CN115724755A - Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device - Google Patents
Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device Download PDFInfo
- Publication number
- CN115724755A CN115724755A CN202110982729.3A CN202110982729A CN115724755A CN 115724755 A CN115724755 A CN 115724755A CN 202110982729 A CN202110982729 A CN 202110982729A CN 115724755 A CN115724755 A CN 115724755A
- Authority
- CN
- China
- Prior art keywords
- diamine
- diamine monomer
- polyimide resin
- monomer
- monomer compound
- 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.)
- Pending
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 117
- 150000004985 diamines Chemical class 0.000 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 title description 2
- 229920005989 resin Polymers 0.000 title description 2
- 229920001721 polyimide Polymers 0.000 claims abstract description 59
- 239000009719 polyimide resin Substances 0.000 claims abstract description 38
- 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 24
- -1 alicyclic diamine Chemical class 0.000 claims description 17
- 150000004984 aromatic diamines Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- 125000004427 diamine group Chemical group 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 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 claims description 3
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 claims description 3
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 3
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 claims description 3
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Chemical group 0.000 abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229920005575 poly(amic acid) Polymers 0.000 description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- 239000011889 copper foil Substances 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000002329 infrared spectrum Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- 239000004642 Polyimide Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000013067 intermediate product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000004988 Nematic liquid crystal Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The application provides a diamine monomer compound, the structural general formula of which is as follows:
wherein n is 1 Is composed of>1 is an integer. The application also provides a preparation method of the diamine monomer compound, polyimide resin prepared by applying the diamine monomer compound, and a flexible film and electronic equipment applying the polyimide resin. The diamine monomer compound introduces a long even-number carbon chain and a liquid crystal unit structure, and the long even-number carbon chain enables a molecular chain to have flexibility, so that the regularity and rigidity of the molecular chain can be effectively reduced, and polyimide resin is convenient for film forming processing; the size stability can be improved, the thermal expansion coefficient can be reduced, the material has excellent mechanical property and thermal property, and the loss factor and the dielectric constant of the material can be effectively reduced.
Description
Technical Field
The application relates to a diamine monomer compound, a preparation method thereof, polyimide resin prepared from the diamine monomer compound, and a flexible film and electronic equipment using the polyimide resin.
Background
Signal transmission losses in printed circuit boards are due in part to losses caused by dielectric layers. The losses caused by the dielectric layer are generally related to the dielectric constant and the dielectric loss factor of the dielectric layer material. In addition, the polarity of the dielectric material affects the stability of electron transmission in the conductive wire, and if the polarity of the molecular structure in the insulating material is too large, the electrons in the conductive wire will be attracted by the dielectric layer after the circuit board is polarized, which seriously affects the stability of electron transmission. Therefore, how to effectively design the polymer structure of the dielectric layer, reduce the dielectric loss of the polymer material of the dielectric layer, and achieve a good insulation effect will become an important issue.
At present, liquid-crystal polymer (LCP) materials are widely used in printed circuit boards because of their Liquid-crystal structure and low dielectric loss. However, the LCP material has a liquid crystal structure with high sequential arrangement, so that the film forming processing characteristic is poor, the limitation of the film forming process is large, and the difficulty of pressing the LCP material and a copper plate after film forming to manufacture a copper-clad plate is also large.
Disclosure of Invention
In view of the above, in order to overcome at least one of the above drawbacks, it is necessary to provide a diamine monomer compound.
In addition, the application also provides a method for preparing the diamine monomer compound, polyimide resin prepared by applying the diamine monomer compound, and a flexible film and electronic equipment applying the polyimide resin.
The application provides a diamine monomer compound, the structural general formula of which is as follows:
wherein n is 1 Is composed of>1 is an integer.
In some possible embodiments, n 1 Is 2,3 or 4.
The application also provides a polyimide resin, which has a structural general formula as follows:
wherein X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, and m is 1 Is composed of>1 integer, m 2 Is composed of>1 integer, n 2 Is composed of>An integer of 1, and a further integer of 1,
the structural formula of Y is:
wherein n is 1 Is composed of>1 is an integer.
In some possible embodiments, the aromatic dianhydride residue or alicyclic dianhydride residue X is derived from one or more of the following compounds: <xnotran> ,3,3',4,4 ' - ,2,3,3 ',4' - ,2,3,5,6- ,2,3,6,7- ,1,4,5,8- ,2,6- -1,4,5,8- ,2,7- -1,4,5,8- ,2,3,6,7- -1,4,5,8- ,3,4,9,10- , -2,3,5,6- , -2,3,4,5- ,2,3,5,6- ,1,2,3,4- , -1,2,3,4- , -1,2,3,4- , -1,2,4,5- , -2,3,5,6- , [2.2.2] -7- -3,4,8,9- ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ', </xnotran> 4' -Diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
In some possible embodiments, the aromatic diamine residue or cycloaliphatic diamine residue R is derived from one or more of the following compounds: <xnotran> 4,4'- ,3,4' - ,1,4- (4- ) , , , ,1,5- ,2,6- , (4- ) , (3- ) , (4- ) , {4- (4- ) } ,4,4'- ,2,2' - -4,4'- ,2,2' - -4,4'- ,3,3' - -4,4'- ,3,3' - -4,4'- ,2,2', 3,3'- -4,4' - ,3,3',4,4' - -4,4'- ,2,2' - ( ) ,2,6,2 ',6' - ( ) ,2,2- [4- (3- ) ] ,2,2- [4- (4- ) ] ,2,2- (4- ) ,2,2- (3- ) 2,2- (3- -4- ) ,1,6- ,1,4- , </xnotran> 1, 3-cyclohexanediamine, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane and 4,4' -diamino-3, 3' -dimethylcyclohexylmethane.
