CN109161018A - A kind of aromatic series super-branched polyimide and its preparation method and application - Google Patents
A kind of aromatic series super-branched polyimide and its preparation method and application Download PDFInfo
- Publication number
- CN109161018A CN109161018A CN201810859390.6A CN201810859390A CN109161018A CN 109161018 A CN109161018 A CN 109161018A CN 201810859390 A CN201810859390 A CN 201810859390A CN 109161018 A CN109161018 A CN 109161018A
- Authority
- CN
- China
- Prior art keywords
- hyperbranched
- aromatic
- polyimide
- preparation
- hyperbranched polyimide
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 73
- 239000004642 Polyimide Substances 0.000 title claims abstract description 67
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 6
- 238000005371 permeation separation Methods 0.000 claims abstract 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 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
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229920005575 poly(amic acid) Polymers 0.000 claims 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 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 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- WULRQNZZLOZPPE-UHFFFAOYSA-N 2,4,6-tris(4-aminophenyl)phenol Chemical compound C1=CC(=CC=C1C2=CC(=C(C(=C2)C3=CC=C(C=C3)N)O)C4=CC=C(C=C4)N)N WULRQNZZLOZPPE-UHFFFAOYSA-N 0.000 description 1
- LDQLRBQBPBAALX-UHFFFAOYSA-N 2,6-diphenylbenzenethiol Chemical compound SC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 LDQLRBQBPBAALX-UHFFFAOYSA-N 0.000 description 1
- SJODITPGMMSNRF-UHFFFAOYSA-N 2-aminofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C2=C1 SJODITPGMMSNRF-UHFFFAOYSA-N 0.000 description 1
- XGEXIZVFGKFXCL-UHFFFAOYSA-N 3-[3,4-bis(3-aminophenyl)phenyl]aniline Chemical compound C1=CC(=CC(=C1)N)C2=CC(=C(C=C2)C3=CC(=CC=C3)N)C4=CC(=CC=C4)N XGEXIZVFGKFXCL-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- GTZJIQDLDUWGMH-UHFFFAOYSA-N 4-aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1.NC(=O)C1=CC=C(N)C=C1 GTZJIQDLDUWGMH-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- HZCOMUABODMLDY-UHFFFAOYSA-N 5-[3,5-bis(5-aminothiophen-2-yl)phenyl]thiophen-2-amine Chemical compound C1=C(SC(=C1)N)C2=CC(=CC(=C2)C3=CC=C(S3)N)C4=CC=C(S4)N HZCOMUABODMLDY-UHFFFAOYSA-N 0.000 description 1
- VGSDPJSSDBNFFN-UHFFFAOYSA-N 6-[3,5-bis(6-aminonaphthalen-2-yl)phenyl]naphthalen-2-amine Chemical compound C1(=CC(=CC(=C1)C=1C=C2C=CC(=CC2=CC=1)N)C=1C=C2C=CC(=CC2=CC=1)N)C=1C=C2C=CC(=CC2=CC=1)N VGSDPJSSDBNFFN-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 108700009934 HBPI Proteins 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明公开的是一种芳香族超支化聚酰亚胺及其制备方法和用途。该类超支化聚酰亚胺材料以芳香族三胺和各种四酸二酐为原料，通过酰亚胺化制成。该类超支化聚酰亚胺具有较高的玻璃化转变温度和热稳定性，较低的热膨胀系数以及优异的溶解性。本发明的合成方法工艺简单、多样，因而适于工业生产。本发明所公开的超支化聚酰亚胺在耐高温领域以及气体渗透分离膜等材料领域具有较好的应用前景。
The invention discloses an aromatic hyperbranched polyimide and its preparation method and application. This type of hyperbranched polyimide material is prepared by imidization with aromatic triamine and various tetraacid dianhydrides as raw materials. Such hyperbranched polyimides have high glass transition temperature and thermal stability, low thermal expansion coefficient and excellent solubility. The synthesis method of the invention is simple and diverse, and thus is suitable for industrial production. The hyperbranched polyimide disclosed in the invention has good application prospects in the field of high temperature resistance and the field of materials such as gas permeation separation membranes.
