CN104341593B - There is polyimides of low dielectric property and its preparation method and application - Google Patents
There is polyimides of low dielectric property and its preparation method and application Download PDFInfo
- Publication number
- CN104341593B CN104341593B CN201310329402.1A CN201310329402A CN104341593B CN 104341593 B CN104341593 B CN 104341593B CN 201310329402 A CN201310329402 A CN 201310329402A CN 104341593 B CN104341593 B CN 104341593B
- Authority
- CN
- China
- Prior art keywords
- polyimides
- low dielectric
- dielectric property
- preparation
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 70
- 239000004642 Polyimide Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000003989 dielectric material Substances 0.000 claims abstract description 6
- 229920005575 poly(amic acid) Polymers 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 229940100630 metacresol Drugs 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 12
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 abstract description 8
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 abstract description 8
- 230000010354 integration Effects 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 150000004984 aromatic diamines Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000007239 Wittig reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- ZULBJCCSDFLSBQ-KEIOHQPYSA-N 4-N-(4-aminophenyl)-4-N-[4-[4-[(E)-2-phenyl-2-[4-[4-(trifluoromethyl)phenyl]phenyl]ethenyl]phenyl]phenyl]benzene-1,4-diamine Chemical compound Nc1ccc(cc1)N(c1ccc(N)cc1)c1ccc(cc1)-c1ccc(\C=C(/c2ccccc2)c2ccc(cc2)-c2ccc(cc2)C(F)(F)F)cc1 ZULBJCCSDFLSBQ-KEIOHQPYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UMLODRIYZXIOLX-UHFFFAOYSA-N CC(C1)C(C)=CC(C(C=C2)=CCC2c(cc2)ccc2F)=C1c(cc(C)c(C)c1)c1-c(cc1F)cc(F)c1F Chemical compound CC(C1)C(C)=CC(C(C=C2)=CCC2c(cc2)ccc2F)=C1c(cc(C)c(C)c1)c1-c(cc1F)cc(F)c1F UMLODRIYZXIOLX-UHFFFAOYSA-N 0.000 description 1
- HFOWPHDMMKHCIA-UHFFFAOYSA-N CC1C(C)=CC(Oc2c(C)c(Oc3cc(C)c(C)cc3)ccc2)=CC1 Chemical compound CC1C(C)=CC(Oc2c(C)c(Oc3cc(C)c(C)cc3)ccc2)=CC1 HFOWPHDMMKHCIA-UHFFFAOYSA-N 0.000 description 1
- WZILJUKERLIPNC-UHFFFAOYSA-N Cc(cc1)c(C)cc1OC1C=CC(Sc(cc2)ccc2Oc2cc(C)c(C)cc2)=CC1 Chemical compound Cc(cc1)c(C)cc1OC1C=CC(Sc(cc2)ccc2Oc2cc(C)c(C)cc2)=CC1 WZILJUKERLIPNC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical group 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 monohaloalkyl benzophenone Chemical compound 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind of polyimides with low dielectric property and its preparation method and application.It is raw material that the polyimides of the present invention uses containing triphenylamine and aromatic diamines and various tetracarboxylic dianhydrides with the big side base containing triphenylethylene/tetraphenyl ethylene, is prepared from by imidizate method.Polyimides of the present invention has ultralow dielectric constant and relatively low dielectric loss, and has the performances such as excellent solubility, higher glass transition temperature and heat stability, excellent mechanical performance and luminescence generated by light.The synthetic method craft of the present invention is simple, various, thus is suitable to commercial production；The polyimides of the present invention can be applicable to prepare dielectric materials, is widely used in the new high-tech industry fields, particularly super large-scale integration field such as electronics, microelectronics, information, luminescent material and Aero-Space.
Description
Technical field
The present invention relates to material science, particularly one class polyimides with low dielectric property and its preparation method and application.
Technical background
High density, at high speed, Mobyneb, high-performance super large-scale integration (ULSI) require large chip area and little characteristic size, wiring density must be increased for this, reduce the distance between the width of metal wire and line.Device density and line density are greatly increased, so that resistance and line capacitance coupling increase rapidly in interconnection system.Make signal transmission delay even distortion, interference noise strengthen and power dissipation increases, become the bottleneck of high-performance super large-scale integration (ULSI) development further.According to signal transmission delay (RC) and the computing formula model of power (P) and correlation theory, the RC realizing reducing integrated circuit postpones and reduces energy consumption P, and the solution of this problem depends on exploitation and the application of material (ILD) between novel low dielectric layer.