In some possible embodiments, the polyimide resin is formed by polymerizing the diamine monomer compound with other aromatic diamine monomer or alicyclic diamine monomer, and aromatic dianhydride monomer or alicyclic dianhydride monomer.
In some possible embodiments, the molar ratio of the diamine monomer compound to the total diamine monomers of the other aromatic diamine monomers or alicyclic diamine monomers is 1.
In some possible embodiments, the ratio of the total moles of the diamine monomer compound and the other aromatic diamine monomer or alicyclic diamine monomer to the total moles of the aromatic dianhydride monomer or alicyclic dianhydride monomer is 0.9 to 1.1.
The present application also provides a method for preparing a diamine monomer compound, the method comprising:
preparation of diacid Compounds
Preparation of dinitro compounds
The dinitro compound (B-2) is subjected to hydrogenation reaction to obtain
Wherein n is 1 Is composed of>1 is an integer of 1.
The present application also provides a flexible film comprising the polyimide resin as described above.
The present application also provides an electronic device comprising a circuit board comprising a flexible film as described above.
Compared with the prior art, the diamine monomer compound introduces long even carbon chains and liquid crystal units, the long even carbon chains enable molecular chains to have flexibility, and compared with the traditional liquid crystal material, the regularity and rigidity of the molecular chains can be effectively reduced, so that the polyimide resin is convenient for film forming processing; long even carbon chains and liquid crystal units are introduced into a main chain, and the liquid crystal units are in rigid and forward arrangement, so that the polyimide resin has a liquid crystal form with high forward arrangement, can be annealed to improve crystallinity and dimensional stability, and has excellent mechanical and thermal properties, and loss factors (D) of the material can be effectively reduced f ) And Coefficient of Thermal Expansion (CTE), in addition, the long even carbon chain structure has hydrophobicity, and can increase the flexibility of the molecular chain, and effectively reduce the dielectric constant (D) of the material k ) And Coefficient of Thermal Expansion (CTE).
Drawings
Fig. 1 is a hydrogen spectrum of intermediate I provided in an example of the present application.
Fig. 2 is an infrared spectrum of intermediate I provided in an embodiment of the present application.
Fig. 3 is a hydrogen spectrum of intermediate II provided in an example of the present application.
Fig. 4 is an infrared spectrum of intermediate II provided in an embodiment of the present application.
FIG. 5 is a hydrogen spectrum of a diamine monomer as provided in an example of the present application.
FIG. 6 is an infrared spectrum of a diamine monomer provided in an example of the present application.
FIG. 7 is a DSC of a diamine monomer as provided in an example of the present application.
Fig. 8 is a polarization microscope photograph of a diamine monomer according to an embodiment of the present application.
Fig. 9 is a hydrogen spectrum of intermediate I' provided in another example of the present application.
FIG. 10 is an infrared spectrum of intermediate I' provided in another embodiment of the present application.
Fig. 11 is a hydrogen spectrum of intermediate II' provided in another example of the present application.
FIG. 12 is an infrared spectrum of intermediate II' provided in another embodiment of the present application.
FIG. 13 is a hydrogen spectrum of a diamine monomer as provided in another embodiment of the present application.
FIG. 14 is an infrared spectrum of a diamine monomer as provided in another embodiment of the present application.
FIG. 15 is a DSC of a diamine monomer provided in another embodiment of the present application.
FIG. 16 is a polarization micrograph of a diamine monomer according to another embodiment of the present application.
FIG. 17 is an XRD spectrum of polymer examples 1-3 of the present application versus comparative example 1.
FIG. 18 is an XRD spectrum of polymers of examples 4-6 of the present application versus comparative example 1.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solution of the present invention will be clearly and completely described with reference to the specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The names of the technical means used in the description of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.
The embodiments described below and the features of the embodiments can be combined with each other without conflict.
To prepare polyimides with an excellent balance of properties, they are generally prepared using rigid aromatic dianhydride and diamine structures to enhance intramolecular and intermolecular interactions. However, the film-forming processability of the polyimide film is also poor. In order to obtain a polyimide having excellent overall properties and being easily filmed, a polyimide is generally usedThe main chain or side chain of the imine is introduced with long carbon chain or flexible group (for example, C = O, -O-, -S-, -SO) 2 -、-CH 2 -、-C(CH 3 ) 2 -) to reduce the rigidity of the backbone, thereby reducing the glass transition temperature (Tg) and melting point (Tm) of the polyimide. The long carbon chain or flexible group is usually introduced by a monomer (diamine monomer, dianhydride monomer) for synthesizing polyimide.
The embodiment of the application provides a diamine monomer compound which can be used for preparing polyimide resin which has good dielectric property, mechanical property and thermal property and is easy to form a film.
The diamine monomer compound has a general structural formula:
wherein n is 1 Is composed of>1 is an integer.
In some embodiments, n 1 Is 2,3 or 4.
