CN104356647B - A kind of crown ether modified polyimide hybridized film and preparation method thereof - Google Patents
A kind of crown ether modified polyimide hybridized film and preparation method thereof Download PDFInfo
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- CN104356647B CN104356647B CN201410612335.9A CN201410612335A CN104356647B CN 104356647 B CN104356647 B CN 104356647B CN 201410612335 A CN201410612335 A CN 201410612335A CN 104356647 B CN104356647 B CN 104356647B
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- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 61
- 229920001721 Polyimide Polymers 0.000 title claims abstract description 58
- 239000004642 Polyimide Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 229920002647 polyamide Polymers 0.000 claims abstract description 7
- 239000011528 polyamide (building material) Substances 0.000 claims abstract description 6
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 47
- 238000001291 vacuum drying Methods 0.000 claims description 26
- YSSSPARMOAYJTE-UHFFFAOYSA-N Dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003379 elimination reaction Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N M-Phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 7
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-Methylenedianiline Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N BPDA Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4,4'-Oxydianiline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-M 2-methylpropanimidate Chemical compound CC(C)C([O-])=N WFKAJVHLWXSISD-UHFFFAOYSA-M 0.000 claims description 2
- AAPZMJNYFJUWHR-UHFFFAOYSA-N 4-propan-2-yl-2-benzofuran-1,3-dione Chemical compound CC(C)C1=CC=CC2=C1C(=O)OC2=O AAPZMJNYFJUWHR-UHFFFAOYSA-N 0.000 claims description 2
- VACCAVUAMIDAGB-UHFFFAOYSA-N Sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000006159 dianhydride group Chemical group 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 37
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005755 formation reaction Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 18
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- GTIBIXIJABCLPL-NTEUORMPSA-N (E)-2-diazonio-1-[[3-(pyridin-2-yldisulfanyl)phenyl]methoxy]ethenolate Chemical compound N#[N+]\C=C(/[O-])OCC1=CC=CC(SSC=2N=CC=CC=2)=C1 GTIBIXIJABCLPL-NTEUORMPSA-N 0.000 description 5
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000006011 modification reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- -1 DMAc Chemical compound 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N Phosphorus pentoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- PMTMAFAPLCGXGK-JMTMCXQRSA-N (15Z)-12-oxophyto-10,15-dienoic acid Chemical compound CC\C=C/C[C@H]1[C@@H](CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-JMTMCXQRSA-N 0.000 description 1
- AIIPIXSXYANFAP-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1=CC(C)(N)C(N)C(C)=C1 AIIPIXSXYANFAP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241000662429 Fenerbahce Species 0.000 description 1
- 229920002521 Macromolecule Polymers 0.000 description 1
- 101700021732 OPR Proteins 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
Abstract
The invention discloses a kind of crown ether modified polyimide hybridized film and preparation method thereof, the method in humidity less than 50%, under room temperature, mechanical agitation, in nitrogen atmosphere, crown ether and aromatic diamine are dissolved in polar organic solvent, after being completely dissolved to crown ether and aromatic diamine, continue stirring and obtain crown ether/diamidogen inclusion complex in solution；Crown ether/diamidogen inclusion complex in solution adds aromatic dianhydride, after aromatic dianhydride adds, continues stirring, obtain crown ether modified polyamide acid solution；By crown ether modified polyamide acid solution uniform application in clean glass sheet, eliminate bubble；Heat up by setup program, be disposed after be cooled to room temperature, demoulding, be dried, obtain crown ether modified polyimide hybridized film.Crown ether molecule of the present invention is enclosed within polyamic acid chain formation Necklet-type supramolecular structure, and polyimide molecule chain is three-dimensional by two-dimensional expansion, and strand compliance reduces, and rigidity gets a promotion.
Description
Technical field
The present invention relates to Kapton and preparation method thereof, be specifically related to a kind of crown ether modified polyimide hybridized film and
Preparation method, belongs to high-molecular organic material technical field of modification.