The advanced low-k materials of research is broadly divided into inorganic, organic and hybrid inorganic-organic three major types at present.Organic polymer itself has low polarity, its dielectric constant relatively low (k=2.0-4.0).But the most glass transition temperature low (Tg < 200 DEG C) of organic polymer, poor heat stability, it is impossible to meet the heatproof requirement in ULSI.And full aromatic polyimide is one of kind that in polymer, heat stability is the highest, become the polymer base dielectric materials that research is the most active.
General Intrinsical PI film is about 3.4；K containing naphthalene side chain and aromatic ether structure PI is 2.78 (Tg=294)；The K of diamantane (obsolete) race homopolymerization PI and alicyclic homopolymerization PI is 2.5-2.8 at the K of 2.5-2.6, linear aliphatic race PI in the K value of 2.8-2.9, the copolymerization PI of linear aliphatic race and diamantane (obsolete) race, there is good dissolubility and film property, hot strength is that 79-88MPa, Tg are 220-225 DEG C；Fluorine-containing PI is up to 2.49 (Tg=234).Main chain contains the K of on-plane surface big conjugated structure PI up to 2.7, and good film-forming property, hot strength is that 115-130MPa, Tg are 360-409 DEG C, has significant advantage in mechanical property and heat stability；Main chain contain fluorene structured non-fluorine-containing PI up to 2.6.Being consulted reference materials display according to us, can reach less than 2.0 except the dielectric constant of the zeolitic material containing porous at present, the dielectric constant of other intrinsic materials fails less than 2.0.
Major part scholar concentrates on the research of nano-porous polymer material and hybrid inorganic-organic materials in recent years, the micro-nano sky of introducing is used to make the dielectric constant of material reach the requirement of current high-performance super large-scale integration dielectric constant, but in these materials, the overwhelming majority fails to reach other performance requirements of ultra-low dielectric constant material, there is also a lot of problem: (1) complex process, be difficult to control to, production cost high；(2) structure in hole is wayward；(3) it is difficult to control the size in aperture, and pore-size distribution is wider；(4) material mechanical performance is bad, and mechanical strength is relatively low；(5) material is easily generated crackle；(6) during removed template method, void collapse is easily caused；(7) template is by selecting different surfactants to regulate hole size, but optional template limited amount, and expensive.
By the advantage that polyimide molecule structure design is strong, some are used simply to synthesize, synthesis has good space steric effect and the new diamine of hypopolarization rate or dianhydride, it is expected to reach this purpose for synthesis of polyimides, and can effectively overcome the defect of the aspects such as mechanical performance, hot property and preparation technology.
Summary of the invention
It is an object of the invention to provide a class and have the polyimides of low dielectric property, it has the performances such as excellent solubility, higher glass transition temperature and heat stability, excellent mechanical performance and luminescence generated by light.
Another object of the present invention is to provide the preparation method of the above-mentioned polyimides with low dielectric property, its preparation technology is simple and various, and condition requires low, thus is suitable to commercial production.
It is a still further object of the present invention to provide a kind of low dielectric polyimide material, there is ultralow dielectric constant and relatively low dielectric loss, and there is the performances such as excellent solubility, higher glass transition temperature and heat stability, excellent mechanical performance and luminescence generated by light, can be applicable to the field such as dielectric materials, optical material.
The object of the present invention is achieved like this: a kind of polyimides with low dielectric property, it is characterised in that containing following construction unit in general formula of molecular structure:
Wherein: n >=1；X is the aromatic hydrocarbyl of tetravalence；Y is diamidogen residue, and its general structure is one or more in I, II or III
Wherein, Ar1Selected from any one of following structural:
Ar2、Ar3And Ar4Selected from any one of following structural:
X is the aromatic hydrocarbyl of tetravalence, includes but not limited to one or more in following general structure:
The preparation method of the above-mentioned polyimides with low dielectric property, the course of reaction of the method is: in argon gas atmosphere, the hybrid diamine by the diamidogen containing Y structure or containing Y structure and the dianhydride containing X architecture are in molar ratio for 1:(0.9～1.1) it is dissolved in polar non-proton organic solvent,-10～40 DEG C of stirring reactions 0.5～72h, obtain homogeneous, transparent, the polyamic acid solution of thickness, finally polyamic acid solution being carried out is dehydrated imidizate method and obtains the polyimides of solubility.