The long carbon chain is introduced into the diamine monomer, and the symmetry and the regularity of the molecular chain of the polyimide polymer are reduced through the structural asymmetry of the long carbon chain, so that the Tg and the Tm of the polyimide are reduced. The selection of the number of carbons in the long carbon chain of the diamine monomer, especially the selection of the odd-numbered carbons and the even-numbered carbons, affects the molecular arrangement and thus the structural configuration of the formed liquid crystal, which is called the parity effect. The odd carbon chains make the molecules more bent, have greater disorder, and require higher temperature to form a liquid crystal phase, and the formed liquid crystal is a bent liquid crystal (also called banana-shaped liquid crystal), which mostly has ferroelectricity, and the ferroelectric material is easily polarized by an electric field to generate a phenomenon of molecular inversion, so that the material containing the odd carbon chains is mostly applied to a storage element or a capacitor. Even carbon chains can facilitate the molecules to form liquid crystal phases, typically common lamellar or smectic liquid crystals. Therefore, the long carbon chain structure introduced into the diamine monomer compound contains even number of carbon, and meanwhile, liquid crystal units with ester groups are introduced into two ends of the even number of carbon chains, so that the regularity of molecular chains can be effectively reduced, the rigidity of the molecular chains is reduced, the flexibility of the molecular chains is increased, the thermal expansion coefficient of materials is favorably reduced, and the dimensional stability is improved.
The embodiment of the present application also provides a polyimide resin obtained by polymerizing the diamine monomer compound, an aromatic or alicyclic diamine monomer different from the diamine monomer compound, and an aromatic or alicyclic dianhydride monomer.
The structural general formula of the polyimide resin is as follows:
In the present application, the aromatic or alicyclic dianhydride monomer, the aromatic or alicyclic diamine monomer, and the diamine monomer compound are monomers polymerized to form the polyimide resin, and the structural formula of the polyimide resin formed by polymerizing the aromatic or alicyclic dianhydride monomer and the aromatic or alicyclic diamine monomer is not a single monomer compound, but a group, and is defined as a residue.
The polyimide resin comprises n 2 A plurality of repeating units, each repeating unit comprising m 1 A sum of m 2 M in the present application 1 A sum of m 2 The polyimide resin is randomly arranged on the main chain of the polyimide resin and is randomly distributed.
The aromatic dianhydride residue or alicyclic dianhydride residue X is derived from one or more of the following compounds: <xnotran> ,3,3',4,4 ' - ,2,3,3 ',4' - ,2,3,5,6- ,2,3,6,7- ,1,4,5,8- ,2,6- -1,4,5,8- ,2,7- -1,4,5,8- ,2,3,6,7- -1,4,5,8- ,3,4,9,10- , -2,3,5,6- , -2,3,4,5- ,2,3,5,6- ,1,2,3,4- , -1,2,3,4- , -1,2,3,4- , -1,2,4,5- , -2,3,5,6- , [2.2.2] -7- -3,4,8,9- ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ', </xnotran> 4' -Diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
The aromatic diamine residue or the alicyclic diamine residue R is derived from one or more of the following compounds: <xnotran> 4,4'- ,3,4' - ,1,4- (4- ) , , , ,1,5- ,2,6- , (4- ) , (3- ) , (4- ) , {4- (4- ) } ,4,4'- ,2,2' - -4,4'- ,2,2' - -4,4'- ,3,3' - -4,4'- ,3,3' - -4,4'- ,2,2', 3,3'- -4,4' - ,3,3',4,4' - -4,4'- ,2,2' - ( ) ,2,6,2 ',6' - ( ) ,2,2- [4- (3- ) ] ,2,2- [4- (4- ) ] ,2,2- (4- ) ,2,2- (3- ) 2,2- (3- -4- ) ,1,6- ,1,4- , </xnotran> 1, 3-cyclohexanediamine, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane and 4,4' -diamino-3, 3' -dimethylcyclohexylmethane.
In the structure of the polyimide resin, long even carbon chains are introduced through the diamine monomer compound, and the long even carbon chains enable the molecular chain to have flexibility, so that compared with the traditional liquid crystal material, the regularity and rigidity of the molecular chain can be effectively reduced, and the polyimide resin is convenient for film forming processing; long even carbon chains and liquid crystal units (such as ester mesogen) are introduced into the main chain, and the liquid crystal units have rigidity and forward arrangement, so that the polyimide resin has a liquid crystal form with high forward arrangement, can be annealed to improve the crystallinity, improve the dimensional stability, enable the material to have excellent mechanical property and thermal property, and simultaneously effectively reduce the loss factor (D) of the material f ) And Coefficient of Thermal Expansion (CTE), in addition, the long even carbon chain structure has hydrophobicity, and can increase the flexibility of the molecular chain, and the dielectric constant (D) of the material can be effectively reduced by matching the liquid crystal unit structure k ) And Coefficient of Thermal Expansion (CTE).
The present application also provides a flexible film comprising the polyimide resin as described above.
The present application also provides an electronic device comprising a circuit board comprising a flexible film as described above.
The flexible film is attached to the surface of the base material, the molecular weight flexibility of the polyimide resin is improved, the polarity is reduced, the film forming property is improved, the interface bonding force between the prepared flexible film and the base material is strong, and the prepared circuit board has excellent mechanical property and electrical property; and the polyimide resin has low thermal expansion coefficient, so that the flexible film can not have the problems of peeling, cracking, warping and the like when the circuit board is prepared.
The present application also provides a method for preparing a diamine monomer compound, the method comprising:
preparation of a composition comprisingEven carbon chain diacid compound
Wherein n is 1 Is composed of>1, in particular n 1 May be 2,3 or 4.
Preparation of dinitro compounds containing even carbon chains and liquid crystal cells
The dinitro compound (B-2) is subjected to hydrogenation reaction to obtain
The preparation method of the polyimide resin comprises the following steps:
preparing diamine monomer compound with the structural general formula
The diamine monomer compound is polymerized with other aromatic diamine monomer or alicyclic diamine monomer and aromatic dianhydride monomer or alicyclic dianhydride monomer to obtain
Wherein X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, and m is 1 Is composed of>1 integer, m 2 Is composed of>1 integer, n 2 Is composed of>1 is an integer of 1.