Technical background
Polyimides (PI) is a kind of special engineering plastics, has superior high and low temperature resistance, mechanical property, electrical property
Energy, dimensional stability, chemical solvent resistance etc., its dielectric constant is 3.4～3.6.Polyimides generally with aromatic dianhydride and
Aromatic diamine is raw material, uses first polymerization to form polyamic acid (PAA), then be prepared by the method for at high temperature hot-imide,
Polyimides application potential in large scale integrated circuit of novel, lower dielectric constant and excellent mechanical performances is huge, can
To meet the use needs of microelectronic component interconnection line interlayer dielectric material largely.By drawing on polyimides main chain
Enter organic group and can improve the performance of material further, and Li Lei etc. (Li Lei. the polyimides macromolecule material containing calixarenes
The preparation of material and performance study [Ph.D. Dissertation] thereof. Donghua University, 2006.) calixarenes is incorporated into polyimide molecule chain
On, make the transparency of thin film be improved with dissolubility, but also cause heat stability, mechanical property etc. to reduce simultaneously.Existing
Technology also uses and first introduces organic group, and recycling organic group decomposes the method for pore and reduces polymide dielectric constant.
Chinese invention patent CN1810857 uses with many amidos or the silicone oil of imido grpup and anhydride reaction, then adds isocyanates and enter
Single step reaction, utilizes the carbon dioxide pore released in imidization, obtains micro-pore organic silicon block polyimides, the party
Polyimide material dielectric constant prepared by method is low, stable performance under moist conditions, have good wave transparent performance, but power
Learning performance substantially to reduce, disclosed organic block ODA-PMDA type polymide dielectric constant is 2.5, but Young mould
Amount only 1.1GPa, hence it is evident that less than unmodified ODA-PMDA type polyimides.
In sum, it has been disclosed that documents and materials show by introduce organic group modification polyimides, though it is normal to reduce dielectric
Number etc., but polyimides heat stability, mechanical property etc. can be caused to be deteriorated simultaneously.
Summary of the invention
The purpose of this method is to provide a kind of crown ether modified polyimide hybridized film and preparation method thereof, and the method utilizes oversubscription
It is poly-that interacting between sub-host and guest compound obtains that dielectric constant reduces, mechanical property is maintained even increasing
Acid imide hybridized film, thus overcome the deficiencies in the prior art.
The present invention contains by utilizing in moleculeBetween crown ether and the aromatic diamine of repetitive
Hydrogen bond and clathration generate crown ether/diamidogen clathrate, then this clathrate and aromatic dianhydride are reacted generation polyamic acid, make
Crown ether molecule is enclosed within polyamic acid chain formation Necklet-type structure supermolecule, and utilize between supermolecule host and guest compound is mutual
Effect, it is thus achieved that low-k and mechanical property are maintained the polyimide hybrid film even increased.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that:
The preparation method of a kind of crown ether modified polyimide hybridized film, comprises the following steps:
(1) in humidity less than 50%, under room temperature, mechanical agitation, in nitrogen atmosphere, be (0.1～0.4) by mol ratio: 1
Crown ether and aromatic diamine are dissolved in polar organic solvent, control crown ether and aromatic diamine gross mass percent in a solvent
It is 12～18%；After being completely dissolved to crown ether and aromatic diamine, it is further continued for stirring 1～1.5 hour, obtains crown ether/diamidogen bag
Polymer solution；Described aromatic diamine be 4,4'-diaminodiphenyl ether, 1,3-phenylenediamine, 2,4,6-trimethyl m-diaminobenzene.,
4,4'-diaminodiphenyl-methane or 2,2'-bis trifluoromethyl-4,4'-benzidine；
(2) in the crown ether prepared by step (1)/diamidogen inclusion complex in solution, according to aromatic dianhydride and aromatic diamine
Mol ratio is 1:(1～1.1) add aromatic dianhydride, after aromatic dianhydride adds, continue stirring 8～12 hours,
Obtain crown ether modified polyamide acid solution；
(3) by described crown ether modified polyamide acid solution uniform application in clean glass sheet, it is then placed into vacuum drying oven
Bubble is eliminated under middle vacuum；Heat up by setup program and at 80～85 DEG C, i.e. keep 1～1.5 hour, keep 1～1.5 at 100～105 DEG C
Hour, keep 1～1.5 hour at 195～200 DEG C, keep carrying out hot-imide in 2～2.5 hours at 295～300 DEG C；Process
It is cooled to room temperature after Biing, places into immersion in deionized water and make film separation, then described film vacuum is dried, obtains thickness
Degree is the crown ether modified polyimide hybridized film of 180～220 μm.