Description
Technical field
The present invention relates to materials science field, especially a kind of aromatic series super-branched polyimide and preparation method thereof.
Technical background
Polyimides refers to the quasi polymer on main chain containing imide ring.It can be divided into according to the difference of its molecular structure
Aroma type polyimides and lard type polyimides.Wherein, aromatic polyimide is with its low-dielectric, high mechanicalness, easily system
Standby, particularly high thermal stability；Therefore, it is widely applied in many high and new technology fields.
However, the high thermal stability of aromatic polyimide makes many polyimides dissolubilities poor, in order to improve
The solubility property and processing performance of aromatic polyimide introduce branched structure in polyimides and prepare super-branched polyimide
(HBPIs).Super-branched polyimide has a series of excellent due to the advantages of that has both both polyimides and dissaving polymer
Comprehensive performance, such as high temperature resistant, high intensity, high dielectric, crystallinity it is low or do not crystallize, solution viscosity is low and dissolubility is good,
To obtain the concern and research of vast researcher.Its product has been developed and applied to gas separation membrane and permeable membrane etc.
Membrane material and other such as photosensitive, optical waveguides, liquid crystal, sensor (detecting electrode) and dielectric material high and new technology material neck
Domain.Relative to linear polyimide material, distance is big between super-branched polyimide strand, this improves its dissolubility, but
It is its heat resistance relative drop, which has limited it in space flight, aviation aircraft structure or function component and rocket, guided missile etc.
Part field extensive use.Therefore, on the basis of keeping super-branched polyimide high solubility, while it is improved
Heat resistance, this is of great significance to its application in high temperature resistant field is expanded.
The present invention introduces multiple rigid aromatic structures in super-branched polyimide main chain, and polymer on the one hand can be improved
Heat resistance since multiple rigid aromatic structures are introduced into super-branched polyimide main chain, polymerization on the other hand can be expanded
The distance between object chain, increases the free volume of polymer, further improves its dissolubility and processing performance, improves its gas infiltration
Permeability energy.Super-branched polyimide of the present invention has high glass-transition temperature and thermal stability, lower thermal expansion system simultaneously
Several and excellent solubility properties has preferable application in the Material Fields such as high temperature resistant field and gas permeability and separation film
Prospect.
Summary of the invention
The object of the present invention is to provide a kind of aromatic series super-branched polyimides.
Another object of the present invention is to provide a kind of above-mentioned preparation methods of aromatic series super-branched polyimide.
The object of the present invention is achieved like this: a kind of aromatic series super-branched polyimide material, general formula of molecular structure
It is as follows:
Wherein: m, z, n are 1~10000, and Y structure is as shown in general formula I:
I:
Wherein Ar1Selected from any one of following structural:
Preferably, the Ar1It is selected from
Wherein Ar2Selected from any one of following structural:
Preferably, the Ar2It is selected from
One of.
X be selected from one of following general structure or more than one:
Preferably, the m, z, the integer that n is 100~5000.
Further, it is preferable to the m, z, the integer that n is 1000~2000.
Another object of the present invention is to provide a kind of preparation method of above-mentioned aromatic series super-branched polyimide, this method
Are as follows: in molar ratio it is 1:(0.8~2.5 by the triamine containing Y structure and the dianhydride containing X architecture in argon atmosphere) it is dissolved in N- methyl
Pyrrolidones, dimethyl sulfoxide, dimethyl sulfone, sulfolane, Isosorbide-5-Nitrae-dioxane, n,N-dimethylacetamide, N, N- dimethyl
In one of formamide, metacresol, tetrahydrofuran or the highly polar aprotic organic solvent of more than one mixing, contain Y structure
Diamines and the dianhydride gross mass containing X architecture account for the 0.5~30% of reaction mass gross mass, be stirred to react 0.5 at -10~55 DEG C
~90h obtains homogeneous ultrabranching polyamide acid solution, and passes through hot-imide or chemistry to ultrabranching polyamide acid glue
Imidizate is dehydrated to obtain super-branched polyimide material.