In some embodiments, the molar ratio of total diamine monomers to total dianhydride monomers in the preparation of the polyimide resin is 0.9 to 1.1, preferably 1. That is, the ratio of the total number of moles of the diamine monomer compound and the other aromatic diamine monomer or alicyclic diamine monomer to the total number of moles of the aromatic dianhydride monomer or alicyclic dianhydride monomer is 0.9 to 1.1.
In some embodiments, the ratio of the moles of the diamine monomer compound to the moles of all of the other aromatic diamine monomers or cycloaliphatic diamine monomers is 1.
The examples of the present application will be further described with reference to specific examples.
Monomer embodiment one
Preparation of monomers:
in the first step, aqueous sodium hydroxide (NaOH 2.0g + deionized water 10 mL) was charged into a 100mL three-necked reactor, 3mL of ethanol was added, parahydroxybenzoic acid (2.76g, 0.02mol) was dissolved in the aqueous sodium hydroxide with stirring, heated to 85 ℃ under reflux, and 1, 4-dibromobutane (2.20g, 0.01mmol) was added dropwise through a feed tube and reacted for 12 hours under a nitrogen atmosphere. And after the reaction is finished, performing air suction filtration on the product, taking a filter cake, dissolving the filter cake in hot water at 60 ℃, dripping hydrochloric acid to acidify until the pH is 2.0, wherein a precipitate appears, performing air suction filtration on the precipitate, taking the filter cake, washing the filter cake with deionized water for a plurality of times, and drying the filter cake in a vacuum environment at 110 ℃ to obtain an intermediate product I.
Hydrogen spectrum from FIG. 1 1 H-NMR(ppm,DMSO-d 6 ) As can be seen, δ =1.87 (2h 1 )，4.10(2H,H 2 )，7.00(2H,H 4 ,H 8 )，7.86(2H,H 5 ,H 7 )，12.63(1H,H 10 ). As can be seen from the infrared spectrum of FIG. 2, the-OH signal peak in the molecular structure disappears at 2400-3500 cm -1 Signal peaks for carboxylic acid were generated, demonstrating successful synthesis of diacid structure.
In the second step, intermediate I (0.933 g) was taken and charged into a 100ml three-necked reactorAdding thionyl chloride (SOCl) 2 10 mL) and adding Dimethylformamide (DMF) as an initiator, reacting for 6h at 65 ℃ for acyl chlorination of the terminal functional group, after the reaction is finished, using a decompression concentration device to extract excessive thionyl chloride to obtain a diacid chloride product, and then pouring tetrahydrofuran (THF, 20 mL) into the diacid chloride product to prepare a diacid chloride solution.
Adding p-nitrophenol (0.776g, 2.79mmol x 2), triethylamine (Et 3N,0.847g,2.79mmol x 3) and tetrahydrofuran (THF, 20 mL) into another three-neck reactor, stirring for 1h while cooling, adding the diacid chloride solution dropwise through a feeding pipe, stirring for 1h, reacting at normal temperature for 12h, naturally precipitating triethylamine salts during the reaction, filtering after the reaction is finished, taking a filter cake, washing the salts, washing with ethanol, and drying in a vacuum environment at 75 ℃ to obtain an intermediate product II.
Hydrogen spectrum from FIG. 3 1 H-NMR (ppm, DMSO-d 6) showed that delta =1.92 (2H 1 )，4.18(2H,H 2 )，7.14(2H,H 4 ,H 8 )，8.09(2H,H 5 ,H 7 )，7.59(2H,H 11 ,H 15 )，8.33(2H,H 12 ,H 14 ). The signal peak for the carboxylic acid group disappeared at 1347cm, as seen by the infrared spectrum (FITR) of FIG. 4 -1 produce-NO 2 Signal peaks. The intermediate product II can be judged to be successfully synthesized by combining the hydrogen spectrum and the infrared spectrum.
Thirdly, adding the intermediate product II (10 g) into a 100mL high-pressure reactor, adding DMF (80 mL) and palladium-carbon (Pd/C, 0.4 g), repeatedly introducing nitrogen for three times, and finally reacting at 50 ℃ under the hydrogen pressure of 140Pa until the hydrogen pressure does not decrease any more, wherein the hydrogen pressure reaches constant pressure, which indicates that the reaction is finished. After the reaction is finished, the diatomite is placed on a ceramic funnel and is paved, air-suction filtration is carried out to remove palladium carbon, the filtrate is collected and poured into deionized water to be separated out, the ethanol is used for cleaning, air-suction filtration is carried out to obtain a filter cake, and the filter cake is dried under the vacuum condition at the temperature of 110 ℃ to obtain the diamine monomer compound A.