The polyimides with low dielectric property proposed by the invention, this quasi-polyimide has ultralow dielectric constant and relatively low dielectric loss, and there is the performances such as excellent solubility, higher glass transition temperature and heat stability, excellent mechanical performance and luminescence generated by light, and its preparation technology is simple and various, condition requires low, thus is suitable to commercial production.The polyimides of the present invention can be applicable to prepare dielectric materials and optical material, is widely used in the new high-tech industry fields, particularly super large-scale integration field such as electronics, microelectronics, information, luminescent material and Aero-Space.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of four kinds of polyimide films in the embodiment of the present invention, wherein:
A corresponds to Tri-TPA-2NH2/ 6-FDA-PI, b correspond to TPA-TPE-2NH2/ 6FDA-PI,
C corresponds to Tetra-TPA-2NH2/ 6-FDA-PI, d correspond to TPE-TPA-CF3-2NH2/ 6FDA-PI,
E corresponds to TPE-TPA-CF3-2NH2/ BPDA-PI, f correspond to TPE-O-TPA-CF3-2NH2/6FDA-PI。
From the figure, it can be seen that at 1775cm-1And 1715cm-1Place occurs in that and absorbs into asymmetrical stretching vibration peak and the symmetrical stretching vibration of carbonyl on acid imide five-membered ring.At 3049cm-1Place occurs in that=the characteristic absorption frequency of C-H, and 1605cm-1And 1502cm-1Place occurs in that the phenyl ring skeleton stretching vibration absworption peak of feature, 820cm-1Place is the characteristic absorption frequency of para-position two replacement Ar-H, 718cm-1The characteristic absorption frequency that absworption peak is monosubstituted Ar-H that place occurs, these all illustrate that synthesized product all has the feature structure of aromatic polyimide.1165cm-1The characteristic absorption peak that absworption peak is C-F that place occurs.
Detailed description of the invention
The present invention is a kind of polyimides with low dielectric property, can be made into powder body material or thin-film material, is applied to prepare dielectric materials.Its general formula of molecular structure is:
Wherein: n >=1；X is the aromatic hydrocarbyl of tetravalence；Y is diamidogen residue, and its general structure is one or more in I, II or III:
Wherein, Ar1Selected from any one of following structural:
Ar2、Ar3And Ar4Selected from any one of following structural:
X is the aromatic hydrocarbyl of tetravalence, includes but not limited to one or more in following general structure:
During preparation, in argon gas atmosphere, the hybrid diamine by the diamidogen containing Y structure or containing Y structure and the dianhydride containing X architecture are in molar ratio for 1:(0.9～1.1) it is dissolved in polar non-proton organic solvent,-10～40 DEG C of stirring reactions 0.5～72h, obtain homogeneous, transparent, the polyamic acid solution of thickness, finally polyamic acid solution being carried out is dehydrated imidizate and obtains the polyimides of solubility.Preferably, the diamidogen containing Y structure or the hybrid diamine containing Y structure account for the 2～50% of reaction mass gross mass with the dianhydride gross mass containing X architecture.The preferred N-Methyl pyrrolidone of described polar non-proton organic solvent, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1,4-dioxane, N, one or more mixture in N-dimethyl acetylamide, DMF, metacresol, oxolane etc..
It is hot-imide or chemical imidization that polyamic acid solution dehydration imidizate obtains the method for polyimides.The step of hot-imide method is: by polyamic acid solution blade coating on clean glass plate, again glass plate is placed in baking oven (preferably vacuum drying oven), temperature programming carries out hot-imide, preferably temperature programming program is: first room temperature is to constant temperature after 50～180 DEG C, whole process 10-240 minute；Constant temperature after being warming up to 180～250 DEG C the most again, whole process 10-240 minute；Constant temperature after being finally warming up to 250 DEG C～380 DEG C, whole process 10-360 minute；Polyimide film is i.e. obtained after cooling.The step of chemical imidization method is: add dehydrant in polyamic acid solution, after the stirring that heats up, it is heated to 50～200 DEG C and continues stirring 0.5～72h, pour into after being cooled to room temperature and methanol or acetone obtain polyimides precipitation, filtration drying, i.e. obtains polyimides powder body；Polyimides powder body is dissolved in N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethyl acetylamide (DMAc), N, in dinethylformamide (DMF), metacresol (m-Cresol) or oxolane (THF), after being heated to being completely dissolved, by polyimide solution blade coating on clean glass plate, 70～300 DEG C are dried removal solvent, i.e. obtain polyimide film after cooling.Preferred pyridine/the acetic anhydride of above-mentioned dehydrant, triethylamine/acetic anhydride or sodium acetate/acetic anhydride.