The concrete operation step of the hot-imide method are as follows: on a glass by ultrabranching polyamide acid glue blade coating,
Glass plate is placed in vacuum drying oven again, is vacuumized, temperature program are as follows: room temperature to the entire mistake of constant temperature after 80 DEG C~120 DEG C
0.8~3h of journey, constant temperature 0.8~2h of whole process, is finally warming up to 300 DEG C~400 after being warming up to 150 DEG C~200 DEG C again later
0.8~2h of constant temperature whole process after DEG C can be taken off super-branched polyimide film or powder after cooling.
The concrete operation step of the chemical imidization method are as follows: in ultrabranching polyamide acid solution liquid be added pyridine/
As dehydrating agent, heating stirring is heated to 40~170 DEG C of continuation for acetic anhydride or triethylamine/acetic anhydride or sodium acetate/acetic anhydride
Stirring 4~for 24 hours, it is poured into after being cooled to room temperature in methanol or ethyl alcohol and obtains super-branched polyimide precipitating, be filtered, washed, dry,
Super-branched polyimide powder is obtained, if you need to prepare membrane material, then polyimides powder can be dissolved in N-Methyl pyrrolidone
(NMP), dimethyl sulfoxide (DMSO), n,N-dimethylacetamide (DMAc), n,N-Dimethylformamide (DMF), metacresol (m-
Cresol it) or in tetrahydrofuran (THF), is heated to after being completely dissolved, on a glass by polyimide solution blade coating, 70~
200 DEG C of vacuum drying remove solvent, can be taken off polyimide film after cooling.
A kind of preparation method of the aromatic series super-branched polyimide proposed is invented, preparation process is simple and various, item
Part requirement is low, thus is suitable for industrial production.The present invention introduces multiple rigid aromatic structures in super-branched polyimide main chain, and one
The heat resistance of polymer can be improved in aspect, on the other hand, since multiple rigid aromatic structures are introduced into hyperbranched polyamides Asia
Amine main chain can expand the distance between polymer chain, increase the free volume of polymer, further improve its dissolubility and add
Work performance improves its gas permeability.Super-branched polyimide of the present invention has high glass-transition temperature and heat steady simultaneously
It is qualitative, lower thermal expansion coefficient and excellent solubility property, in the materials such as high temperature resistant field and gas permeability and separation film
Material field is with good application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of Examples 1 to 7 super-branched polyimide, in which:
A corresponding embodiment 3
B corresponding embodiment 5
C corresponding embodiment 1
D corresponding embodiment 2
E corresponding embodiment 4
F corresponding embodiment 6
G corresponding embodiment 7
It can see from infrared spectrogram, in 1781 and 1716cm-1It is nearby the asymmetric and right of carbonyl on imide ring
Claim stretching vibration, in 1360cm-1There is apparent C-N key stretching vibration characteristic absorption peak in place, these all illustrate Examples 1 to 7
All successfully synthesize.
Specific embodiment
Example is given below so that the present invention will be described in more detail, it is necessary to be pointed out that following embodiment cannot be explained
For the limitation to invention protection scope, the person skilled in the art in the field makes the present invention according to foregoing invention content some
Nonessential modifications and adaptations should belong to the scope of protection of the present invention.