Hydrogen spectrum from FIG. 5 1 H-NMR (ppm, DMSO-d 6) showed that delta =1.91 (2H 1 )、4.15(2H,H 2 )，6.56(2H,H 4 ,H 8 )，6.85(2H,H5,H7)，7.09(2H,H 12 ,H 14 )，8.02(2H,H 11 ,H 15 )，5.10(2H,H 16 ). 1347cm as seen by the infrared Spectrum (FITR) of FIG. 6 -1 of-NO 2 The signal peak disappeared, yielding a peak at 3342cm -1 And 3454cm -1 Of (2) is-NH 2 The stretching vibration peak of (1). The successful synthesis of diamine A can be judged by combining the hydrogen spectrum and the infrared spectrum. The melting point range was 173 ℃ to 222 ℃, the melting endotherm was 195 ℃ and the enthalpy (Delta H) was 90.76J/g, as judged by the endotherm in the differential scanning thermal analysis (DSC) chart of FIG. 7. Wherein FIG. 8 is a polarizing microscope (POM) diagram of diamine A, wherein the temperature rise rate of diamine A is 10 ℃/min, diamine A has no liquid crystal phase at room temperature and 200 ℃, when the temperature reaches 220 ℃, liquid crystal phase begins to form, and as the temperature rises, the liquid crystal phase appears in large quantity, the maximum liquid crystal phase is displayed at 250 ℃ and the liquid crystal phase flows slowly, and the liquid crystal phase is nematic liquid crystal; the diamine A remains crystalline again when the temperature reaches 300 ℃. By contrast with DSC and POM, it was observed that diamine A having a long carbon chain of four carbons maintained a liquid crystal state even at the cyclization temperature, and it was found that diamine residues having even carbon chains still had a regularly aligned liquid crystal state after cyclization of polyamic acid to form polyimide.
Monomer example II
Preparation of monomers (monomers structurally different from example one):
in the first step, aqueous sodium hydroxide (NaOH 2.0g + deionized water 10 mL) was charged into a 100mL three-necked reactor, 3mL of ethanol was added, parahydroxybenzoic acid (2.76g, 0.02mol) was dissolved in the aqueous sodium hydroxide with stirring, heated to 85 ℃ under reflux, and 1, 6-dibromohexane (2.44g, 0.01mmol) was added dropwise through a feed tube and reacted for 12 hours under a nitrogen atmosphere. And after the reaction is finished, performing air suction filtration on the product, taking a filter cake, dissolving the filter cake in hot water at 60 ℃, dripping hydrochloric acid into the hot water to acidify until the pH is 2.0, wherein a precipitate appears, performing air suction filtration on the precipitate, taking the filter cake, washing the filter cake with deionized water for a plurality of times, and drying the filter cake in a vacuum environment at 110 ℃ to obtain an intermediate product I'.
Hydrogen spectrum from FIG. 9 1 H-NMR(ppm,DMSO-d 6 ) As can be seen, δ =1.44 (4h 1 )，1.73(4H,H 2 )，4.0(4H,H 3 )，6.96(2H,H 5 ,H 9 ),7.87(2H,H 6 ,H 8 )，12.6(1H,H 11 ). As can be seen from the infrared spectrum of FIG. 10, the-OH signal peak in the molecular structure disappeared at 2400-3500 cm -1 Signal peaks for carboxylic acid were generated, demonstrating successful synthesis of diacid structure.
In the second step, intermediate I' (1.0 g) was taken and charged in a 100ml three-necked reactor, and thionyl chloride (SOCl) was added 2 10 mL) and Dimethylformamide (DMF) was added as an initiator, and the reaction was carried out at 65 ℃ for 6 hours for terminal functional group acylation, after the reaction was completed, excess thionyl chloride was removed using a vacuum concentration apparatus to obtain a diacylchloride product, and then tetrahydrofuran (THF, 20 mL) was poured into the diacylchloride product to prepare a diacylchloride solution.
Adding p-nitrophenol (0.776g, 2.79mmol x 2), triethylamine (Et 3N,0.847g,2.79mmol x 3) and tetrahydrofuran (THF, 20 mL) into another three-neck reactor, stirring for 1h in an ice bath, dropwise adding the diacid chloride solution into the reactor by using a feeding pipe, stirring for 1h, reacting at normal temperature for 12h, naturally precipitating triethylamine salts in the reaction process, filtering after the reaction is finished, taking a filter cake, washing the salts, washing the filter cake by using ethanol, and drying the filter cake in a vacuum environment at 75 ℃ to obtain an intermediate product II'.
Hydrogen spectrum from FIG. 11 1 H-NMR (ppm, DMSO-d 6) showed that δ =1.52 (4H 1 )，1.77(4H,H 2 )，4.17(4H,H 3 )，7.11(4H,H 5 ,H 9 )，7.58(4H,H 12 ,H 16 )，8.10(4H,H 6 ,H 8 )，8.32(4H,H 13 ,H 15 ). The signal peak for the carboxylic acid group disappeared at 1347cm, as seen by the infrared spectrum (FITR) in FIG. 12 -1 produce-NO 2 Signal peaks. The intermediate product II' can be judged to be successfully synthesized by combining the hydrogen spectrum and the infrared spectrum.
And thirdly, adding the intermediate product II' (10 g) into a 100mL high-pressure reactor, adding DMF (80 mL) and palladium-carbon (Pd/C, 0.4 g), repeatedly introducing nitrogen for three times, and finally reacting at 50 ℃ under the hydrogen pressure of 140Pa until the hydrogen pressure does not decrease any more, wherein the hydrogen pressure reaches constant pressure, namely the reaction is finished. After the reaction is finished, the diatomite is placed on a ceramic funnel and is paved, air-extracting filtration is carried out to remove palladium carbon, the filtrate is collected and poured into deionized water to be separated out, the ethanol is used for cleaning, air-extracting filtration is carried out to obtain a filter cake, and the filter cake is dried under the vacuum condition at the temperature of 110 ℃ to obtain the diamine monomer compound B.