nullFor the diamidogen containing Y structure，Those skilled in the art can design synthetic route according to actually required concrete molecular structure，Use Witting、Witting-Horner、The series reaction synthesis such as Suzuki，Such as may comprise steps of: (A1) utilizes benzophenone to pass through Wittig or Wittig-Horner reaction and change into the big conjugated system monomer containing a halogen atom with triphenylethylene/tetraphenyl ethylene structure，Or，Utilize the substitution reaction of two halogen atoms in monohaloalkyl benzophenone or dihalo benzophenone monomer，Obtain the one monomers containing big conjugated system，Its ketone carbonyl changes into the big conjugated system monomer containing a halogen atom with triphenylethylene/tetraphenyl ethylene structure by Wittig or Wittig-Horner reaction again；(A2) halogen atom of the big conjugated system monomer containing a halogen atom with triphenylethylene/tetraphenyl ethylene structure of step (A1) gained is utilized, reacted by step Suzuki, or by multistep reaction, obtain the monoamine monomer containing the big conjugated system of triphenylethylene/tetraphenyl ethylene；(A3) the monoamine monomer containing the big conjugated system of triphenylethylene/tetraphenyl ethylene utilizing step (A2) gained reacts with halogenated nitrobenzene, obtains containing triphenylamine and the dinitro monomer of the big conjugated system of triphenylethylene/tetraphenyl ethylene；(A4) the dinitro monomer reduction containing triphenylamine conjugated system big with triphenylethylene/tetraphenyl ethylene of step (A3) gained is become diamidogen.
Example is given below so that the present invention will be described in more detail; it is important to point out that following example can not be construed to the restriction to invention protection domain; some nonessential improvement and adjustment that the present invention is made by the person skilled in the art in this field according to foregoing invention content, must belong to protection scope of the present invention.
Embodiment 1
Benzophenone is utilized to react to obtain Tri-Br by Wittig or Wittig-Horner；Then reacted by step Suzuki or by multistep reaction, obtain TrP-NHi2；React with p-fluoronitrobenzene again, obtain Tri-TPA-2NO2；Finally reduction obtains Tri-TAP-2NH2。
Under room temperature, by 5.2967g (0.01mol) (Tri-TPA-2NH2) and 64.9g (68.8ml) N, dinethylformamide adds to the there-necked flask of 100ml, it is passed through argon, stirring, after being completely dissolved, add 4.4424g (0.01mol) 4,4-hexafluoro isopropyl phthalic anhydride (6-FDA), continue stirring reaction 12h, it is thus achieved that the polyamic acid solution of homogeneous thickness.Gained polyamic acid solution is scratched on cleaned glass plate, again glass plate is placed in vacuum drying oven, evacuation, heating schedule is: constant temperature (whole process 1h) after room temperature to 100 DEG C → 100 DEG C be warming up to 200 DEG C after constant temperature (whole process 1h) → 200 DEG C be warming up to 300 DEG C after constant temperature (whole process 1h), can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 1.89, and dielectric loss is 0.009, and the thermal weight loss temperature of 5% is 528 DEG C, and glass transition temperature is 270 DEG C, and its fluorescence highest peak corresponding wavelength is 528nm, it is seen that light transmission rate is 85%, and infrared spectrogram is as shown in Figure 1.
Polyimides (the Tri-TPA-2NH with low dielectric property in the present embodiment2/ 6-FDA-PI) molecular structural formula of thin film is as follows:
Embodiment 2
Under room temperature, by 5.2967g (0.01mol) (TPA-TPE-2NH2) and 64.9g (68.8ml) N, dinethylformamide adds to the there-necked flask of 100ml, it is passed through argon, stirring, after being completely dissolved, adds 4.4424g (0.01mol) 4,4-hexafluoro isopropyl phthalic anhydride (6-FDA), continue stirring reaction 12h, it is thus achieved that the polyamic acid solution of homogeneous thickness, its molecular weight is 32.6 × 104, molecular weight distribution is 2.08.Gained polyamic acid solution is scratched on cleaned glass plate, again glass plate is placed in vacuum drying oven, evacuation, heating schedule is: constant temperature (whole process 1h) after room temperature to 100 DEG C → 100 DEG C be warming up to 200 DEG C after constant temperature (whole process 1h) → 200 DEG C be warming up to 300 DEG C after constant temperature (whole process 1h), can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 1.44, and dielectric loss is 0.003, and the thermal weight loss temperature of 5% is 543 DEG C, and glass transition temperature is 306 DEG C, and its fluorescence highest peak corresponding wavelength is 547nm, it is seen that light transmission rate is 88%, and infrared spectrogram is as shown in Figure 1.