Embodiment 1
Three mouthfuls of burnings are added in pyromellitic acid anhydride (PMDA) 0.4362g (2mmol) and N,N-dimethylformamide 36ml
In bottle, it is passed through argon gas, is warming up to 30 DEG C, by Triamine monomer 4,4 "-diamino-5'- (4-aminophenyl)-[1,1':3',
1 "-terphenyl] -2'-ol 0.3674g (1mmol) is dissolved into 40ml N,N-dimethylformamide constant pressure funnel and exists
1~2h is dropped evenly in three-necked flask, then proceedes to reaction 16h, 6ml acetic anhydride and 2ml triethylamine is then added, is warming up to
45 DEG C of the reaction was continued 12h, reaction terminate to discharge in ethanol after being cooled to room temperature, filter, washing repeats 2~3 times, most postposition
Drying for 24 hours, obtains filemot super-branched polyimide polymer, structural formula is as follows in 80 DEG C of vacuum ovens:
Embodiment 2
Pyromellitic acid anhydride (PMDA) 0.4515g (2.07mmol) and DMAC N,N' dimethyl acetamide 15ml is added three mouthfuls
In flask, be passed through argon gas, be warming up to 30 DEG C, by Triamine monomer 5,5', 5 "-(benzene-1,3,5-triyl) tris
(thiophen-2-amine) 0.3695g (1mmol) is dissolved into 16ml DMAC N,N' dimethyl acetamide constant pressure funnel 1
~2h is dropped evenly in three-necked flask, then proceedes to reaction 14h, 6.2ml acetic anhydride and 2.1ml triethylamine is then added, rise
To 45 DEG C of the reaction was continued 14h, reaction terminates to discharge in ethanol after being cooled to room temperature temperature, filters, washing, repeats 2~3 times, most
It is placed on drying in 80 DEG C of vacuum ovens and for 24 hours, obtains lurid super-branched polyimide polymer, structural formula is as follows:
Embodiment 3
By 3,3', 4,4'-- bibenzene tetracarboxylic dianhydride (BPDA) 0.4413g (1.5mmol) and N-Methyl pyrrolidone 10ml
It is added in three-necked flask, is passed through argon gas, is warming up to 30 DEG C, by the "-diamino-5'- (4-aminophenyl)-of Triamine monomer 4,4
[1,1':3', 1 "-terphenyl] -2'-thiol 0.3835g (1mmol) is dissolved into 8ml N-Methyl pyrrolidone constant pressure
Dropping funel drops evenly in three-necked flask in 1~2h, then proceedes to reaction 26h, 12ml acetic anhydride and 3ml tri- is then added
Ethamine is warming up to 45 DEG C the reaction was continued 18h, and reaction terminates to discharge in methyl alcohol after being cooled to room temperature, filter, washing, repeat 2~
It 3 times, is finally placed in drying in 80 DEG C of vacuum ovens and for 24 hours, obtains the super-branched polyimide polymer of reddish brown, structure
Formula is as follows:
Embodiment 4
6,6', 6 "-(benzene-1,3,5-triyl) tris (naphthalen-2-amine) 1.0032g (2mmol) and
N,N-Dimethylformamide 8ml is added in three-necked flask, is passed through argon gas, is warming up to 30 DEG C, by 3,3', 4,4'- benzophenone tetracids
Dianhydride (BTDA) 0.6444g (2mmol) is dissolved into 8ml N,N-dimethylformamide uniform in 1~2h with constant pressure funnel
It is added dropwise in three-necked flask, then proceedes to reaction 16h.Gained super-branched polyimide acid glue is scratched into the glass in dried and clean
In glass plate, then glass plate is placed in vacuum drying oven, vacuumized, 80 lower dry 3h, the entire mistake of constant temperature after then raising temperature to 120 DEG C
Journey 2h, from 120 DEG C be warming up to 200 DEG C after constant temperature whole process 2h, 350 DEG C of constant temperature whole process 1h are warming up to from 200 DEG C, it is cold
But, super-branched polyimide film is taken out, structural formula is as follows:
Embodiment 5
N,N'-(5'-(4-(4-aminobenzamido)phenyl)-[1,1':3',1″-terphenyl]-4,4″-
Diyl) bis (4-aminobenza mide) 1.4176g (2mmol) and n,N-dimethylacetamide 5ml is added in three-necked flask,
It is passed through argon gas, is warming up to 30 DEG C, hexafluorodianhydride (6FDA) (6FDA) 0.8618g (1.94mmol) is dissolved into 5.5ml N, N- dimethyl second
It is dropped evenly in three-necked flask with constant pressure funnel in 1~2h in amide, then proceedes to reaction 20h, 6ml second is then added
Acid anhydrides and 2ml triethylamine are warming up to 45 DEG C the reaction was continued 14h, and reaction terminates to discharge in methyl alcohol after being cooled to room temperature, and filtering is washed
It washs, repeats 2~3 times, be finally placed in drying in 80 DEG C of vacuum ovens and for 24 hours, obtain super-branched polyimide polymerization russet
Object, structural formula are as follows:
Embodiment 6
4'-(3-aminophenyl)-[1,1':2',1″-terphenyl]-3,3″-diamine 0.3515g(1mmol)
It is added in three-necked flask with n,N-dimethylacetamide 50ml, is passed through argon gas, is warming up to 30 DEG C, by diphenyl ether tetraformic dianhydride
(ODPA) 0.2482g (0.8mmol) is dissolved into 50ml DMAC N,N' dimethyl acetamide uniform in 1~2h with constant pressure funnel
It is added dropwise in three-necked flask, then proceedes to reaction 20h.Gained super-branched polyimide acid glue is scratched into the glass in dried and clean
In glass plate, then glass plate is placed in vacuum drying oven, vacuumized, 80 lower dry 3h, the entire mistake of constant temperature after then raising temperature to 120 DEG C
Journey 2h, from 120 DEG C be warming up to 200 DEG C after constant temperature whole process 2h, 350 DEG C of constant temperature whole process 1h are warming up to from 200 DEG C, it is cold
But, super-branched polyimide film is taken out, structural formula is as follows:
Embodiment 7
7,7',7″-(benzene-1,3,5-triyl)tris(2-amino-9H-fluoren-9-one)0.6578g
(1mmol) and tetrahydrofuran 2ml are added in three-necked flask, are passed through argon gas, are warming up to 30 DEG C, by cyclobutanetetracarboxylic dianhydride
(CBDA) 0.2353g (1.2mmol) is dissolved into 1.5ml tetrahydrofuran is dropped evenly in 1~2h into three with constant pressure funnel
In mouth flask, reaction 18h is then proceeded to.By gained super-branched polyimide acid glue blade coating on the glass plate of dried and clean,
Glass plate is placed in vacuum drying oven again, is vacuumized, 80 lower dry 3h, constant temperature whole process 2h after then raising temperature to 120 DEG C, from
120 DEG C be warming up to 200 DEG C after constant temperature whole process 2h, be warming up to 350 DEG C of constant temperature whole process 1h from 200 DEG C, it is cooling, take out it is super
Branched polyimide film, structural formula are as follows:
Using the differential scanning calorimeter (DSC204) of Nai Chi company and the thermogravimetric analyzer (Q50) of TA company respectively to reality
It applies super-branched polyimide prepared by example 1~7 and carries out glass transition temperature (Tg) and the survey of 5% thermal weight loss temperature (T5%)
Examination, test result is as shown in table 1, and the solubility property data of super-branched polyimide are as shown in table 2.
The hot property of 1 super-branched polyimide of table
The dissolubility of 2 super-branched polyimide of table
Note: ++ representing room temperature can be completely dissolved
As can be seen from Table 1 and Table 2, super-branched polyimide of the present invention has high glass-transition temperature and thermostabilization
Property, excellent dissolubility.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810859390.6A CN109161018A (en) | 2018-07-31 | 2018-07-31 | A kind of aromatic series super-branched polyimide and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810859390.6A CN109161018A (en) | 2018-07-31 | 2018-07-31 | A kind of aromatic series super-branched polyimide and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109161018A true CN109161018A (en) | 2019-01-08 |
Family
ID=64898450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810859390.6A Pending CN109161018A (en) | 2018-07-31 | 2018-07-31 | A kind of aromatic series super-branched polyimide and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109161018A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112354381A (en) * | 2020-10-13 | 2021-02-12 | 中山大学 | 'full polyimide' mixed matrix gas separation membrane and preparation method and application thereof |
| CN114014742A (en) * | 2021-11-01 | 2022-02-08 | 上海八亿时空先进材料有限公司 | Triarylbenzene derivative, luminescent material, luminescent element and consumer product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
| CN105566633A (en) * | 2016-03-08 | 2016-05-11 | 湖南工业大学 | Novel hyperbranched polyimide containing carbazole structure, and preparation method and application thereof |
| WO2018126141A1 (en) * | 2016-12-31 | 2018-07-05 | Sabic Global Technologies B.V. | Branched polyimide compositions, method of manufacture, and uses thereof |
-
2018
- 2018-07-31 CN CN201810859390.6A patent/CN109161018A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
| CN105566633A (en) * | 2016-03-08 | 2016-05-11 | 湖南工业大学 | Novel hyperbranched polyimide containing carbazole structure, and preparation method and application thereof |
| WO2018126141A1 (en) * | 2016-12-31 | 2018-07-05 | Sabic Global Technologies B.V. | Branched polyimide compositions, method of manufacture, and uses thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112354381A (en) * | 2020-10-13 | 2021-02-12 | 中山大学 | 'full polyimide' mixed matrix gas separation membrane and preparation method and application thereof |
| CN114014742A (en) * | 2021-11-01 | 2022-02-08 | 上海八亿时空先进材料有限公司 | Triarylbenzene derivative, luminescent material, luminescent element and consumer product |
| CN114014742B (en) * | 2021-11-01 | 2024-05-10 | 上海八亿时空先进材料有限公司 | Triarylbenzene derivative, luminescent material, luminescent element and consumer product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105566633B (en) | A kind of super-branched polyimide containing carbazole structure and its production and use | |
| CN101700474B (en) | A kind of high molecular weight polyimide gas separation membrane and its preparation method | |
| CN109535069B (en) | Diamine monomer and preparation method thereof, and polyimide and preparation method thereof | |
| CN103846023A (en) | Copolymerization polyimide gas separation membrane material, preparation method and application of copolymerization polyimide gas separation membrane material | |
| CN108530673A (en) | A kind of linear polyimides aeroge and preparation method thereof | |
| CN104341593A (en) | Polyimide with low dielectric properties, and preparation method and application thereof | |
| CN106279685A (en) | Polyimide material, its preparation method and application of based on Teller lattice alkali structure | |
| CN102321244B (en) | Soluble functional polyimide containing rigid non-planar conjugated structure, and preparation method and application thereof | |
| CN114591503B (en) | Soluble poly (benzimidazole-co-imide) polymer and preparation and application thereof | |
| CN103102488B (en) | High dielectric constant polyimide containing bipyrimidine structure and preparation method | |
| Lai et al. | Highly soluble fluorinated polyimides with promising gas transport performance and optical transparency | |
| CN108586740A (en) | A kind of polyimides and its preparation method and application containing fluorenes or Fluorenone structure | |
| CN109833784A (en) | A kind of Silicone Containing Polyimides gas separation membrane and preparation method | |
| CN109161018A (en) | A kind of aromatic series super-branched polyimide and its preparation method and application | |
| CN102824857A (en) | Preparation method of gas separation carbon membrane | |
| CN111808423B (en) | Polyimide film with high heat resistance and low thermal expansion coefficient and preparation method thereof | |
| CN103910882A (en) | A kind of high Tg soluble polyimide and preparation method thereof | |
| CN108997578B (en) | High-heat-resistance hyperbranched polyimide and preparation method and application thereof | |
| CN115869788B (en) | Polyimide random copolymer with triptycene structure, and preparation method and application thereof | |
| CN105906808A (en) | Class I soluble polyimide containing tertiary butyl and multi-element aromatic ether structure and preparation method thereof | |
| CN104861162B (en) | Containing the soluble polyimide and preparation method thereof of the tertiary butyl and fluorine-triphenylamine structure | |
| CN109053582A (en) | Diamine monomer, heat-proof polyimide containing aromatic rings and glyoxaline structure and preparation method thereof | |
| CN109054017A (en) | A kind of super-branched polyimide of the structure containing phenanthrene ring and its preparation method and application | |
| CN109251315A (en) | A kind of super-branched polyimide of the structure containing anthracene and its preparation method and application | |
| Abbasi et al. | A new category of thermally stable poly (ether amide ether imide) s with increased solubility |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190108 |