CN102643544B - Fluorine-containing polyimide infrared low-emissivity thin film material and preparation method thereof - Google Patents
Fluorine-containing polyimide infrared low-emissivity thin film material and preparation method thereof Download PDFInfo
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- CN102643544B CN102643544B CN2012100603052A CN201210060305A CN102643544B CN 102643544 B CN102643544 B CN 102643544B CN 2012100603052 A CN2012100603052 A CN 2012100603052A CN 201210060305 A CN201210060305 A CN 201210060305A CN 102643544 B CN102643544 B CN 102643544B
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- 0 CC(C1)C(Oc2ccc(cccc3)c3c2-c2c(cccc3)c3ccc2Oc(cc2)cc(C(N3c(cc4)ccc4Oc4ccc(C(C(F)(F)F)(C(F)(F)F)c(cc5)ccc5Oc5ccc(C(C)(*)*)cc5)cc4)=O)c2C3=O)=CC(C(N2C(C)(*)*)=O)=C1C2=O Chemical compound CC(C1)C(Oc2ccc(cccc3)c3c2-c2c(cccc3)c3ccc2Oc(cc2)cc(C(N3c(cc4)ccc4Oc4ccc(C(C(F)(F)F)(C(F)(F)F)c(cc5)ccc5Oc5ccc(C(C)(*)*)cc5)cc4)=O)c2C3=O)=CC(C(N2C(C)(*)*)=O)=C1C2=O 0.000 description 1
Abstract
The invention discloses a fluorine-containing polyimide infrared low-emissivity thin film material and a preparation method thereof. The thin film material is prepared through polymerization by using diamine and dianhydride which is synthesized by R-shaped or S-shaped 1, 1'-binaphthyl-2, 2'-diphenol monomers. A binaphthyl group is introduced into fluorine-containing polyimide formed in a polyimide chain. The thermal stability is good, the chain structure is adjustable, the crystallization performance is good, the solvent resistance is good and the average infrared emissivity at an 8-14mum band is 0.30-0.70. Therefore, the fluorine-containing polyimide infrared low-emissivity thin film material can be used as a high-performance novel infrared stealth material and the application prospect in the technical field of military use and civil use is better.
Description
Technical field
The invention belongs to the macromolecule membrane technical field, be specifically related to a kind of fluorinated polyimide infrared low-emissivity thin-film material and preparation method thereof, can be used as the infrared stealth material and be applied to military or civil area.
Background technology
Stealth material is the key of stealthy technique, is the indispensable basic substance of stealthy weapon, and each developed country of the world all gives primary study and exploitation.Wherein, infrared stealth require to reduce the infrared intensity of target, is all generally by cooling, infraredly blocks, with the low infrared emissivity coating, realizes.The material that is used for infrared stealth generally should have low infrared emittance or stronger temperature control ability, has rational surface tissue and lower solar absorptance, can be compatible with other wave band.The new infrared stealth material that research and comparison is many at present mainly contains conductive polymers, inorganic nano film, ultramicron, strong magnetic material, semiconductor material etc.Be difficult to be reduced to the limit of requirement due to the temperature difference between target and background, so the infrared emittance of regulating the Stealthy Target surface is an effective means.The core that reduces infrared emittance be exactly search out have excellent processing characteristics, low infrared emissivity material that structure is adjustable.
Publication number is that the Chinese patent application of CN101863152A discloses a kind of nano periodic structure infrared low-emissivity thin-film material, and this kind thin-film material is composited mutually by composite Nano germanium and the zinc sulfide film in five cycles.Publication number is silicon carbide infrared stealth material and the preparation technology thereof that the Chinese patent application of CN1657585A discloses a kind of coated with barium ferrite film.Publication number is that the Chinese patent application of CN1552660A discloses a kind of indium tin oxide films and preparation method who has low-launch-rate at infrared band.The low infrared emissivity materials'use that these patent applications relate to be all inorganics, seldom relate to and utilize the organic polymer thin film material to prepare infrared low-emissivity material.
Organic polymer thin film is widely used because having the advantages such as structure is adjustable, diversified, lightweight, density is low, physical and chemical performance is unique, and wherein fluoro-containing copolymer film is the novel high polymer mould material that development in recent years is got up.On structure, fluorine element is introduced in polymkeric substance, can effectively improve its optical transparence and solubility, reduce specific inductivity, and do not sacrifice its good thermal characteristics.