For realizing the object of the invention further, it is preferable that described crown ether be 15-crown ether-5, hexaoxacyclooctadecane-6-6, bicyclohexane also
-hexaoxacyclooctadecane-6-6 or dibenzo-18-crown-6 (DB18C6).
The preparation method of a kind of crown ether modified polyimide hybridized film according to claim 1, it is characterised in that described
Aromatic dianhydride be 1,2,4,5-pyromellitic acid anhydride, 3,3', 4,4'-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracid two
The double phthalic anhydride of acid anhydride, 4,4-oxygen or 4,4-hexafluoro isopropyl phthalic anhydride.
Polar organic solvent described in step (1) is N methyl pyrrolidone, N, N dimethylformamide, N, N dimethyl
Acetamide, dimethyl sulfoxide or oxolane.
Described aromatic dianhydride is divided into many parts of equivalent, and every part of interval adds for 20～30 minutes.
Described vacuum drying is that described thin film is placed in 50～70 DEG C of baking ovens vacuum drying 10～12 hours.
The time soaked in described deionized water is 15～30 minutes；The time of described elimination bubble is 4～6 hours.
The thickness of described crown ether modified polyimide hybridized film is 180～220 μm.
A kind of crown ether modified polyimide hybridized film, is prepared by above-mentioned preparation method.
The present invention utilizes the hydrogen bond between crown ether with aromatic diamine and Mr. clathration to become crown ether/diamidogen clathrate, then should
Clathrate and aromatic dianhydride react generation polyamic acid, make crown ether molecule be enclosed within polyamic acid chain formation Necklet-type structure and surpass
Molecule, the heat stability of such crown ether increases, after 295～300 DEG C of hot-imides, crown ether molecule still stable existence
In polyimides main chain, and polyimide molecule chain is the most also three-dimensional by two-dimensional expansion, and strand compliance reduces, just
Property gets a promotion；Additionally the polarity of crown ether is low compared with polyimides, and the active force of polyimide molecule interchain is had certain shielding
Effect, therefore polyimide molecule interchain interaction power reduces, and sliding is easier to, and makes the elongation at break of thin film increase,
Dielectric constant then reduces.The present invention utilizes the method forming super molecular compound between host and guest compound to obtain low dielectric
Constant and mechanical property are maintained the polyimide hybrid film even increased.
It is an advantage of the current invention that:
Crown ether modified polyimide hybridized film dielectric constant obtained by the present invention is down to 2.90 from the 3.59 of body polyimides,
Reduce by 19%；And Young's modulus is increased to 5.06GPa by 2.81GPa, hot strength is increased to 133.2MPa by 119.3MPa,
Elongation at break is increased to 36.6% by 22.0%, and energy to failure is increased to 37.0MPa by 20.9MPa, increase by 80% respectively, 12%,
66% and 77%, while obtaining relatively low-k, rigidity increases with toughness, and use value is big.
Accompanying drawing explanation
Fig. 1 is gained hexaoxacyclooctadecane-6-6/ODA inclusion complex in solution and pure ODA (deuterated DMSO) in specific embodiment 11H-NMR spectrum.
Fig. 2 is the modified PMDA-ODA type polyamic acid (hexaoxacyclooctadecane-6-6/PAA) of gained hexaoxacyclooctadecane-6-6 in specific embodiment 1
PMDA-ODA type polyamic acid (PAA) pure with comparative example1H-NMR spectrum.
Detailed description of the invention
In order to be more fully understood that present disclosure, below in conjunction with embodiment, the invention will be further described, but embodiment is also
Do not constitute limiting the scope of the present invention.
Between 4,4'-diaminodiphenyl ether (ODA) used by example below, 1,3-phenylenediamine (MPDA), 2,4,6-trimethyl
Phenylenediamine (TMPDA), 4,4'-diaminodiphenyl-methane (MDA), 2,2'-bis trifluoromethyl-4,4'-benzidine
(TFDB), 1,2,4,5-pyromellitic acid anhydride (PMDA), 3,3', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-
The double phthalic anhydride (ODPA) of benzophenone tetracarboxylic dianhydride (BTDA), 4,4-oxygen and 4,4-hexafluoroisopropyli,ene-O-phthalic
Anhydride (6FDA) is this reagent company limited (Adamas) product of Shanghai Adama；15 crown ether 5,18 crown ethers 6,
Bicyclohexane also-hexaoxacyclooctadecane-6-6 and dibenzo-18-crown-6 (DB18C6) be Shanghai Aladdin reagent company limited (Aladdin) product；
Methanol, N methyl pyrrolidone (NMP), N, N dimethylformamide (DMF), N, N dimethyl acetylamide (DMAc)
It is Jiangsu city prosperity functionalized chemical limited company (Enox) with dimethyl sulfoxide (DMSO) or oxolane (THF)
Product；Anhydrous calcium chloride (CaCl2), phosphorus pentoxide (P2O5) it is Tianjin great Mao chemical reagent work (DAMAO) product.