Hydrogen spectrum from FIG. 13 1 H-NMR (ppm, DMSO-d 6) showed that δ =1.50 (2H 1 )，1.78(2H,H 2 )，4.07(2H,H 3 )，5.05(2H,H 17 )，6.58(2H,H 5 ,H 9 )，6.85(2H,H 6 ,H 8 )，7.07(2H,H 13 ,H 15 )，8.04(2H,H 12 ,H 16 ). 1346cm as seen by the infrared Spectrum (FITR) of FIG. 14 -1 of-NO 2 The signal peak disappeared and it appeared to be at 3367cm -1 And 3460cm -1 Of (2) is-NH 2 The stretching vibration peak of (1). The successful synthesis of diamine B can be judged by combining the hydrogen spectrum and the infrared spectrum. The melting point range was 183 ℃ to 204 ℃, the melting endotherm was 195 ℃ and the enthalpy (Delta H) was 107.89J/g, as judged by the endotherms in the differential scanning thermal analysis (DSC) plot of FIG. 15. Wherein FIG. 16 is a polarization microscope of diamine BA mirror (POM) diagram, wherein the heating rate of the diamine B is 10 ℃/min, the diamine B does not have any liquid crystal phase at room temperature and 200 ℃, the liquid crystal phase begins to form when the temperature reaches 220 ℃, the liquid crystal phase appears in a large amount along with the temperature rise, the maximum liquid crystal phase is displayed at 240 ℃ and the liquid crystal phase slowly flows, and the liquid crystal phase is nematic liquid crystal; the diamine B remains crystalline again when the temperature reaches 300 ℃. By contrast with DSC and POM, it was observed that diamine B having a long carbon chain of four carbons maintained a liquid crystal state even at the cyclization temperature, and it was found that diamine residues having even carbon chains still had a regularly aligned liquid crystal state after cyclization of polyamic acid to form polyimide.
Example 1 Polymer
Diamine a (0.57g, 1.11mmol) and 4,4' -diaminodiphenyl ether (ODA, 2.00g, 9.99mmol) as a monomer were charged into a reaction flask under nitrogen protection, and N, N-dimethylacetamide (DMAc, 14.97 g) as a solvent was added thereto and stirred at room temperature until dissolved, and then pyromellitic dianhydride (PMDA, 2.42g, 11.1mmol) as a monomer was slowly added and stirred at room temperature for 24 hours to obtain a polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m, and annealing to improve the crystallinity.
Example II Polymer
Diamine A (0.96g, 1.87mmol) and the monomer 4,4' -diaminodiphenyl ether (ODA, 1.50g, 7.49mmol) were charged into a reaction flask under nitrogen protection, and the solvent N, N-dimethylacetamide (DMAc, 13.51 g) was added thereto and stirred at room temperature until dissolved, and then the monomer pyromellitic dianhydride (PMDA, 2.04g, 9.36mmol) was slowly added thereto and stirred at room temperature for 24 hours to obtain a polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m, and annealing to improve the crystallinity.
Polymer example III
Diamine a (1.10g, 2.14mmol) and 4,4' -diaminodiphenyl ether (ODA, 1.00g.4.99mmol) as a monomer were charged into a reaction flask under nitrogen protection, and N, N-dimethylacetamide (DMAc, 10.96 g) as a solvent was added thereto, and the mixture was stirred at room temperature until the solvent was dissolved, and then pyromellitic dianhydride (PMDA, 1.56g, 9.36mmol) as a monomer was slowly added thereto, and the mixture was stirred at room temperature for 24 hours, thereby obtaining a polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m, and annealing to improve the crystallinity.
Polymer example four
Diamine B (0.6 g, 1.11mmol) and monomer 4,4' -diaminodiphenyl ether (ODA, 2.00g, 9.99mmol) were added to a reaction flask under nitrogen protection, solvent N, N-dimethylacetamide (DMAc, 15.06 g) was added thereto and stirred at room temperature until dissolved, monomer pyromellitic dianhydride (PMDA, 2.42g, 11.1mmol) was slowly added thereto and stirred at room temperature for 24 hours to obtain a polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m, and annealing to improve the crystallinity.
Polymer example five
Diamine B (1.01g, 1.87mmol) and the monomer 4,4' -diaminodiphenyl ether (ODA, 1.50g, 7.49mmol) were charged into a reaction flask under nitrogen protection, and the solvent N, N-dimethylacetamide (DMAc, 13.66 g) was added thereto and stirred at room temperature until dissolved, and then the monomer pyromellitic dianhydride (PMDA, 2.04g, 9.36mmol) was slowly added thereto and stirred at room temperature for 24 hours to obtain a polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m, and annealing to improve the crystallinity.
Polymer example six
Diamine B (1.16g, 2.14mmol) and monomer 4,4' -diaminodiphenyl ether (ODA, 1.00g.4.99mmol) were added to a reaction flask under nitrogen protection, solvent N, N-dimethylacetamide (DMAc, 11.14 g) was added thereto and stirred at room temperature until dissolved, monomer pyromellitic dianhydride (PMDA, 1.56g, 9.36mmol) was slowly added thereto and stirred at room temperature for 24 hours to obtain a polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m, and annealing to improve the crystallinity.
Comparative Polymer example 1
Under the protection of nitrogen, monomer 4,4' -diaminodiphenyl ether (ODA, 2.00g, 9.99mmol) is added into a reaction bottle, solvent N, N-dimethylacetamide (DMAc, 12.54 g) is added, stirring is carried out at room temperature until the monomer is dissolved, monomer pyromellitic dianhydride (PMDA, 2.18g, 9.99mmol) is slowly added, and stirring is carried out at room temperature for 24 hours, so as to obtain the polyamic acid composition.
