CN104629362A - Fluorine-containing polyimide composite film material with low infrared emissivity and preparation method thereof - Google Patents

Fluorine-containing polyimide composite film material with low infrared emissivity and preparation method thereof Download PDF

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CN104629362A
CN104629362A CN201310552583.4A CN201310552583A CN104629362A CN 104629362 A CN104629362 A CN 104629362A CN 201310552583 A CN201310552583 A CN 201310552583A CN 104629362 A CN104629362 A CN 104629362A
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fluorinated polyimide
film
laminated film
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陈景
刘秉鑫
陈修碧
薛立新
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention provides a fluorine-containing polyimide composite film material with a low infrared emissivity and a preparation method thereof. The composite material is prepared by adding 1 to 10% of nano inorganic substances into a fluorine-containing polyimide material, and the nano inorganic substances are actually crystal particles dispersed in the fluorine-containing polyimide. The experiment results show that the thermal stability, environment resistant performance, and low infrared emissivity property of the composite material containing the inorganic substances are all improved, especially the infrared emissivity is greatly reduced, so the provided material can be used to prepare infrared stealth materials having a high requirement on stability and has a good application prospect in the military and civilian fields.

Description

Fluorinated polyimide infrared low-emissivity composite film material and preparation method thereof
Technical field
The present invention relates to infrared stealth and camouflage field, be specifically related to a kind of fluorinated polyimide infrared low-emissivity composite film material and preparation method thereof.
Background technology
Traditional infrared stealth and camouflage mainly utilize low-emissivity material that the appearance profile of target is split to be out of shape and to reach stealthy object.Although the infrared stealth of this material to the passive target of static state can play certain effect, but to high-temperature targets and have thermal source target, as the engine etc. of aircraft engine nozzle, naval vessels, tank, effective infrared stealth cannot be implemented, its major cause is the design preparation of low-emissivity material is the difficult point of infrared stealth always, and current low-launch-rate can not accomplish very low level.Thus, reducing the core of infrared emittance is exactly search out to have excellent processing characteristics, low infrared emissivity material that structure is adjustable.
Authorization Notice No. is that the Chinese patent of CN101863152B discloses a kind of infrared radiation inhibiting material with nano periodic structure and preparation method thereof, and this kind of thin-film material is composited mutually by the composite Nano germanium in five cycles and zinc sulfide film.But this infrared radiation inhibiting material belongs to inorganic material.
Fluoro-containing copolymer film material is adjustable because have structure, variation, lightweight, density is low, advantages such as physical and chemical performance is unique and being widely used, publication number is that the Chinese patent application of CN102643544A discloses a kind of fluorinated polyimide infrared low-emissivity thin-film material and preparation method thereof, this material has good solvent resistance, thermostability, and higher optical property, it is a kind of rising infrared stealth novel material, its investigation and application has potential economic benefit and social benefit, good application prospect is had in military and civilian technology field.
Summary of the invention
Technical purpose of the present invention is the disclosed fluorinated polyimide film of Chinese invention patent application " a kind of fluorinated polyimide infrared low-emissivity thin-film material and preparation method thereof " of CN102643544A for publication number, the performance of further this film of raising, especially while keeping the performance such as heat-resisting, solvent resistant, printing opacity of this film, how to improve its infrared low-emissivity energy further, it is made to meet the requirements at the higher level of practical application, especially as the requirement of Infrared stealthy materials in military or civilian field.
The present inventor finds after further investigation with experimental verification: when introducing the nano-inorganic substance of certain content in this fluorinated polyimide infrared low-emissivity thin-film material, the interfacial interaction (as Van der Waals force, hydrogen bond, coordinate bond etc.) between the high-absorbable of this inorganics and polymeric system can be utilized to improve the over-all properties of material, especially improve its infrared low-emissivity energy.