NMP carries out except water processes before use, method particularly includes: add appropriate P2O5, sealing, it is little that ambient temperatare puts 12
Shi Hou, decompression distillation, obtain anhydrous NMP；In addition add the most anhydrous before DMF, DMAc, DMSO, THF use
CaCl2After refluxing 12 hours, distilation；ODA, MPDA, TMPDA, MDA and TFDB are placed in vacuum drying oven
In, it is vacuum dried 48 hours at 60 DEG C；PMDA, BPDA, BTDA, OPDA and 6FDA are placed in vacuum drying oven,
It is vacuum dried 48 hours at 140 DEG C.
Sheet glass (120mm × 100mm × 3mm) uses deionized water to clean up and is placed in 80 DEG C of baking ovens dry 12
After hour standby.
Embodiment 1:
(1) 40% humidity, 32 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0040mol
4,4'-diaminodiphenyl ethers (ODA), 0.0016mol hexaoxacyclooctadecane-6-6 and 12g DMSO, complete to hexaoxacyclooctadecane-6-6 and ODA
After CL, it is further continued for stirring 1 hour, obtains hexaoxacyclooctadecane-6-6/ODA inclusion complex in solution；Solvent is made with deuterated DMSO
Hexaoxacyclooctadecane-6-6/ODA the inclusion complex in solution of preparation is with pure ODA's (in deuterated DMSO)1H-NMR spectrum compares as attached
Fig. 1, from the figure it may be seen that after ODA acts on hexaoxacyclooctadecane-6-6, on primary amine, the chemical shift of hydrogen atom is by original 4.777
Ppm moves to 4.811ppm, and on phenyl ring, the chemical shift of hydrogen atom does not the most offset, still 6.497 and 6.630ppm,
The chemical shift (3.543ppm) of the hydrogen atom of crown ether own also offsets, and shows the hydrogen on ODA primary amine and hexaoxacyclooctadecane-6
There is strong hydrogen bond action between oxygen in-6, define Host-guest inclusion complex, be i.e. hexaoxacyclooctadecane-6-6/ODA clathrate；
(2) under mechanical agitation, by 0.0040mol 1,2,4,5-pyromellitic acid anhydrides (PMDA) are divided into four parts of equivalent,
Joined in above-mentioned there-necked flask at interval of 30 minutes, after adding to PMDA, continue stirring 10 hours, obtain 18-
Modified PMDA-ODA type polyamic acid (the being designated as hexaoxacyclooctadecane-6-6/PAA) solution of crown ether-6；Weigh this polyamic acid of 0.5g molten
Liquid, adds 2g DMSO agitation and dilution, is added dropwise in methanol by the polyamic acid solution after dilution, has Precipitation,
Filtering, filter cake is placed in 60 DEG C of vacuum drying ovens and is dried 24 hours, then takes to be dissolved on a small quantity in deuterated DMSO and carry out nuclear-magnetism altogether
Vibration analysis, gained1H-NMR spectrum such as accompanying drawing 2；And by made for the comparative example PMDA-ODA not having hexaoxacyclooctadecane-6-6 modification
Type polyamic acid (being designated as PAA)1H-NMR puts in accompanying drawing 2 and contrasts, as can be seen from Figure 2, in pure polyamic acid
The chemical shift of the upper hydrogen of-COOH is split due to configuration difference and is divided into 10.528 and 10.499ppm, and hexaoxacyclooctadecane-6-6 is modified
The chemical shift of the upper hydrogen atom of PMDA-ODA type-COOH is moved to low field, occurs in 10.540 and 10.511ppm, poly-
In amic acid, on phenyl ring, hydrogen atom chemical shift does not the most offset, and in crown ether, the chemical shift (3.543ppm) of hydrogen does not occurs yet
Skew, shows the formation of the modified PMDA-ODA type polyamic acid of hexaoxacyclooctadecane-6-6, and polyamic acid may shape with hexaoxacyclooctadecane-6-6
Become the Host-guest inclusion complex of Necklet-type supramolecular structure；
(3) take the polyamic acid solution uniform application of the above-mentioned preparation of 10g in clean glass sheet, be then placed into vacuum and do
Dry case eliminates bubble under vacuo 5 hours；Heat up by setup program and i.e. keep at 80 DEG C 1 hour, keep at 100 DEG C
1 hour, keep 1 hour at 200 DEG C, keep carrying out hot-imide in 2 hours at 300 DEG C；Room it is cooled to after being disposed
Temperature, places into immersion in deionized water and makes film separation in 20 minutes, then this thin film is placed in 55 DEG C of baking ovens vacuum drying
12 hours, obtain the modified PMDA-ODA type polyimide hybrid film of hexaoxacyclooctadecane-6-6 that thickness is 200 μm.