Summary of the invention
Technical purpose of the present invention is the state of the art for existing infrared low-emissivity material, and a kind of fluorinated polyimide infrared low-emissivity thin-film material and preparation method thereof is provided.This thin-film material has good thermostability, adjustable chain structure, good crystal property and good solvent resistance, can have as infrared band the material of low-launch-rate, is used for the technical fields such as polymeric substrates of infrared stealth material.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: a kind of fluorinated polyimide infrared low-emissivity thin-film material, and its general structure is:
Wherein, polymerization degree n is 1～1000; R
1And/or R
2In comprise fluorine atom, and R
1Be selected from a kind of in following structure:
R
2Be selected from a kind of in following structure:
In technique scheme:
As preferably, described fluorinated polyimide infrared low-emissivity thin-film material is 0.30～0.70 in the average infrared emittance of 8～14 mu m wavebands, more preferably 0.40～0.60.
As preferably, the glass transition temp of described fluorinated polyimide infrared low-emissivity thin-film material is greater than 200 ℃, more preferably 220～240 ℃.
As preferably, the heat decomposition temperature of described fluorinated polyimide infrared low-emissivity thin-film material is greater than 250 ℃, more preferably 270～300 ℃.
The preparation method of a kind of fluorinated polyimide infrared low-emissivity of the present invention thin-film material is: fluorine-containing polyimide film adopts three-step approach to synthesize,
Step 1: adopt following route A or route B to synthesize and contain 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol;
Route A:
(1) at N
2Under protection, will appropriate (R)-or after (S)-binaphthol, 4-nitro phthalic nitrile and salt of wormwood mixes, add enough anhydrous DMF, stirred under room temperature 15～30 hours, the mixture that obtains is poured suction filtration in enough dilute hydrochloric acid into, then be washed to neutrality with deionized water, the mixed solvent recrystallization with methyl alcohol and acetonitrile, obtain intermediate compound one;
(2) get appropriate intermediate compound one, sodium hydroxide, H
2O
2After mixing with water, stirred 10～30 hours under 40～80 ℃, refluxed afterwards 30～60 hours, obtain white solid, suction filtration, with using the concentrated hydrochloric acid acidifying after the deionized water dilution, obtain intermediate compound two;
(3) get appropriate intermediate compound two and be dissolved in dimethylbenzene, 100～250 ℃ were refluxed 1～10 hour, and the solid cooled that obtains, suction filtration, vacuum-drying, obtain containing 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol;
Route B:
(1) appropriate trimellitic anhydride chloride and pyridine are dissolved in enough toluene, obtain solution one; Will appropriate (R)-or (S)-binaphthol be dissolved in toluene, obtain solution two; Solution two is slowly added in solution one and obtains mixing solutions, mixing solutions slowly is warming up to temperature of reaction, lasting stirring obtains reaction soln;
(2) reaction soln is poured in enough normal hexanes and separated out solid, washing, suction filtration, vacuum-drying, the mixed solvent recrystallization with acetic anhydride and acetic acid, obtain containing 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol;
Step 2: with what step 1 obtained, contain 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol and diamine monomer reacting by heating in organic solvent, with after the gained solution filter on the sheet glass of cleaning plastic film mulch, then be placed in the baking oven imidization, then soak demoulding in distilled water, obtain the fluorinated polyimide film after drying.
In above-mentioned preparation method, described diamines is O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-(hexafluoro sec.-propyl) pentanoic, 4,4 '-(4,4 '-hexafluoro isopropyl diphenyl base-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 described in second step is one or more the combination in DMF, DMAc, DMSO, acetonitrile.
As preferably, in described route B, mixing solutions slowly is warming up to temperature of reaction, continue to stir 1～8 hour.
As preferably, the temperature of reaction in described route B is 50～100 ℃, more preferably 70～90 ℃
Compared with prior art, fluorinated polyimide infrared low-emissivity thin-film material of the present invention has following features:
(1) the dinaphthalene group is introduced in the polyimide chain, formed stable fluorinated polyimide.This type of polymer thermostable and conformational stability are excellent, can be applicable to the infrared stealth material very high to stability requirement.