Polyimides (the TPA-TPE-2NH with low dielectric property in the present embodiment2/ 6-FDA-PI) molecular structural formula of thin film is as follows:
Embodiment 3
Polyamic acid solution is prepared with the method that embodiment 1 is identical, then chemical imidization is used to prepare polyimides, step is such as: adds 5mL acetic anhydride in gained polyamic acid solution, continues stirring, be slow added into 2.5mL triethylamine, and it is warming up to 70 DEG C, after continuing stirring 6h, solution scratches on cleaned glass plate, then is placed in vacuum drying oven by glass plate, evacuation, 100 DEG C of dry 12h, can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 1.58, dielectric loss is 0.003, the thermal weight loss temperature of 5% is 531 DEG C, glass transition temperature is 302 DEG C, its fluorescence highest peak corresponding wavelength is 539nm, visible light transmissivity is 87%, and the solubility test result of polyimide film and infrared spectrogram are same as in Example 1.
Embodiment 4
Under room temperature, by 1.2115g (2mmol) (Tetra-TPA-2NH2) and 64.9g (68.8ml) N, dinethylformamide adds to the there-necked flask of 100ml, is passed through argon, stirring, after being completely dissolved, add 0.6445g (2mmol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), continue stirring reaction 12h, it is thus achieved that the polyamic acid solution of homogeneous thickness, its molecular weight is 37.4 × 104, molecular weight distribution is 1.65.Gained polyamic acid solution is scratched on cleaned glass plate, again glass plate is placed in vacuum drying oven, evacuation, heating schedule is: constant temperature (whole process 1h) after room temperature to 100 DEG C → 100 DEG C be warming up to 200 DEG C after constant temperature (whole process 1h) → 200 DEG C be warming up to 300 DEG C after constant temperature (whole process 1h), can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 2.44, and dielectric loss is 0.019, and the thermal weight loss temperature of 5% is 545 DEG C, and glass transition temperature is 306 DEG C, and its fluorescence highest peak corresponding wavelength is 616nm, it is seen that light transmission rate is 85%, and infrared spectrogram is as shown in Figure 1.
Polyimides (the Tetra-TPA-2NH with low dielectric property in the present embodiment2/ 6-FDA-PI) molecular structural formula of thin film is as follows:
Embodiment 5
The substitution reaction utilizing 4-bromine benzophenone obtains PTBM, and its ketone carbonyl changes into TPE-CF by Wittig or Wittig-Horner reaction again3-Br；Then reacted by step Suzuki or by multistep reaction, obtain TPE-CF3-NH2；Carry out reaction with p-fluoronitrobenzene again and obtain TPE-TPA-CF3-2NO2；Finally reduction obtains TPE-TPA-CF3-2NH2。
Under room temperature, by 6.7377g (0.01mol) (E)-N1-(4-aminophenyl)-N1-(4'-(2-phenyl-2-(4'-(trifluoromethyl)-biphenyl-4-yl) vinyl) biphenyl-4-yl) benzene-1,4-diamine. (TPE-TPA-CF3-2NH2) and 74.5g (79ml) N, dinethylformamide adds to the there-necked flask of 100ml, it is passed through argon, stirring, after being completely dissolved, adds 4.4424g (0.01mol) 4,4-hexafluoro isopropyl phthalic anhydride (6-FDA), continue stirring reaction 12h, it is thus achieved that the polyamic acid solution of homogeneous thickness, its molecular weight is 29.7 × 104, molecular weight distribution is 2.23.Gained polyamic acid solution is scratched on cleaned glass plate, again glass plate is placed in vacuum drying oven, evacuation, heating schedule is: constant temperature (whole process 1h) after room temperature to 100 DEG C → 100 DEG C be warming up to 200 DEG C after constant temperature (whole process 1h) → 200 DEG C be warming up to 300 DEG C after constant temperature (whole process 1h), can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 1.52, and dielectric loss is 0.008, and the thermal weight loss temperature of 5% is 472 DEG C, and glass transition temperature is 280 DEG C, and its fluorescence highest peak corresponding wavelength is 542nm, it is seen that light transmission rate is 85%, and infrared spectrogram is as shown in Figure 1.