Embodiment 2:
45% humidity, 35 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0045mol 2,4,6-
Trimethyl m-diaminobenzene. (TMPDA), 0.00045mol hexaoxacyclooctadecane-6-6 and 12g NMP, to hexaoxacyclooctadecane-6-6 and TMPDA
After being completely dissolved, it is further continued for stirring 1.2 hours, obtains hexaoxacyclooctadecane-6-6/TMPDA inclusion complex in solution；By 0.0049mol
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is divided into four parts of equivalent, joins in above-mentioned there-necked flask at interval of 28 minutes,
After BPDA adds, continue stirring 9 hours, obtain the modified TMPDA-BPDA type polyamic acid of hexaoxacyclooctadecane-6-6
Solution；
Take 9.5g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven under vacuum
Eliminate bubble 4.5 hours；Heat up by setup program i.e. keep at 81 DEG C 1.2 hours, keep at 102 DEG C 1.5 hours, 198
Keep at DEG C 1.3 hours, keep at 298 DEG C carrying out hot-imide in 2.1 hours；It is cooled to room temperature after being disposed, then puts
Enter deionized water soaks and make film separation in 15 minutes, then this thin film is placed in 60 DEG C of baking ovens vacuum drying 10.5 hours,
Obtain the modified TMPDA-BPDA type polyimide hybrid film of hexaoxacyclooctadecane-6-6 that thickness is 190 μm.
Embodiment 3:
40% humidity, 25 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0034mol 1,3-
Phenylenediamine (MPDA), 0.00068mol hexaoxacyclooctadecane-6-6 and 12g DMF, after being completely dissolved to hexaoxacyclooctadecane-6-6 and MPDA,
It is further continued for stirring 1.4 hours, obtains hexaoxacyclooctadecane-6-6/MPDA inclusion complex in solution；Under mechanical agitation, by 0.0034mol
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is divided into four parts of equivalent, joins in above-mentioned there-necked flask at interval of 20 minutes,
After adding to BTDA, continue stirring 8 hours, obtain the modified MPDA-BTDA type polyamic acid of hexaoxacyclooctadecane-6-6
Solution；
Take 9g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven in vacuum
Lower elimination bubble 4 hours；Heat up by setup program i.e. keep at 82 DEG C 1.5 hours, keep at 103 DEG C 1.3 hours, 192
Keep at DEG C 1.4 hours, keep at 295 DEG C carrying out hot-imide in 2.4 hours；It is cooled to room temperature after being disposed, then puts
Enter deionized water soaks and make film separation in 20 minutes, then this thin film is placed in 50 DEG C of baking ovens vacuum drying 10 hours,
Obtain the modified MPDA-BTDA type polyimide hybrid film of hexaoxacyclooctadecane-6-6 that thickness is 180 μm.