Coating the polyamic acid composition on a copper foil substrate, keeping the temperature of the copper foil substrate at 100-150 ℃ for 10-15min, removing the solvent to form a polyamic acid film, and then keeping the temperature of the copper foil substrate at 300 ℃ for 30-60 min in a nitrogen environment to cyclize the polyamic acid to form a polyimide film with the thickness of about 12-50 mu m.
TABLE 1
Note: CET results from thermomechanical analysis (TMA) testing.
The temperature at which the nematic liquid crystal phase of the diamine A and diamine B monomers is formed can be found by the above DSC and POM analysisThe range is 240 ℃ to 270 ℃, the liquid crystal phase is still kept at 300 ℃, diamine A or diamine B is further reacted with ODA and PMDA to prepare polyamic acid, the polyamic acid is coated on a copper foil substrate and is kept at the temperature of 100 ℃ to 150 ℃ for 10 min to 15min, a solvent is removed, a polyamic acid film is formed, then high-temperature cyclization is carried out at the temperature of 300 ℃ in a nitrogen environment to prepare a Polyimide (PI) film, the PI films of polymer examples 1 to 6 are identified by a high-resolution X-ray diffractometer (XRD), as shown in figures 17 and 18, 2 theta of comparative example 1 and polymer examples 1 to 6 has a wide absorption peak near 19 degrees, the typical absorption peak of nematic liquid crystal is consistent with the POM analysis result of diamine A or diamine B, and the fact that a diamine monomer (diamine A or diamine B) forms a film in the nematic liquid crystal phase is confirmed. In addition, examples 1-3 have crystal absorption peaks (2 θ is 38 ° and 44 °), while examples 4-6 have no significant crystal absorption peak, and the increase of the carbon chain length of the even carbon chain structure is verified, which is helpful for increasing the molecular chain flexibility of the PI film, thereby increasing the toughness of the polymer film, reducing the crystallinity (examples 4-6 have no significant crystal absorption peaks at 2 θ of 38 ° and 44 °), and increasing the crystallinity arrangement structure, thereby reducing the loss factor (D) f ) And Coefficient of Thermal Expansion (CTE).
The diamine A is adopted in polymer examples 1-3, and the diamine B is adopted in polymer examples 4-6, wherein the diamine B has a long carbon chain with more carbon atoms, increased molecular chain flexibility, increased crystalline arrangement structure and reduced polarity, and is more favorable for reducing the loss factor (D) of the material than the diamine A with less carbon atoms f ) And Coefficient of Thermal Expansion (CTE), the presence of long even carbon chains in combination with the liquid crystal cell structure effectively improved the toughness and coefficient of thermal expansion of the material, thus, polymer examples 4-6D f Better CTE and toughness.
By introducing long even carbon chains and liquid crystal cells in the main chain, the loss factor (D) is significantly reduced compared to comparative example 1 f ) (reduction by 10-70%) and dielectric constant (D) k ) (by 2-9%), meanwhile, compared with the comparative example 1, the polymer examples 1-6 have better dielectric property and mechanical property, good thermal property and excellent film forming processability, and are beneficial to reducing the film forming processing difficulty of the high polymer material with the liquid crystal unit structure.
In conclusion, the diamine monomer compound introduces long even carbon chains and liquid crystal units, and the long even carbon chains enable the molecular chain to have flexibility, so that compared with the traditional liquid crystal material, the regularity and rigidity of the molecular chain can be effectively reduced, and the polyimide resin is convenient for film forming processing; the long even carbon chains and the liquid crystal unit (such as an ester liquid crystal cell) are introduced into the main chain, and the liquid crystal unit has rigidity and forward arrangement, so that the polyimide resin has a liquid crystal form with high forward arrangement, can be annealed to improve the crystallinity, and improve the dimensional stability, so that the material has excellent mechanical property and thermal property, and can effectively reduce the loss factor and the thermal expansion coefficient of the material.
Claims (11)
1. A diamine monomer compound, wherein the diamine monomer compound has a general structural formula:
wherein n is 1 Is composed of>1 is an integer.
2. Diamine monomer compound according to claim 1, characterized in that n1 takes on the value 2,3 or 4.
3. A polyimide resin is characterized in that the structural general formula of the polyimide resin is as follows:
wherein X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, m 1 Is composed of>1 integer, m 2 Is composed of>1, n is an integer of 2 Is composed of>An integer of 1, and a further integer of 1,
the structural formula of Y is:
wherein n is 1 Is composed of>1 is an integer.
4. The polyimide resin of claim 3, wherein the aromatic dianhydride residue or the alicyclic dianhydride residue X is derived from one or more of the following compounds: <xnotran> ,3,3',4,4 ' - ,2,3,3 ',4' - ,2,3,5,6- ,2,3,6,7- ,1,4,5,8- ,2,6- -1,4,5,8- ,2,7- -1,4,5,8- ,2,3,6,7- -1,4,5,8- ,3,4,9,10- , -2,3,5,6- , -2,3,4,5- ,2,3,5,6- ,1,2,3,4- , -1,2,3,4- , -1,2,3,4- , -1,2,4,5- , -2,3,5,6- , [2.2.2] -7- -3,4,8,9- ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ',4' - ,3,3',4,4 ' - ,2,2 ',3,3' - ,2,3,3 ', </xnotran> 4' -Diphenyl ether tetracarboxylic dianhydride, 2- [ bis (3, 4-dicarboxyphenyl) ] hexafluoropropane dianhydride, 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
5. The polyimide resin of claim 3, wherein the aromatic diamine residues or cycloaliphatic diamine residues R are derived from one or more of the following compounds: <xnotran> 4,4'- ,3,4' - ,1,4- (4- ) , , , ,1,5- ,2,6- , (4- ) , (3- ) , (4- ) , {4- (4- ) } ,4,4'- ,2,2' - -4,4'- ,2,2' - -4,4'- ,3,3' - -4,4'- ,3,3' - -4,4'- ,2,2', 3,3'- -4,4' - ,3,3',4,4' - -4,4'- ,2,2' - ( ) ,2,6,2 ',6' - ( ) ,2,2- [4- (3- ) ] ,2,2- [4- (4- ) ] ,2,2- (4- ) ,2,2- (3- ) 2,2- (3- -4- ) ,1,6- ,1,4- , </xnotran> 1, 3-cyclohexanediamine, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane and 4,4' -diamino-3, 3' -dimethylcyclohexylmethane.
6. The polyimide resin according to claim 3, wherein the diamine monomer compound is formed by polymerizing the diamine monomer compound with another aromatic diamine monomer or alicyclic diamine monomer and an aromatic dianhydride monomer or alicyclic dianhydride monomer.
7. The polyimide resin according to claim 6, wherein the molar ratio of the diamine monomer compound to the total diamine monomers of the other aromatic diamine monomers or alicyclic diamine monomers is 1.
8. The polyimide resin according to claim 6, wherein the ratio of the total number of moles of the diamine monomer compound and the other aromatic diamine monomer or alicyclic diamine monomer to the total number of moles of the aromatic dianhydride monomer or alicyclic dianhydride monomer is 0.9 to 1.1.
9. A method for producing a diamine monomer compound, comprising:
preparation of diacid Compounds
Preparation of dinitro compounds
The dinitro compound (B-2) is subjected to hydrogenation reaction to obtain
Wherein n is 1 Is composed of>1 is an integer.
10. A flexible film comprising the polyimide resin according to any one of claims 3 to 8.
11. An electronic device, characterized in that the electronic device comprises a circuit board comprising the flexible film of claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110982729.3A CN115724755A (en) | 2021-08-25 | 2021-08-25 | Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110982729.3A CN115724755A (en) | 2021-08-25 | 2021-08-25 | Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115724755A true CN115724755A (en) | 2023-03-03 |
Family
ID=85289677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110982729.3A Pending CN115724755A (en) | 2021-08-25 | 2021-08-25 | Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115724755A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212464A (en) * | 2013-05-29 | 2014-12-17 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polyamide acid and imidized polymers thereof, and diamine compound |
| CN104419429A (en) * | 2013-09-02 | 2015-03-18 | Jsr株式会社 | Liquid crystal aligning agent and film thereof, display component, film and manufacturing method thereof, polymer and compound |
-
2021
- 2021-08-25 CN CN202110982729.3A patent/CN115724755A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212464A (en) * | 2013-05-29 | 2014-12-17 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polyamide acid and imidized polymers thereof, and diamine compound |
| CN104419429A (en) * | 2013-09-02 | 2015-03-18 | Jsr株式会社 | Liquid crystal aligning agent and film thereof, display component, film and manufacturing method thereof, polymer and compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101492597B1 (en) | Liquid Crystal Thermoset Monomer or oligomer and Thermosetting Liquid Crystal Polymer Composition Comprising The Same and Printed Circuit Board Using The Same | |
| KR101866834B1 (en) | Liquid crystal aligning agent and liquid crystal display device | |
| KR101148384B1 (en) | Composition for forming substrate, and prepreg and substrate using the same | |
| JP5814503B2 (en) | Thermosetting composition and printed wiring board using the same | |
| KR20100120498A (en) | Composition for forming substrate, and prepreg and substrate using the same | |
| JP2009286854A (en) | Polyesterimide precursor and polyesterimide | |
| TW202140613A (en) | Liquid crystal polyester, method for producing liquid crystal polyester, resin solution, metal-clad laminate and method for producing metal-clad laminate | |
| JP5231174B2 (en) | Substrate-forming composition, prepreg, substrate and thermosetting aromatic oligomer | |
| CN112625017B (en) | Amide dianhydride, preparation method and application thereof | |
| CN116003789A (en) | Polyamide acid solution, polyimide film, and preparation methods and applications thereof | |
| CN115724755A (en) | Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device | |
| CN112409311A (en) | Dianhydride, polyimide film and application thereof | |
| TWI833110B (en) | Diamine monomer compound and method for preparing the same, resin, flexible film and electronic device | |
| JP5721570B2 (en) | Composition for producing thermosetting resin, cured product thereof, prepreg and prepreg laminate including the cured product, and metal foil laminate and printed wiring board employing the prepreg or prepreg laminate | |
| KR20090045843A (en) | Composition for forming board and printed circuit board using the same | |
| JP2009286853A (en) | Polyesterimide precursor and polyesterimide | |
| CN115724757A (en) | Diamine monomer compound, preparation method thereof, resin, flexible film and electronic device | |
| US20230086746A1 (en) | Diamine monomer compound, method for preparing the same, resin, flexible film, and electronic device | |
| JP2883769B2 (en) | Polyimide copolymer and method for producing the same | |
| CN112831183B (en) | High-strength high-heat-stability high-transparency low-glass-transition-temperature polyimide film and preparation method thereof | |
| TWI833608B (en) | Polyimide precursor and polyimide made therefrom | |
| CN114656635B (en) | Preparation method of polyimide printed circuit board with high peel strength and low dielectric constant | |
| JP6462236B2 (en) | Polyimide and heat resistant film | |
| JP4017034B2 (en) | New polyimide film | |
| CN117794048A (en) | Metal-clad laminate, circuit board, electronic device, and electronic apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |