.1mL (13.53mmol) pyridine, for by PAA imidizations, it is small to stir 12 at ambient temperature
When, then again 60,80 and 100 DEG C of difference it is each reaction 6,2 and 2 hours, by obtained clear yellow viscous solution in absolute ethyl alcohol
Precipitating, lurid flocculent deposit is obtained, filtered, and drying in 24 hours is dried in 100 DEG C of baking ovens, produced；
S3. the preparation of nanogold/polyimide composite film：The polyimides for taking the anhydride group prepared in S2 to block
0.45g is dissolved in 5mL NMP, obtains the nmp solution of the polyimides of anhydride group end-blocking, its concentration is 90g/L, is taken in S1
The nmp solution of the polyimides of the nmp solution 4mL of the nano Au particle of the Cysteamine-stabilized of preparation and above-mentioned anhydride group end-blocking
5mL is mixed, and is sufficiently stirred at room temperature, by obtained thick liquid on glass plate or silica gel plate casting film-forming, afterwards 80,
100th, it is each at a temperature of 150,180,220,250 and 280 DEG C to dry 8,2,2,2,1,2/3 and 2/3 hours, obtain nanogold/polyamides
Imines laminated film, the thickness of the film is 1mm, and the particle diameter of nano Au particle is 30-60nm thereon, wherein nano Au particle with
The part by weight of the polyimides of the anhydride group end-blocking is 0.327：100.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of nanogold/polyimide composite film, it is characterised in that by the nano Au particle and acid anhydrides of Cysteamine-stabilized
The polyimides of base end-blocking is combined by the amidation process between the amino of mercaptoethylmaine and the anhydride group of polyimides,
The part by weight of the polyimides of nano Au particle and the anhydride group end-blocking of the Cysteamine-stabilized is 0.065-0.327：
100。
A kind of 2. nanogold/polyimide composite film according to claim 1, it is characterised in that the mercaptoethylmaine
The particle diameter of stable nano Au particle is 30-60nm.
A kind of 3. nanogold/polyimide composite film according to claim 1, it is characterised in that the anhydride group envelope
The polyimides at end is by 4,4- diaminodiphenyl ethers, Bisphenol A Type Diether Dianhydride and 4,4- biphenyl ether dianhydrides according to 2：1：1 mole
Than copolymerization, the Bisphenol A Type Diether Dianhydride that molal quantity is 0.1-0.2 times of 4, the 4- biphenyl ether dianhydride is added afterwards and is blocked, most
Chemical imidization is carried out afterwards to be made.
4. a kind of preparation method of nanogold/polyimide composite film as described in any one of claims 1 to 3, its feature
It is, comprises the following steps：
S1. prepared by the nmp solution of the nano Au particle of Cysteamine-stabilized：By appropriate NaBH4Ethanol solution, the second of gold chloride
The ethanol solution of alcoholic solution and mercaptoethylmaine is stirred and fully reacted at normal temperatures, obtains the nano-scale gold particle of Cysteamine-stabilized
The ethanol solution of son, adds appropriate nmp solvent, is sufficiently stirred rear rotary evaporation and falls ethanol, obtain receiving for Cysteamine-stabilized
The nmp solution of rice gold particle, the wherein concentration of nano Au particle is 0.55-1.25g/L, the nanogold of the Cysteamine-stabilized
The particle diameter of particle is 30-60nm；
S2. the preparation of the polyimides of anhydride group end-blocking：The nmp solution of 4,4- diaminodiphenyl ethers is prepared, wherein 4,4- diaminos
Yl diphenyl ether concentration is 0.15-0.25mol/L, and it is described that molal quantity is added in the nmp solution of 4,4- diaminodiphenyl ethers
The Bisphenol A Type Diether Dianhydride and 4,4- biphenyl ether dianhydride solid powder of 4,4- 0.5 times of diaminodiphenyl ethers, room temperature and nitrogen are protected
Under be stirred and fully react, continuously add the bisphenol A-type diether that molal quantity is 0.1-0.2 times of 4, the 4- biphenyl ether dianhydride
Dianhydride carries out anhydride group end-blocking, obtains the polyamic acid solution of anhydride group end-blocking, adds appropriate acetic anhydride and pyridine, the acetic acid
The molal quantity of acid anhydride and pyridine is respectively 9-11 times and 5-7 times of 4, the 4- biphenyl ether dianhydrides, is sufficiently stirred at room temperature, heating is filled
Divide reaction to carry out chemical imidization, obtain clear yellow viscous solution, absolute ethyl alcohol precipitating, filter and be simultaneously fully dried to obtain anhydride group envelope
The polyimides at end；
S3. the preparation of nanogold/polyimide composite film：Prepare the NMP of the polyimides of the anhydride group end-blocking prepared in S2
Solution, its concentration are 75-100g/L, by the nmp solution and anhydride group of the nano Au particle of the Cysteamine-stabilized prepared in S1
The nmp solution of the polyimides of end-blocking is according to 1-4：5 volume ratio mixing, is sufficiently stirred, the thick liquid that will be obtained at room temperature
The casting film-forming on glass plate or silica gel plate, it is each at a temperature of 80,100,150,180,220,250 and 280 DEG C afterwards dry 8,
2nd, 2,2,1,2/3 and 2/3 hours, nanogold/polyimide composite film is obtained.
A kind of 5. preparation method of nanogold/polyimide composite film according to claim 4, it is characterised in that S1
Middle NaBH4Ethanol solution, gold chloride ethanol solution and mercaptoethylmaine ethanol solution concentration be followed successively by 2mol/L,
0.13-17g/L、2mol/L。
A kind of 6. preparation method of nanogold/polyimide composite film according to claim 5, it is characterised in that institute
State NaBH4Ethanol solution, gold chloride ethanol solution and mercaptoethylmaine ethanol solution according to 1：1：600 volume ratio is mixed
Close.
A kind of 7. preparation method of nanogold/polyimide composite film according to claim 5, it is characterised in that institute
The ethanol solution of gold chloride is stated by aqueous solution of chloraurate and absolute ethyl alcohol according to 1：600 volume ratio is mixed to prepare, the chlorine gold
The concentration of aqueous acid is 80-100g/L.
A kind of 8. preparation method of nanogold/polyimide composite film according to claim 4, it is characterised in that S2
The mol ratio of middle acetic anhydride and pyridine is 2：1.
A kind of 9. preparation method of nanogold/polyimide composite film according to claim 4, it is characterised in that S2
The middle heating process that fully reaction carries out chemical imidization is that it is small that each reaction 6,2 and 2 are distinguished at a temperature of 60,80 and 100 DEG C
When.
10. a kind of preparation method of nanogold/polyimide composite film according to any one of claim 4 to 9, it is special
Sign is that the thickness of the nanogold/polyimide composite film obtained in S3 is 0.25-1mm.
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| US5575955A (en) * | 1994-07-22 | 1996-11-19 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive polyimide film containing gold (III) ions, composition, and process of making |
| CN101235201A (en) * | 2008-02-02 | 2008-08-06 | 上海市合成树脂研究所 | Method for preparing polyimide nano composite thin film |
| US8568867B2 (en) * | 2006-06-26 | 2013-10-29 | Sabic Innovative Plastics Ip B.V. | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
| CN104818463A (en) * | 2015-04-09 | 2015-08-05 | 河南科技大学 | Method for preparing nano platinum-coated gold particles film composite material |
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|---|---|---|---|---|
| US5575955A (en) * | 1994-07-22 | 1996-11-19 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive polyimide film containing gold (III) ions, composition, and process of making |
| US8568867B2 (en) * | 2006-06-26 | 2013-10-29 | Sabic Innovative Plastics Ip B.V. | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
| CN101235201A (en) * | 2008-02-02 | 2008-08-06 | 上海市合成树脂研究所 | Method for preparing polyimide nano composite thin film |
| CN104818463A (en) * | 2015-04-09 | 2015-08-05 | 河南科技大学 | Method for preparing nano platinum-coated gold particles film composite material |
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