(2) select diamines allocate and optimize.By structure design, the capable of regulating polymer architecture, and then reach the purpose of regulation and control polymer chain structure and polymkeric substance infrared emittance.
(3) this fluorinated polyimide thin-film material has the advantages such as film forming properties excellence, processing characteristics is superior, density is low, cost is few.
Therefore, fluorinated polyimide thin-film material processing characteristics of the present invention is superior, cost is low, have good solvent resistance, good thermostability and conformational stability, higher optical property, the substrate that not only can be used as infrared low-emissivity material is used, and can be directly as the infrared stealth materials'use, it is a kind of rising infrared stealth novel material, its research and application have potential economic benefit and social benefit, in military and civilian technology field, application prospect are preferably arranged.
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 it is not played any restriction effect.
Embodiment 1:
In the present embodiment, the structural formula of fluorinated polyimide infrared low-emissivity thin-film material is:
The preparation method of above-mentioned fluorinated polyimide infrared low-emissivity thin-film material is as follows:
Step 1: adopt synthetic 2,2 '-two-(3,4 '-di carboxyl phenyloxy)-1 of following reaction scheme one, 1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3), specific as follows:
At N
2Under protection, with 2.86g (R)-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 20 hours under room temperature, the mixture that obtains is poured in the dilute hydrochloric acid of 50mL2mol/L, suction filtration, be washed to neutrality with deionized water,, with the mixed solvent recrystallization of methyl alcohol and acetonitrile, make 2,2 '-two-(3,4 '-dicyano phenoxy group)-1,1 '-naphthyl naphthalene (1).
With 2,2 ' of 5.39g-two-(3,4 '-dicyano phenoxy group)-1, the sodium hydroxide of 1 '-naphthyl naphthalene (1), 8.0g, 10mL mass percent concentration are 30% H
2O
2After mixing with 50mL water, stirred 12 hours under 80 ℃.Refluxed afterwards 48 hours, and obtained white solid, suction filtration, after the deionized water dilution, use the concentrated hydrochloric acid acidifying, makes 2,2 '-two-(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene (2).
Get 2 of 6.14g, 2 '-two-(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene (2) is dissolved in 10mL dimethylbenzene, 170 ℃ were refluxed 3 hours, the solid cooled that obtains, suction filtration, vacuum-drying, make 2,2 '-two-(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 the fluorinated polyimide film, be specially:
At N
2Under protection; with 4 of 0.274g; 4 '-(hexafluoro sec.-propyl) pentanoic is dissolved in the DMAc of anhydrous 4mL; then join slowly that 0.5785g step 1 makes 2; 2 '-two-(3,4 '-di carboxyl phenyloxy)-1, in 1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3); heated and stirred 12 hours, obtain the liquid of thickness.Liquid, through strainer filtering, is vacuumized bubble removing, and plastic film mulch on the sheet glass of cleaning, then be placed in the baking oven imidization.Take out sheet glass from baking oven, soak half an hour in distilled water after, carry out demoulding, dry and obtain the fluorinated polyimide film.
After measured, the second-order transition temperature of the above-mentioned fluorinated polyimide film for preparing is 250 ℃, 280 ℃ of heat decomposition temperatures, and the average infrared emittance of 8～14 mu m wavebands is 0.483.
Reaction scheme two:
Embodiment 2:
In the present embodiment, the structural formula of fluorinated polyimide infrared low-emissivity thin-film material is:
The preparation method of above-mentioned fluorinated polyimide infrared low-emissivity thin-film material is as follows:
Step 1: adopt synthetic 2,2 '-two-(3,4 '-di carboxyl phenyloxy)-1 of following reaction scheme one, 1 '-naphthyl naphthalene-dicarboxylic anhydride-dibasic acid esters acid anhydride (5), specific as follows:
16.18g trimellitic anhydride chloride and 6.2mL pyridine are dissolved in 50mL toluene, obtain solution one; With 10.00g (R)-or (S)-binaphthol be dissolved in 50mL toluene, obtain solution two; Solution two is slowly added in solution one, mixing solutions slowly is warming up to 80 ℃, continue to stir 4 hours.Mixing solutions is poured in the normal hexane of q.s after reaction, separates out solid, wash suction filtration 2 times, vacuum-drying, the mixed solvent recrystallization of use acetic anhydride and acetic acid 2 times, obtain 2,2 '-two-(3,4 '-di carboxyl phenyloxy)-1,1 '-naphthyl naphthalene-dicarboxylic anhydride-dibasic acid esters acid anhydride (5).
Reaction scheme one:
Step 2: adopt following reaction scheme two to prepare the fluorinated polyimide film, be specially:
At N
2Under protection; with 0.274g4; 4 '-(hexafluoro sec.-propyl) pentanoic is dissolved in anhydrous 4mL DMAc; then join slowly that 0.6345g step 1 makes 2; 2 '-two-(3,4 '-di carboxyl phenyloxy)-1, in 1 '-naphthyl naphthalene-dicarboxylic anhydride-dibasic acid esters acid anhydride (5); heated and stirred 12 hours, obtain the liquid of thickness.Liquid, through strainer filtering, is vacuumized bubble removing, and plastic film mulch on the sheet glass of cleaning, then be placed in the baking oven imidization.Take out sheet glass from baking oven, soak half an hour in distilled water after, carry out demoulding, dry and obtain the fluorinated polyimide film.
After measured, 260 ℃ of the above-mentioned fluorinated polyimide film glass transition temperatures for preparing, 290 ℃ of heat decomposition temperatures, the average infrared emittance of 8～14 mu m wavebands is 0.575.
Reaction scheme two:
Embodiment 3:
In the present embodiment, the structural formula of fluorinated polyimide infrared low-emissivity thin-film material is:
The preparation method of above-mentioned fluorinated polyimide infrared low-emissivity thin-film material is as follows:
Step 1: adopt and synthetic 2,2 '-two-(3,4 '-di carboxyl phenyloxy)-1 of the identical reaction scheme one of embodiment 1,1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3), specifically see also the step 1 of implementing in 1.
Step 2: adopt following reaction scheme two to prepare the fluorinated polyimide film, be specially:
At N
2Under protection; with 0.428g4; 4 '-(4,4 '-hexafluoro isopropyl diphenyl base-1,1 '-dioxy) pentanoic is dissolved in anhydrous 4mL DMAc; then join slowly that 0.5785g step 1 makes 2; 2 '-two-(3,4 '-di carboxyl phenyloxy)-1, in 1 '-naphthyl naphthalene-dicarboxylic anhydride-bis ether acid anhydride (3); heated and stirred 12 hours, obtain the liquid of thickness.This liquid, through strainer filtering, is vacuumized bubble removing, and plastic film mulch on the sheet glass of cleaning, then be placed in the baking oven imidization.Take out sheet glass from baking oven, soak half an hour in distilled water after, carry out demoulding, dry and obtain the fluorinated polyimide film.
After measured, 250 ℃ of the second-order transition temperatures of this fluorinated polyimide film, 280 ℃ of heat decomposition temperatures, the average infrared emittance of 8～14 mu m wavebands is 0.584.
Reaction scheme two:
Embodiment 4:
In the present embodiment, the structural formula of fluorinated polyimide infrared low-emissivity thin-film material is:
The preparation method of above-mentioned fluorinated polyimide infrared low-emissivity thin-film material is as follows:
Step 1: adopt and synthetic 2,2 '-two-(3,4 '-di carboxyl phenyloxy)-1 of the identical reaction scheme one of embodiment 2,1 '-naphthyl naphthalene-dicarboxylic anhydride-dibasic acid esters acid anhydride (5), specifically see also the step 1 of implementing in 2.
Step 2: adopt following reaction scheme two to prepare the fluorinated polyimide film, be specially:
At N
2Under protection; with 0.428g4; 4 '-(4,4 '-hexafluoro isopropyl diphenyl base-1,1 '-dioxy) pentanoic is dissolved in anhydrous 4mL DMAc; then join slowly that 0.6345g step 1 makes 2; 2 '-two-(3,4 '-di carboxyl phenyloxy)-1, in 1 '-naphthyl naphthalene-dicarboxylic anhydride-dibasic acid esters acid anhydride (5); heated and stirred 12 hours, obtain the liquid of thickness.This liquid, through strainer filtering, is vacuumized bubble removing, and plastic film mulch on the sheet glass of cleaning, then be placed in the baking oven imidization.Take out sheet glass from baking oven, soak half an hour in distilled water after, carry out demoulding, dry and obtain the fluorinated polyimide film.
After measured, 260 ℃ of the second-order transition temperatures of the above-mentioned fluorinated polyimide film for preparing, 290 ℃ of heat decomposition temperatures, the average infrared emittance of 8～14 mu m wavebands is 0.697.
Reaction scheme two:
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any modifications of making in principle scope of the present invention, supplement or similar fashion substitutes etc., within all should being included in protection scope of the present invention.
Claims (11)
1. fluorinated polyimide infrared low-emissivity thin-film material, it is characterized in that: its general structure is:
Wherein, polymerization degree n is 1～1000; R
1And/or R
2In comprise fluorine atom, and R
1Be selected from a kind of in following structure:
R
2Be selected from a kind of in following structure:
2. fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 1, it is characterized in that: the average infrared emittance of 8～14 mu m wavebands is 0.30～0.70.
3. fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 1, it is characterized in that: the average infrared emittance of 8～14 mu m wavebands is 0.45～0.60.
4. fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 1, it is characterized in that: glass transition temp is greater than 200 ℃.
5. fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 1, it is characterized in that: heat decomposition temperature is greater than 250 ℃.
6. fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 4, it is characterized in that: described glass transition temp is 220～240 ℃.
7. fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 5, it is characterized in that: described heat decomposition temperature is 270～300 ℃.
8. the preparation method of fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 1, is characterized in that: comprise the steps:
Step 1: adopt following route A or route B to synthesize and contain 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol;
Route A:
(1) at N
2Under protection, will appropriate (R)-or after (S)-binaphthol, 4-nitro phthalic nitrile and salt of wormwood mixes, add enough anhydrous DMF, stirred under room temperature 15～30 hours, the mixture that obtains is poured suction filtration in enough dilute hydrochloric acid into, then be washed to neutrality with deionized water, the mixed solvent recrystallization with methyl alcohol and acetonitrile, obtain intermediate compound one;
(2) get appropriate intermediate compound one, sodium hydroxide, H
2O
2After mixing with water, stirred 10～30 hours under 40～80 ℃, refluxed afterwards 30～60 hours, obtain white solid, suction filtration, with using the concentrated hydrochloric acid acidifying after the deionized water dilution, obtain intermediate compound two;
(3) get appropriate intermediate compound two and be dissolved in dimethylbenzene, 100～250 ℃ were refluxed 1～10 hour, and the solid cooled that obtains, suction filtration, vacuum-drying, obtain containing 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol;
Route B:
(1) appropriate trimellitic anhydride chloride and pyridine are dissolved in enough toluene, obtain solution one; Will appropriate (R)-or (S)-binaphthol be dissolved in toluene, obtain solution two; Solution two is slowly added in solution one and obtains mixing solutions, mixing solutions slowly is warming up to temperature of reaction, lasting stirring obtains reaction soln;
(2) reaction soln is poured in enough normal hexanes and separated out solid, washing, suction filtration, vacuum-drying, the mixed solvent recrystallization with acetic anhydride and acetic acid, obtain containing 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol;
Step 2: with what step 1 obtained, contain 1,1 '-dinaphthalene-2, the dianhydride monomer of 2 '-diphenol and diamine monomer reacting by heating in organic solvent, with after the gained solution filter on the sheet glass of cleaning plastic film mulch, then be placed in the baking oven imidization, then soak demoulding in distilled water, obtain the fluorinated polyimide film after drying.
9. the preparation method of fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 8, it is characterized in that: described diamines is O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-(hexafluoro sec.-propyl) pentanoic, 4,4 '-(4,4 '-hexafluoro isopropyl diphenyl base-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 thin-film material 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.
11. the preparation method of fluorinated polyimide infrared low-emissivity thin-film material as claimed in claim 8 is characterized in that: in described route B, temperature of reaction is 50～100 ℃.
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| CN110483771A (en) * | 2019-08-12 | 2019-11-22 | 天津理工大学 | A kind of purposes of polyimide resin and its synthetic method and the resin film based on binaphthalene ether skeleton structure |
| CN111363148B (en) * | 2020-03-26 | 2022-08-23 | 天津理工大学 | Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation |
| KR20240022455A (en) * | 2021-06-22 | 2024-02-20 | 미츠비시 가스 가가쿠 가부시키가이샤 | Thermoplastic resin and optical lens containing the same |
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