Embodiment 4:
35% humidity, 30 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0050mol 4,4'-
Diaminodiphenyl-methane (MDA), 0.0015mol hexaoxacyclooctadecane-6-6 and 12g DMAc, complete to hexaoxacyclooctadecane-6-6 and MDA
After CL, it is further continued for stirring 1.5 hours, obtains hexaoxacyclooctadecane-6-6/MDA inclusion complex in solution；Under mechanical agitation, by 0.0055
The double phthalic anhydride (ODPA) of mol 4,4-oxygen is divided into four parts of equivalent, joins in above-mentioned there-necked flask at interval of 25 minutes,
After adding to ODPA, continue stirring 12 hours, obtain the modified MDA-ODPA type polyamic acid of hexaoxacyclooctadecane-6-6 molten
Liquid；
Take 11g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven in vacuum
Lower elimination bubble 6 hours；Heat up by setup program i.e. keep at 85 DEG C 1.3 hours, keep at 105 DEG C 1.2 hours, 195
Keep at DEG C 1.4 hours, keep at 295 DEG C carrying out hot-imide in 2.2 hours；It is cooled to room temperature after being disposed, then puts
Enter deionized water soaks and make film separation in 30 minutes, then this thin film is placed in 70 DEG C of baking ovens vacuum drying 11 hours,
Obtain the modified MDA-ODPA type polyimide hybrid film of hexaoxacyclooctadecane-6-6 that thickness is 220 μm.
Embodiment 5:
45% humidity, 25 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0024mol 2,2'-
Bis trifluoromethyl-4,4'-benzidine (TFDB), 0.0010mol hexaoxacyclooctadecane-6-6 and 12g THF, to hexaoxacyclooctadecane-6-6 and
After TFDB is completely dissolved, it is further continued for stirring 1 hour, obtains hexaoxacyclooctadecane-6-6/TFDB inclusion complex in solution；Under mechanical agitation,
0.0024mol 4,4-hexafluoroisopropyli,ene-phthalic anhydride (6FDA) is divided into four parts of equivalent, at interval of 30 minutes
Join in above-mentioned there-necked flask, after adding to 6FDA, continue stirring 11 hours, obtain hexaoxacyclooctadecane-6-6 modified
TFDB-6FDA type polyamic acid solution；
Take 10g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven in vacuum
Lower elimination bubble 5.5 hours；Heat up by setup program i.e. keep at 80 DEG C 1 hour, keep at 104 DEG C 1.1 hours, 199
Keep at DEG C 1.2 hours, keep at 299 DEG C carrying out hot-imide in 2.1 hours；It is cooled to room temperature after being disposed, then puts
Enter deionized water soaks and make film separation in 20 minutes, then this thin film is placed in 60 DEG C of baking ovens vacuum drying 12 hours,
Obtain the modified TFDB-6FDA type polyimide hybrid film of hexaoxacyclooctadecane-6-6 that thickness is 200 μm.
Embodiment 6:
40% humidity, 20 DEG C, under mechanical agitation, be passed through nitrogen, add in the there-necked flask of 50ml 0.0042mol ODA,
0.0017mol 15-crown ether-5 and 12g NMP, after being completely dissolved to 15-crown ether-5 and ODA, is further continued for stirring 1.3 little
Time, obtain 15-crown ether-5/ODA inclusion complex in solution；Under mechanical agitation, 0.0046mol PMDA is divided into four parts of equivalent,
Joined in above-mentioned there-necked flask at interval of 25 minutes, after adding to PMDA, continue stirring 10 hours, obtain 15-
The modified PMDA-ODA type polyamic acid solution of crown ether-5；
Take 10.5g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven very
Empty lower elimination bubble 5 hours；Heat up by setup program i.e. keep at 80 DEG C 1.4 hours, keep at 102 DEG C 1.3 hours,
Keep at 195 DEG C 1.5 hours, keep at 296 DEG C carrying out hot-imide in 2.5 hours；Room temperature it is cooled to after being disposed, then
Put into deionized water soaks and make film separation in 25 minutes, then this thin film is placed in 65 DEG C of baking ovens vacuum drying 12 hours,
Obtain the modified PMDA-ODA type polyimide hybrid film of 15-crown ether-5 that thickness is 210 μm.
Embodiment 7:
35% humidity, 30 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0037mol 4,4'-
Diaminodiphenyl ether (ODA), 0.0015mol bicyclohexane also-hexaoxacyclooctadecane-6-6 and 12g DMSO, to bicyclohexane also-18-
After crown ether-6 and ODA are completely dissolved, be further continued for stirring 1.1 hours, obtain bicyclohexane also-hexaoxacyclooctadecane-6-6/ODA inclusion
Thing solution；Under mechanical agitation, by 0.0037mol 1,2,4,5-pyromellitic acid anhydrides (PMDA) are divided into four parts of equivalent,
Joined in above-mentioned there-necked flask at interval of 27 minutes, after adding to PMDA, continue stirring 12 hours, obtain bicyclo-
Hexane also-the modified PMDA-ODA type polyamic acid solution of hexaoxacyclooctadecane-6-6；
Take 9.5g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven very
Empty lower elimination bubble 4 hours；Heat up by setup program i.e. keep at 84 DEG C 1.1 hours, keep at 104 DEG C 1.3 hours,
Keep at 200 DEG C 1.1 hours, keep at 300 DEG C carrying out hot-imide in 2.2 hours；Room temperature it is cooled to after being disposed, then
Put into deionized water soaks and make film separation in 30 minutes, then this thin film is placed in 50 DEG C of baking ovens vacuum drying 11 hours,
Obtain bicyclohexane that thickness is 190 μm also-the modified PMDA-ODA type polyimide hybrid film of hexaoxacyclooctadecane-6-6.
Embodiment 8:
35% humidity, 25 DEG C, under mechanical agitation, be passed through nitrogen, add in the there-necked flask of 50ml 0.0038mol ODA,
0.0015mol dibenzo-18-crown-6 (DB18C6) and 12g DMF, after being completely dissolved to dibenzo-18-crown-6 (DB18C6) and ODA, followed by
Continuous stirring 1.5 hours, obtains dibenzo-18-crown-6 (DB18C6)/ODA inclusion complex in solution；Under mechanical agitation, by 0.0041mol PMDA
It is divided into four parts of equivalent, joined in above-mentioned there-necked flask at interval of 22 minutes, after adding to PMDA, continue stirring 9
Hour, obtain dibenzo-18-crown-6 (DB18C6) modification PMDA-ODA type polyamic acid solution；
Take 11g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven in vacuum
Lower elimination bubble 6 hours；Heat up by setup program i.e. keep at 85 DEG C 1 hour, keep at 105 DEG C 1.1 hours, 197
Keep at DEG C 1.2 hours, keep at 296 DEG C carrying out hot-imide process in 2.3 hours；Room temperature it is cooled to after being disposed,
Place into deionized water soaks and make film separation in 28 minutes, then this thin film is placed in 70 DEG C of baking ovens vacuum drying 11.5
Hour, obtain the dibenzo-18-crown-6 (DB18C6) modification PMDA-ODA type polyimide hybrid film that thickness is 220 μm.
Comparative example:
40% humidity, 32 DEG C, under mechanical agitation, be passed through nitrogen, in the there-necked flask of 50ml, add 0.0051mol ODA
With 12g DMSO, it is completely dissolved to ODA, obtains colourless transparent solution；0.0051mol PMDA is divided into equivalent
Four parts, joined in above-mentioned there-necked flask at interval of 30 minutes, after adding to PMDA, continue stirring 10 hours,
To PMDA-ODA type polyamic acid solution；
Take 10g above-mentioned polyamic acid solution uniform application in clean glass sheet, be then placed in vacuum drying oven in vacuum
Lower elimination bubble 5 hours；Heat up by setup program i.e. keep at 80 DEG C 1 hour, keep at 100 DEG C 1 hour, 200
Keep at DEG C 1 hour, keep at 300 DEG C carrying out hot-imide in 2 hours；It is cooled to room temperature after being disposed, places into
Ionized water soaks and within 20 minutes, makes film separation, then this thin film is placed in 55 DEG C of baking ovens vacuum drying 12 hours, obtains
Thickness is the PMDA-ODA type polyimide film of 200 μm.
According to the Young's modulus of GB/T 1040.3-2006 canonical measure composite, survey according to GB/T 1040.3-2006 standard
Amount hot strength, according to GB/T1040.3-2006 canonical measure elongation at break, by the integral area under load-deformation curve
Obtain energy to failure, according to GB/T 1409-2006 canonical measure dielectric constant.Prepared by embodiment 1～8 and comparative example, polyamides is sub-
The mechanical property of amine film and dielectric constant result such as table 1.