Polyimides (the TPE-TPA-CF with low dielectric property in the present embodiment3-2NH2/ 6FDA-PI) molecular structural formula of thin film is as follows:
Embodiment 6
Under room temperature, by 6.7377g (0.01mol) (E)-N1-(4-aminophenyl)-N1-(4'-(2-phenyl-2-(4'-(trifluoromethyl)-biphenyl-4-yl) vinyl) biphenyl-4-yl) benzene-1,4-diamine. (TPE-TPA-CF3-2NH2) and 64.3g (68.1ml) N, dinethylformamide adds to the there-necked flask of 100ml, it is passed through argon, stirring, after being completely dissolved, add 2.9027g (0.01mol) 4,4'-bibenzene tetracarboxylic dianhydride (BPDA), continue stirring reaction 12h, it is thus achieved that the polyamic acid solution of homogeneous thickness.Gained polyamic acid solution is scratched on cleaned glass plate, again glass plate is placed in vacuum drying oven, evacuation, heating schedule is: constant temperature (whole process 1h) after room temperature to 100 DEG C → 100 DEG C be warming up to 200 DEG C after constant temperature (whole process 1h) → 200 DEG C be warming up to 300 DEG C after constant temperature (whole process 1h), can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 1.94, and dielectric loss is 0.008, and the thermal weight loss temperature of 5% is 465 DEG C, and glass transition temperature is 284 DEG C, and its fluorescence highest peak corresponding wavelength is 559nm, it is seen that light transmission rate is 84%, and infrared spectrogram is as shown in Figure 1.
Polyimides (the TPE-TPA-CF with low dielectric property in the present embodiment3-2NH2/ BPDA-PI) molecular structural formula of thin film is as follows:
Embodiment 7
Under room temperature, by 7.6586g (0.01mol) (TPE-O-TPA-CF3-2NH2) and 80.7g (85.5ml) N, dinethylformamide adds to the there-necked flask of 100ml, it is passed through argon, stirring, after being completely dissolved, add 4.4424g (0.01mol) 4,4-hexafluoro isopropyl phthalic anhydride (6-FDA), continue stirring reaction 12h, it is thus achieved that the polyamic acid solution of homogeneous thickness.Gained polyamic acid solution is scratched on cleaned glass plate, again glass plate is placed in vacuum drying oven, evacuation, heating schedule is: constant temperature (whole process 1 h) after room temperature to 100 DEG C → 100 DEG C be warming up to 200 DEG C after constant temperature (whole process 1h) → 200 DEG C be warming up to 320 DEG C after constant temperature (whole process 1h), can be taken off polyimide film after cooling.The dielectric constant of this polyimide film is up to 2.33, and dielectric loss is 0.02, and the thermal weight loss temperature of 5% is 515 DEG C, and glass transition temperature is 253 DEG C, and its fluorescence highest peak corresponding wavelength is 553nm, it is seen that light transmission rate is 84%, and infrared spectrogram is as shown in Figure 1.
Polyimides (the TPE-O-TPA-CF with low dielectric property in the present embodiment3-2NH2/ 6FDA-PI) molecular structural formula of thin film is as follows:
。
Claims (10)
1. a polyimides with low dielectric property, it is characterised in that general formula of molecular structure contains following construction unit:
Wherein: n >=1；X is the aromatic hydrocarbyl of tetravalence, and Y is diamidogen residue, general structure be in I, II or III one or both with
Upper:
Wherein, Ar1Selected from any one of following structural:
Ar2、Ar3And Ar4Selected from any one of following structural:
The polyimides with low dielectric property the most according to claim 1, it is characterised in that: X is the aromatic hydrocarbyl of tetravalence, is selected from
One or more in following general structure:
The polyimides with low dielectric property the most according to claim 1 and 2, it is characterised in that: described polyimides is powder body material
Material or thin-film material.
4. the preparation method of the polyimides with low dielectric property described in claim 1 or 2, it is characterised in that: in argon gas atmosphere, will contain
The diamidogen of Y structure or the hybrid diamine containing Y structure are 1:(0.9～1.1 in molar ratio with the dianhydride containing X architecture) to be dissolved in aprotic, polar organic molten
In agent ,-10～40 DEG C of stirring reactions 0.5～72h, obtain homogeneous, transparent, the polyamic acid solution of thickness, finally to polyamic acid solution
Carry out being dehydrated imidizate and obtain the polyimides of solubility.