Concrete technical scheme of the present invention is: a kind of fluorinated polyimide infrared low-emissivity laminated film, is made up of fluorinated polyimide and nano-inorganic substance; Described nano-inorganic substance is with crystalline phase particle disperse in fluorinated polyimide, and this nano inorganic amount accounts for 1% ~ 10% of this laminated film total mass; Described fluorinated polyimide has following general structure:
Wherein, polymerization degree n is 1 ~ 1000; R 1and/or R 2in comprise fluorine atom, and R 1be selected from the one in following structure:
R 2be selected from the one in following structure:
In technique scheme:
Described nano-inorganic substance is selected from but is not limited to one or more the mixture in nano titanium oxide, nano silicon, tin indium oxide (ITO), CNT (carbon nano-tube), nano zine oxide, nano zircite, polynite, nanometer sulfide etc.
As preferably, described nano inorganic amount accounts for 1% ~ 5% of this laminated film total mass, most preferably is 5%.
Present invention also offers a kind of method preparing above-mentioned fluorinated polyimide infrared low-emissivity laminated film, the method is specifically: by fluorinated polyimide film or fluorinated polyimide powder organic solvent dissolution or heat up and softeningly make fluid, then nano-inorganic substance powder is added, be stirred into dispersed system, be finally made into film.The method of described dispersed system film forming is not limit, and comprises casting method, rolling process, compression molding or evaporating solvent method.As preferably, described organic solvent is one or more the mixture in DMF (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetonitrile.
Wherein, the preparation method of fluorinated polyimide film with publication number for the preparation method of the thin-film material of fluorinated polyimide infrared low-emissivity disclosed in the Chinese invention patent of CN102643544A is identical, specific as follows:
Step 1: adopt following route A or route B synthesis containing 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer;
Route A:
(1) at N 2under protection, after appropriate (R)-or (S)-binaphthol, 4-nitro phthalic nitrile and salt of wormwood mixing, add enough anhydrous DMF, stirred at ambient temperature 15 ~ 30 hours, the mixture obtained pours suction filtration in enough dilute hydrochloric acid into, then be washed to neutrality with deionized water, with the mixed solvent recrystallization of methyl alcohol and acetonitrile, obtain intermediate compound one;
(2) appropriate intermediate compound one, sodium hydroxide, H is got 2o 2with water mixing after, at 40 ~ 80 DEG C stir 10 ~ 30 hours, reflux afterwards 30 ~ 60 hours, obtain white solid, suction filtration, with deionized water dilution after use concentrated hydrochloric acid acidifying, obtain intermediate compound two;
(3) getting appropriate intermediate compound two is dissolved in dimethylbenzene, and 100 ~ 250 DEG C are refluxed 1 ~ 10 hour, the solid cooled obtained, suction filtration, vacuum-drying, obtains containing 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer;
Route B:
(1) appropriate trimellitic anhydride chloride and pyridine are dissolved in sufficient toluene, obtain solution one; To (R)-or (S)-binaphthol be dissolved in toluene in right amount, obtain solution two; Slowly added in solution one by solution two and obtain mixing solutions, mixing solutions is slowly warming up to temperature of reaction, and Keep agitation obtains reaction soln;
(2) reaction soln is poured in enough normal hexanes separate out solid, washing, suction filtration, vacuum-drying, with the mixed solvent recrystallization of acetic anhydride and acetic acid, obtain containing 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer;
Step 2: what step 1 obtained contains 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol monomer and diamine monomer reacting by heating in organic solvent, by gained solution filter after on the sheet glass of cleaning plastic film mulch, then baking oven imidization is placed in, then in distilled water, soak demoulding, after drying, obtain fluorinated polyimide film.
In above-mentioned preparation method, described diamines is O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-(hexafluoro isopropyl) pentanoic, 4,4 '-(4,4 '-hexafluoro isopropyl phenylbenzene-1,1 '-dioxy) pentanoic, 4, the mixture of one or more diamines in 4 '-diaminobenzene anilide, quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine.
As preferably, the organic solvent in described step 2 is one or more the combination in DMF, DMAc, DMSO, acetonitrile.
As preferably, in described route B, mixing solutions is slowly warming up to temperature of reaction, Keep agitation 1 ~ 8 hour.
As preferably, the temperature of reaction in described route B is 50 ~ 100 DEG C, more preferably 70 ~ 90 DEG C
The preparation method of fluorinated polyimide powder with publication number for the preparation method of the thin-film material of fluorinated polyimide infrared low-emissivity disclosed in the Chinese invention patent of CN102643544A is substantially identical, uniquely unlike in step 2, carry out drying after being filtered by gained solution and obtain powder, but not on the sheet glass of cleaning film forming, namely this step 2 specifically: what step 1 obtained contains 1, 1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol monomer and diamine monomer reacting by heating in organic solvent, drying treatment is carried out after being filtered by gained solution, obtain fluorinated polyimide powder.
In sum, the nanometer organism of 1% ~ 10% is with the addition of in the fluorinated polyimide thin-film material that the patent that the present invention is CN102643544A at publication number provides, the interfacial interaction between the high-absorbable of this inorganics and fluorinated polyimide is utilized to improve the over-all properties of material, experiment confirms, add the thermostability of the matrix material after inorganics, environmental resistance, and its infrared low-emissivity can all increase, especially its infrared emittance reduction amplitude is larger, even can be reduced to former about 50%, therefore, it is possible to meet the requirement to the very high Infrared stealthy materials of stability requirement.In addition, this this fluorinated polyimide composite film material has the advantages such as film forming properties excellence, processing characteristics is superior, consistency is excellent, cost is few, therefore be a kind of rising infrared stealth novel material, its investigation and application has potential economic benefit and social benefit, has good application prospect in military and civilian technology field.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Comparative example 1:
The present embodiment is the comparative example of following examples 1-10.
In the present embodiment, fluorinated polyimide infrared low-emissivity film in embodiment 1 disclosed in the Chinese invention patent specification sheets that fluorinated polyimide film and preparation method thereof employing publication number is CN102643544A and preparation method thereof.That is, the structural formula of this fluorinated polyimide film is:
The preparation method of above-mentioned fluorinated polyimide film is as follows:
Step 1: adopt following reaction scheme one to synthesize 2,2 '-bis--(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3), specific as follows:
At N 2under protection, by (R)-of 2.86g or (S)-binaphthol, the 4-nitro phthalic nitrile of 3.82g and the K of 4.74g 2cO 3after mixing, add the anhydrous DMF of 30mL, stirred at ambient temperature 20 hours, the mixture obtained is poured in the dilute hydrochloric acid of 50mL2mol/L, suction filtration, neutrality is washed to deionized water, with the mixed solvent recrystallization of methyl alcohol and acetonitrile, obtained 2,2 '-bis--(3,4 '-dicyano phenoxy group)-1,1 '-naphthyl naphthalene (1).
Be the H of 30% by 2 of 5.39g, 2 '-bis--(3,4 '-dicyano phenoxy group)-1,1 '-naphthyl naphthalene (1), the sodium hydroxide of 8.0g, 10mL mass percent concentration 2o 2after the mixing of 50mL water, stir 12 hours at 80 DEG C.Reflux 48 hours afterwards, obtain white solid, suction filtration, after deionized water dilution, use concentrated hydrochloric acid acidifying, obtained 2,2 '-bis--(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene (2).
Get 2 of 6.14g, 2 '-bis--(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene (2) are dissolved in 10mL dimethylbenzene, 170 DEG C are refluxed 3 hours, the solid cooled obtained, suction filtration, vacuum-drying, obtained 2,2 '-bis--(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3).
Reaction scheme one:
Step 2: adopt following reaction scheme two to prepare fluorinated polyimide film, be specially:
At N 2under protection; by 4 of 0.274g; 4 '-(hexafluoro isopropyl) pentanoic is dissolved in the DMAc of anhydrous 4mL; then slowly join 0.5785g step 1 obtained 2; in 2 '-bis--(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3); heated and stirred 12 hours, obtains the liquid of thickness.By liquid through strainer filtering, vacuumize bubble removing, plastic film mulch on the sheet glass of cleaning, be then placed in baking oven imidization.From baking oven, take out sheet glass, soak half an hour in distilled water after, carry out demoulding, dry and obtain fluorinated polyimide film.
Reaction scheme two:
After measured, the second-order transition temperature of the above-mentioned fluorinated polyimide film prepared is 250 DEG C, heat decomposition temperature 280 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.483.
Embodiment 1:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, and wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in comparative example 1, is:
ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in comparative example 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide film 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 280 DEG C, heat decomposition temperature 297 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.33.
Embodiment 2:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, and wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1.ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide film 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 285 DEG C, heat decomposition temperature 300 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.40.
Embodiment 3:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 273 DEG C, heat decomposition temperature 290 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.38.
Embodiment 4:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 295 DEG C, heat decomposition temperature 312 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.22.
Embodiment 5:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 290 DEG C, heat decomposition temperature 300 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.34.
Embodiment 6:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 300 DEG C, heat decomposition temperature 320 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.43.
Embodiment 7:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 290 DEG C, heat decomposition temperature 320 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.47.
Embodiment 8:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 288 DEG C, heat decomposition temperature 315 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.41.
Embodiment 9:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 280 DEG C, heat decomposition temperature 300 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.45.
Embodiment 10:
In the present embodiment, the composition structure of infrared low transmitting laminated film is identical with the composition structure of the infrared low transmitting laminated film in embodiment 1.
The preparation method of above-mentioned laminated film is as follows:
(1) Kapton powder is prepared
This method preparing Kapton powder is basic substantially identical with the preparation method of the fluorinated polyimide film in comparative example 1, uniquely unlike in step (1), carry out drying after being filtered by gained solution and obtain powder, but not on the sheet glass of cleaning film forming, namely this step 2 specifically: what step 1 obtained contains 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol monomer and diamine monomer reacting by heating in organic solvent, carry out drying treatment after being filtered by gained solution, obtain fluorinated polyimide powder.
(2) getting fluorinated polyimide powder 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the average infrared emittance of the second-order transition temperature of the above-mentioned laminated film prepared, heat decomposition temperature and 8 ~ 14 mu m wavebands is all substantially the same manner as Example 1.
Comparative example 2:
The present embodiment is the comparative example of following examples 11-19.
In the present embodiment, fluorinated polyimide infrared low-emissivity film in embodiment 3 disclosed in the Chinese invention patent specification sheets that fluorinated polyimide film and preparation method thereof employing publication number is CN102643544A and preparation method thereof, that is, the structural formula of this fluorinated polyimide film is:
Its preparation method specifically refers to the Chinese invention patent specification sheets that publication number is CN102643544A.
After measured, the second-order transition temperature of the above-mentioned fluorinated polyimide film prepared is 250 DEG C, heat decomposition temperature 280 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.584.
Embodiment 11:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, and wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in comparative example 3, is:
ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in comparative example 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide film 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 290 DEG C, heat decomposition temperature 306 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.38.
Embodiment 12:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, and wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1.ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide film 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 300 DEG C, heat decomposition temperature 328 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.47.
Embodiment 13:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 282 DEG C, heat decomposition temperature 300 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.43.
Embodiment 14:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 296 DEG C, heat decomposition temperature 330 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.25.
Embodiment 15:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 290 DEG C, heat decomposition temperature 320 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.38.
Embodiment 16:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 311 DEG C, heat decomposition temperature 348 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.46.
Embodiment 17:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 308 DEG C, heat decomposition temperature 340 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.52.
Embodiment 18:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 296 DEG C, heat decomposition temperature 320 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.42.
Embodiment 19:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 285 DEG C, heat decomposition temperature 305 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.48.
Comparative example 3:
The present embodiment is the comparative example of following examples 20-28.
In the present embodiment, fluorinated polyimide infrared low-emissivity film in embodiment 4 disclosed in the Chinese invention patent specification sheets that fluorinated polyimide film and preparation method thereof employing publication number is CN102643544A and preparation method thereof, that is, the structural formula of this fluorinated polyimide film is:
Its preparation method specifically refers to the Chinese invention patent specification sheets that publication number is CN102643544A.
After measured, the second-order transition temperature of the above-mentioned fluorinated polyimide film prepared is 260 DEG C, heat decomposition temperature 290 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.697.
Embodiment 20:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, and wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in comparative example 4, is:
ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in comparative example 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide film 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 305 DEG C, heat decomposition temperature 330 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.41.
Embodiment 21:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, and wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1.ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide film 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 320 DEG C, heat decomposition temperature 347 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.52.
Embodiment 22:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and ITO, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, ITO in fluorinated polyimide film-forming resin, forms heterogeneous solid film with crystalline phase particle disperse; The mass ratio of fluorinated polyimide and ITO is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds ITO in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and ITO is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 288 DEG C, heat decomposition temperature 305 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.49.
Embodiment 23:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 310 DEG C, heat decomposition temperature 340 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.30.
Embodiment 24:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 300 DEG C, heat decomposition temperature 335 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.40.
Embodiment 25:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and CNT (carbon nano-tube), wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, CNT (carbon nano-tube) is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds CNT (carbon nano-tube) in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and CNT (carbon nano-tube) is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 325 DEG C, heat decomposition temperature 358 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.43.
Embodiment 26:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9:1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9:1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 310 DEG C, heat decomposition temperature 338 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.60.
Embodiment 27:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9.5:0.5.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9.5:0.5, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 298 DEG C, heat decomposition temperature 322 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.49.
Embodiment 28:
In the present embodiment, infrared low transmitting laminated film is made up of fluorinated polyimide film and nano zine oxide, wherein the structural formula of fluorinated polyimide is identical with the structural formula of the fluorinated polyimide film in embodiment 1, nano zine oxide is dispersed in fluorinated polyimide film-forming resin, forms heterogeneous solid film; The mass ratio of fluorinated polyimide and nano zine oxide is 9.9:0.1.
The preparation method of above-mentioned laminated film is as follows:
(1) preparation method in embodiment 1 is utilized to prepare fluorinated polyimide film;
(2) getting fluorinated polyimide 8g is dissolved in 150mLDMAc organic solvent, adds nano zine oxide in gained clear liquor, and wherein the mass ratio of fluorinated polyimide and nano zine oxide is 9.9:0.1, and sonic oscillation makes suspension liquid in 20 minutes; Then, by this suspension liquid on a glass curtain coating, dry into from suspension type film; Finally, take film after keeping half an hour in 40 DEG C of air dry ovens, thickness is 20 μm ~ 100 μm, and film quality is soft, and arbitrarily angled convolution does not ftracture.Deposit 2 days under air atmosphere after, its outward appearance is without considerable change.
After measured, the second-order transition temperature of the above-mentioned laminated film prepared is 290 DEG C, heat decomposition temperature 310 DEG C, and the average infrared emittance of 8 ~ 14 mu m wavebands is 0.53.

Claims (10)

1. a fluorinated polyimide infrared low-emissivity laminated film, is characterized in that: be made up of fluorinated polyimide and nano-inorganic substance; Described nano-inorganic substance is with crystalline phase particle disperse in fluorinated polyimide, and this nano inorganic amount accounts for 1% ~ 10% of this laminated film total mass; Described fluorinated polyimide has following general structure:
Wherein, polymerization degree n is 1 ~ 1000; R 1and/or R 2in comprise fluorine atom, and R 1be selected from the one in following structure:
R 2be selected from the one in following structure:
2. fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 1, is characterized in that: described nano-inorganic substance is one or more the mixture in nano titanium oxide, nano silicon, tin indium oxide, CNT (carbon nano-tube), nano zine oxide, nano zircite, polynite, nanometer sulfide.
3. fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 1 or 2, is characterized in that: described nano inorganic amount accounts for 1% ~ 5% of this laminated film total mass.
4. fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 3, is characterized in that: described nano inorganic amount accounts for 5% of this laminated film total mass.
5. the preparation method of fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 1 or 2, it is characterized in that: by described fluorinated polyimide film or fluorinated polyimide powder organic solvent dissolution or heat up and softeningly make fluid, then nano-inorganic substance powder is added, be stirred into dispersed system, be finally made into film.
6. the preparation method of fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 5, is characterized in that: method dispersed system being made film comprises casting method, rolling process, compression molding or evaporating solvent method.
7. the preparation method of fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 5, it is characterized in that: described organic solvent is N, one or more mixture in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetonitrile.
8. the preparation method of fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 5, is characterized in that: described fluorinated polyimide film or the preparation method of fluorinated polyimide powder specific as follows:
Step 1: adopt following route A or route B synthesis containing 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer;
Route A:
(1) at N 2under protection, after appropriate (R)-or (S)-binaphthol, 4-nitro phthalic nitrile and salt of wormwood mixing, add enough anhydrous DMF, stirred at ambient temperature 15 ~ 30 hours, the mixture obtained pours suction filtration in enough dilute hydrochloric acid into, then be washed to neutrality with deionized water, with the mixed solvent recrystallization of methyl alcohol and acetonitrile, obtain intermediate compound one;
(2) appropriate intermediate compound one, sodium hydroxide, H is got 2o 2with water mixing after, at 40 ~ 80 DEG C stir 10 ~ 30 hours, reflux afterwards 30 ~ 60 hours, obtain white solid, suction filtration, with deionized water dilution after use concentrated hydrochloric acid acidifying, obtain intermediate compound two;
(3) getting appropriate intermediate compound two is dissolved in dimethylbenzene, and 100 ~ 250 DEG C are refluxed 1 ~ 10 hour, the solid cooled obtained, suction filtration, vacuum-drying, obtains containing 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer;
Route B:
(1) appropriate trimellitic anhydride chloride and pyridine are dissolved in sufficient toluene, obtain solution one; To (R)-or (S)-binaphthol be dissolved in toluene in right amount, obtain solution two; Slowly added in solution one by solution two and obtain mixing solutions, mixing solutions is slowly warming up to temperature of reaction, and Keep agitation obtains reaction soln;
(2) reaction soln is poured in enough normal hexanes separate out solid, washing, suction filtration, vacuum-drying, with the mixed solvent recrystallization of acetic anhydride and acetic acid, obtain containing 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer;
Step 2: what step 1 obtained contains 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol monomer and diamine monomer reacting by heating in organic solvent, by gained solution filter after on the sheet glass of cleaning plastic film mulch, then baking oven imidization is placed in, then in distilled water, soak demoulding, after drying, obtain fluorinated polyimide film; Or what step 1 obtained contains 1, the dianhydride monomer of 1 '-dinaphthalene-2,2 '-diphenol monomer and diamine monomer reacting by heating in organic solvent, drying treatment after being filtered by gained solution, obtains fluorinated polyimide powder.
9. the preparation method of fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 8, it is characterized in that: described diamines is O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-(hexafluoro isopropyl) pentanoic, 4,4 '-(4,4 '-hexafluoro isopropyl phenylbenzene-1,1 '-dioxy) pentanoic, 4, the mixture of one or more diamines in 4 '-diaminobenzene anilide, quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine.
10. the preparation method of fluorinated polyimide infrared low-emissivity laminated film as claimed in claim 8, is characterized in that: the organic solvent in described step 2 is one or more the combination in DMF, DMAc, DMSO, acetonitrile.
CN201310552583.4A 2013-11-08 2013-11-08 Fluorine-containing polyimide composite film material with low infrared emissivity and preparation method thereof Pending CN104629362A (en)

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CN105218435A (en) * 2015-10-12 2016-01-06 吉林大学 2,2-bis-[5-amino-2-pyridyloxy]-1,1-dinaphthalene and preparation method thereof
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CN110643041A (en) * 2019-10-23 2020-01-03 合肥中汇睿能能源科技有限公司 Colorless transparent polyimide film with adjustable refractive index and preparation method thereof
WO2022270367A1 (en) * 2021-06-22 2022-12-29 三菱瓦斯化学株式会社 Thermoplastic resin and optical lens including same
CN115504907A (en) * 2022-09-15 2022-12-23 河北工业大学 Phthalonitrile monomer containing binaphthyl structure and resin thereof
CN115504907B (en) * 2022-09-15 2023-11-17 河北工业大学 Phthalonitrile monomer containing binaphthyl structure and resin thereof
CN118006205A (en) * 2024-02-28 2024-05-10 安徽大汗建设有限责任公司 Infrared stealth coating and preparation method thereof

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