The mechanical property of table 1. embodiment 1～8 and comparative example and dielectric constant
As known from Table 1, the crown ether modified polyimide hybridized film of the present invention is compared with comparative example gained polyimide film, and dielectric is normal
Number declines, and Young's modulus, hot strength, elongation at break, energy to failure the most all have increase in various degree, show rigidity with
Toughness improves.The crown ether modified polyimide hybridized film (embodiment 8) will prepared by aromatic diamine of the same race and aromatic dianhydride
The body polyimide film prepared with comparative example compares, it is found that dielectric constant is down to 2.90 by 3.59, reduces by 19%,
Young's modulus is then increased to 5.06GPa by the 2.81GPa of body polyimide film, and hot strength is increased to by 119.3MPa
133.2MPa, elongation at break is increased to 36.6% by 22.0%, and energy to failure is increased to 37.0MPa by 20.9MPa, increases respectively
80%, 12%, 66% and 77%；Crown ether modified polyimide hybridized film the most of the present invention is obtaining relatively low-k
Meanwhile, rigidity improves with toughness, and use value is big.
Claims (8)
1. the preparation method of a crown ether modified polyimide hybridized film, it is characterised in that comprise the following steps:
(1) in humidity less than 50%, under room temperature, mechanical agitation, in nitrogen atmosphere, be (0.1～0.4) by mol ratio: 1
Crown ether and aromatic diamine are dissolved in polar organic solvent, control crown ether and aromatic diamine gross mass percent in a solvent
It is 12%～18%；After being completely dissolved to crown ether and aromatic diamine, it is further continued for stirring 1～1.5 hour, obtains crown ether/diamidogen bag
Polymer solution；Described aromatic diamine be 4,4'-diaminodiphenyl ether, 1,3-phenylenediamine, 2,4,6-trimethyl m-diaminobenzene.,
4,4'-diaminodiphenyl-methane or 2,2'-bis trifluoromethyl-4,4'-benzidine；Described crown ether is bicyclohexane also-18-
Crown ether-6 or dibenzo-18-crown-6 (DB18C6)；
(2) in the crown ether prepared by step (1)/diamidogen inclusion complex in solution, according to aromatic dianhydride and aromatic diamine
Mol ratio is 1:(1～1.1) add aromatic dianhydride, after aromatic dianhydride adds, continue stirring 8～12 hours,
Obtain crown ether modified polyamide acid solution；
(3) by described crown ether modified polyamide acid solution uniform application in clean glass sheet, it is then placed into vacuum drying oven
Bubble is eliminated under middle vacuum；Heat up by setup program and at 80～85 DEG C, i.e. keep 1～1.5 hour, keep 1～1.5 at 100～105 DEG C
Hour, keep 1～1.5 hour at 195～200 DEG C, keep carrying out hot-imide in 2～2.5 hours at 295～300 DEG C；Process
It is cooled to room temperature after Biing, places into immersion in deionized water and make film separation, then described film vacuum is dried, obtains crown ether
Modified polyimide hybridized film.
The preparation method of a kind of crown ether modified polyimide hybridized film the most according to claim 1, it is characterised in that institute
The aromatic dianhydride stated is 1,2,4,5-pyromellitic acid anhydride, 3,3', 4,4'-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracid
The double phthalic anhydride of dianhydride, 4,4-oxygen or 4,4-hexafluoro isopropyl phthalic anhydride.
The preparation method of a kind of crown ether modified polyimide hybridized film the most according to claim 1, it is characterised in that step
Suddenly the polar organic solvent described in (1) is N methyl pyrrolidone, N, N dimethylformamide, N, N dimethyl acetylamide,
Dimethyl sulfoxide or oxolane.
The preparation method of a kind of crown ether modified polyimide hybridized film the most according to claim 1, it is characterised in that institute
Stating aromatic dianhydride and be divided into many parts of equivalent, every part of interval adds for 20～30 minutes.
The preparation method of a kind of crown ether modified polyimide hybridized film the most according to claim 1, it is characterised in that institute
Stating vacuum drying is that described thin film is placed in 50～70 DEG C of baking ovens vacuum drying 10～12 hours.
The preparation method of a kind of crown ether modified polyimide hybridized film the most according to claim 1, it is characterised in that institute
The time of immersion in deionized water of stating is 15～30 minutes；The time of described elimination bubble is 4～6 hours.
The preparation method of a kind of crown ether modified polyimide hybridized film the most according to claim 1, it is characterised in that institute
The thickness stating crown ether modified polyimide hybridized film is 180～220 μm.
8. a crown ether modified polyimide hybridized film, it is characterised in that it is by preparation method described in any one of claim 1～7
Prepare.
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