The preparation method of the polyimides with low dielectric property the most according to claim 4, it is characterised in that: the diamidogen containing Y structure
Or the hybrid diamine containing Y structure accounts for the 2～50% of reaction mass gross mass with the dianhydride gross mass containing X architecture.
The preparation method of the polyimides with low dielectric property the most according to claim 4, it is characterised in that: described aprotic, polar has
Machine solvent selected from N-Methyl pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, Isosorbide-5-Nitrae-dioxane, N,N-dimethylacetamide,
One or more mixture in DMF, metacresol, oxolane.
The preparation method of the polyimides with low dielectric property the most according to claim 4, it is characterised in that: described polyamic acid solution
It is hot-imide or chemical imidization that dehydration imidizate obtains the method for polyimides.
The preparation method of the polyimides with low dielectric property the most according to claim 7, it is characterised in that: described hot-imide
The step of method is: by polyamic acid solution blade coating on clean glass plate, then being placed in baking oven by glass plate, temperature programming carries out hot acid imide
Changing, heating schedule is: first room temperature is to constant temperature after 50～180 DEG C, whole process 10-240 minute；After being warming up to 180～250 DEG C the most again
Constant temperature, whole process 10-240 minute；Constant temperature after being finally warming up to 250 DEG C～380 DEG C, whole process 10-360 minute；After cooling and get final product
To polyimide film.
The preparation method of the polyimides with low dielectric property the most according to claim 7, it is characterised in that: described chemical acid imide
The step of change method is: add dehydrant in polyamic acid solution, after the stirring that heats up, is heated to 50～200 DEG C and continues stirring 0.5～72h,
Pour into after being cooled to room temperature and methanol or acetone obtain polyimides precipitation, filtration drying, i.e. obtain polyimides powder body；By polyimides powder body
It is dissolved in N-Methyl pyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, DMF, metacresol or oxolane,
After being heated to being completely dissolved, by polyimide solution blade coating on clean glass plate, 70～300 DEG C are dried removal solvent, are i.e. gathered after cooling
Acid imide film.
10. the polyimides with low dielectric property described in claim 1 or 2 is applied to prepare dielectric materials, optical material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310329402.1A CN104341593B (en) | 2013-07-31 | 2013-07-31 | There is polyimides of low dielectric property and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310329402.1A CN104341593B (en) | 2013-07-31 | 2013-07-31 | There is polyimides of low dielectric property and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104341593A CN104341593A (en) | 2015-02-11 |
| CN104341593B true CN104341593B (en) | 2016-12-28 |
Family
ID=52498103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310329402.1A Active CN104341593B (en) | 2013-07-31 | 2013-07-31 | There is polyimides of low dielectric property and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104341593B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861162B (en) * | 2015-05-20 | 2016-04-27 | 上海交通大学 | Containing the soluble polyimide and preparation method thereof of the tertiary butyl and fluorine-triphenylamine structure |
| CN105820368B (en) * | 2016-05-25 | 2018-11-27 | 中国科学院长春应用化学研究所 | A kind of polyimide nano foam and preparation method thereof |
| CN107057065B (en) | 2017-02-16 | 2020-01-14 | 中山大学 | Polymer with low dielectric constant and molecular structure design method for reducing dielectric constant of polymer |
| CN108504294A (en) * | 2017-02-24 | 2018-09-07 | 昆山雅森电子材料科技有限公司 | A kind of coloured ultra-thin cover film of high frequency and preparation method |
| CN107118349A (en) * | 2017-06-23 | 2017-09-01 | 中山大学 | A kind of high-performance light-transmitting polyimide and its preparation method and application |
| CN107501573B (en) * | 2017-08-02 | 2021-01-22 | 中山大学 | Amorphous polymer with low dielectric constant and preparation method and application thereof |
| CN109912615A (en) * | 2019-03-20 | 2019-06-21 | 浙江福斯特新材料研究院有限公司 | Benzo alicyclic dianhydride and low dielectric coefficient polyimide precursor film |
| CN110128632B (en) * | 2019-04-01 | 2022-04-22 | 华南理工大学 | Organic electroluminescent polymer material containing tetraphenylethylene, preparation and application thereof |
| CN110423203B (en) * | 2019-07-31 | 2022-11-01 | 湘潭大学 | Fluorescent amine compound with aggregation-induced emission property and preparation method and application thereof |
| CN113416335A (en) * | 2021-07-22 | 2021-09-21 | 常州市啸朗机电有限公司 | Preparation method and production device of electronic-grade PI film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659865A (en) * | 2009-09-16 | 2010-03-03 | 中山大学 | Gathering induced luminescence material containing triphenyl thylene structure, synthesis method and application thereof |
| CN102321244A (en) * | 2011-07-22 | 2012-01-18 | 中山大学 | Soluble functional polyimide containing rigid non-planar conjugated structure, and preparation method and application thereof |
| CN102757560A (en) * | 2012-08-08 | 2012-10-31 | 中山大学 | Soluble functional polyimide with carbazole structure and preparation method and application thereof |
| CN103145581A (en) * | 2013-02-27 | 2013-06-12 | 中山大学 | Aromatic diamine compound containing imide structure as well as preparation method and application thereof |
-
2013
- 2013-07-31 CN CN201310329402.1A patent/CN104341593B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659865A (en) * | 2009-09-16 | 2010-03-03 | 中山大学 | Gathering induced luminescence material containing triphenyl thylene structure, synthesis method and application thereof |
| CN102321244A (en) * | 2011-07-22 | 2012-01-18 | 中山大学 | Soluble functional polyimide containing rigid non-planar conjugated structure, and preparation method and application thereof |
| CN102757560A (en) * | 2012-08-08 | 2012-10-31 | 中山大学 | Soluble functional polyimide with carbazole structure and preparation method and application thereof |
| CN103145581A (en) * | 2013-02-27 | 2013-06-12 | 中山大学 | Aromatic diamine compound containing imide structure as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis and Properties of High-Performance Functional Polyimides Containing Rigid Nonplanar Conjugated Tetraphenylethylene Moieties";Liu Yiwu 等;《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》;20121218;第51卷;1302-1314 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104341593A (en) | 2015-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104341593B (en) | There is polyimides of low dielectric property and its preparation method and application | |
| CN105566633B (en) | A kind of super-branched polyimide containing carbazole structure and its production and use | |
| CN106928481A (en) | The optimization preparation method of Kapton | |
| CN104672477B (en) | A kind of application of the preparation method of low roughness polyimide film, product and product | |
| CN110903649A (en) | Low-dielectric polyimide film and preparation method and application thereof | |
| CN108864454B (en) | High-transparency and high-flexibility polyimide film for electronic device and preparation method | |
| CN102352039B (en) | Soluble functional polyimide based on fluorene structure as well as preparation method and application thereof | |
| CN102807675A (en) | Flexible transparent polyimide film material and preparation method thereof | |
| CN105461925B (en) | A kind of polyimides and its preparation method and application containing carbazole structure | |
| CN105153445A (en) | Method for preparing polyimide film from reactive end-capped polyamic acid resin | |
| JP7220025B2 (en) | Films comprising polyimides or poly(amide-imide) copolymers, displays comprising such films, and methods of making such films | |
| CN108794748B (en) | Polyimide film with low dielectric constant and preparation method thereof | |
| CN102321244B (en) | Soluble functional polyimide containing rigid non-planar conjugated structure, and preparation method and application thereof | |
| CN111040164A (en) | Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof | |
| CN114656790A (en) | Flexible printed circuit board containing polyimide material with low dielectric constant and high light transmittance | |
| CN111253744B (en) | Polyimide film and preparation method and application thereof | |
| CN103755987A (en) | Preparation method for heat-resisting and high-transparence polyimide thin film | |
| Zheng et al. | Soluble polyimides containing bulky rigid terphenyl groups with low dielectric constant and high thermal stability | |
| CN115490853A (en) | High-performance polyimide flexible copper clad laminate and preparation method thereof | |
| CN105440286B (en) | A kind of polyimides containing fluorenes or Fluorenone structure and its preparation method and application | |
| CN111808423B (en) | Polyimide film with high heat resistance and low thermal expansion coefficient and preparation method thereof | |
| CN111825867A (en) | Low-dielectric modified polyimide film and preparation method thereof | |
| CN105085912B (en) | A kind of transparent polyester imide resin and preparation method thereof | |
| CN109912618A (en) | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film | |
| CN108997578A (en) | A kind of high heat resistance super-branched polyimide and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |