CN115490857A - Fluorine-containing thermoplastic polyimide resin and preparation method and application thereof - Google Patents
Fluorine-containing thermoplastic polyimide resin and preparation method and application thereof Download PDFInfo
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- CN115490857A CN115490857A CN202211175589.XA CN202211175589A CN115490857A CN 115490857 A CN115490857 A CN 115490857A CN 202211175589 A CN202211175589 A CN 202211175589A CN 115490857 A CN115490857 A CN 115490857A
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- polyimide resin
- fluorine
- dianhydride monomer
- containing thermoplastic
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- 239000009719 polyimide resin Substances 0.000 title claims abstract description 109
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 60
- 239000011737 fluorine Substances 0.000 title claims abstract description 60
- 229920006259 thermoplastic polyimide Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 100
- 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 abstract description 78
- 229920001721 polyimide Polymers 0.000 claims abstract description 70
- 238000002834 transmittance Methods 0.000 claims abstract description 28
- 125000004427 diamine group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 27
- 230000003287 optical effect Effects 0.000 claims description 23
- 150000004985 diamines Chemical class 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 230000004580 weight loss Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- 229920005575 poly(amic acid) Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000012024 dehydrating agents Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000013307 optical fiber Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 9
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 9
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 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 3
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- -1 (4-amino)Phenoxy Chemical group 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- ATRFGXJHIQLQHF-UHFFFAOYSA-N 5,5,5-trifluoro-4-(trifluoromethyl)pent-2-ene Chemical group CC=CC(C(F)(F)F)C(F)(F)F ATRFGXJHIQLQHF-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004383 yellowing Methods 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1046—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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic 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
- C08G73/1067—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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the field of high-performance engineering plastics, and discloses a fluorine-containing thermoplastic polyimide resin, and a preparation method and application thereof. The fluorine-containing thermoplastic polyimide resin comprises a structural unit M shown in a formula I and a structural unit N shown in a formula II;
wherein Ar is 1 And Ar 2 Is dianhydride monomer residue, B is diamine monomer residue; ar (Ar) 1 At least one selected from the group consisting of:
Ar 2 at least one selected from the group consisting of:
Description
Technical Field
The invention relates to the field of high-performance engineering plastics, in particular to a fluorine-containing thermoplastic polyimide resin and a preparation method and application thereof.
Background
With the rapid development of optical materials in recent years, the use of polymer optical materials is also more and more extensive, and simultaneously, higher requirements are put on the performance of the polymer optical materials. Poor heat resistance and easy deformation in high-temperature use are the biggest defects for limiting the application of polymer optical materials, and the heat distortion temperature of the main varieties used at present, such as polycarbonate, polymethyl methacrylate and the like, is lower than 140 ℃, so that the use requirements under the high-temperature environment cannot be met.
The aromatic polyimide resin has a rigid main chain and strong intermolecular forces, is a polymer material with excellent heat resistance, and is one of ideal materials in the field of optical devices. However, the rigid molecular structure of the aromatic polyimide resin also causes poor melt processability, and therefore, molding and processing by injection molding, extrusion, or the like cannot be performed, and it is difficult to meet the processing requirements of precision optical devices. In addition, charge transfer is easy to occur in and among aromatic polyimide molecules to generate a Charge Transfer Complex (CTC), so that the transmittance of the aromatic polyimide in ultraviolet-visible light bands is low, and the polyimide material is often required to be subjected to high-temperature thermal imidization (more than 350 ℃) in the preparation process, so that the color of the material is deepened, and the product is generally brown yellow. The large processing difficulty, the low transmittance and the deep color are main reasons for limiting the application of the aromatic polyimide resin in the field of optical devices, so that the aromatic polyimide resin is modified by adopting a molecular structure design method, and the aromatic polyimide resin has good thermoplastic processing performance and optical performance and becomes the direction of efforts of researchers.
Disclosure of Invention
The invention aims to solve the problems that the aromatic polyimide resin in the prior art is high in processing difficulty and deep in product color and cannot meet the use requirement of an optical material, and provides a fluorine-containing thermoplastic polyimide resin, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a fluorine-containing thermoplastic polyimide resin, comprising a structural unit M represented by formula I and a structural unit N represented by formula II;
wherein Ar is 1 And Ar 2 Is dianhydride monomer residue, B is diamine monomer residue;
Ar 1 at least one selected from the group consisting of:
Ar 2 at least one selected from the group consisting of:
the molar ratio of the structural unit M to the structural unit N is 1:0.1-0.4.
The second aspect of the present invention provides a method for producing a fluorine-containing thermoplastic polyimide resin, characterized in that the method comprises:
(1) Dissolving a dianhydride monomer I, a dianhydride monomer II and a diamine monomer in a polar solvent, and carrying out copolymerization reaction to obtain a polyamic acid solution;
(2) Mixing the polyamic acid solution, a dehydrating agent and a catalyst, and then carrying out chemical imidization reaction;
(3) Mixing a precipitator and the product obtained in the step (2) to separate out polyimide resin;
(4) Carrying out heat treatment on the polyimide resin to obtain the fluorine-containing thermoplastic polyimide resin;
the dianhydride monomer I is at least one selected from the group consisting of the following compounds:
the dianhydride monomer II is selected from at least one of the following compounds:
the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.1-0.4.
The third aspect of the present invention provides a fluorine-containing thermoplastic polyimide resin obtained by the above method.
The fourth aspect of the present invention provides an application of the above fluorine-containing thermoplastic polyimide resin in at least one of an optical waveguide device, a photorefractive material, a resin lens, a precision lens, a transparent film and an optical fiber.
By the technical scheme, the fluorine-containing thermoplastic polyimide resin and the preparation method and application thereof provided by the invention have the following beneficial effects:
in the fluorine-containing thermoplastic polyimide resin provided by the invention, a flexible group (such as dianhydride monomer residue Ar containing flexible ether bond) is introduced into a molecular main chain 1 ) Or by introducing bulky side groups (e.g. containing-CF) 3 Dianhydride monomer residue Ar of 2 And diamine monomer residue B), effectively reducing the rigidity of molecular main chains, and destroying the close packing among the molecular chains, so that the polyimide resin has low melt viscosity, and the processability of the polyimide resin is improved; at the same time, dianhydride monomer residue Ar selected from fluorine-containing group or alicyclic group is introduced into the molecular main chain 2 The fluorine-containing thermal polyimide resin provided by the invention has excellent heat resistance, thermoplastic processability, high transmittance and low yellowness index.
In the method for preparing the fluorine-containing thermoplastic polyimide resin, chemical imidization is adopted to replace thermal imidization, so that the heat treatment temperature can be obviously reduced, and the influence of high temperature on the color of a resin product is effectively avoided. The fluorine-containing thermoplastic polyimide resin prepared by the method is suitable for the fields of optical waveguide devices, photorefractive materials, resin lenses, precision lenses, transparent films, optical fibers and the like.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The first aspect of the present invention provides a fluorine-containing thermoplastic polyimide resin, characterized in that the fluorine-containing thermoplastic polyimide resin comprises a structural unit M represented by formula I and a structural unit N represented by formula II;
wherein Ar is 1 And Ar 2 Is dianhydride monomer residue, B is diamine monomer residue;
Ar 1 at least one selected from the group consisting of:
Ar 2 at least one selected from the group consisting of:
the molar ratio of the structural unit M to the structural unit N is 1:0.1-0.4.
In the invention, the molecular main chain of the fluorine-containing thermoplastic polyimide resin comprises a structural unit M shown in a formula I and a structural unit N shown in a formula II, specifically, a large-volume fluorine-containing group, a flexible ether bond and the like are introduced into the polyimide molecular main chain through the structural unit M and the structural unit N, so that the rigidity of the molecular main chain is reduced, the close accumulation among molecular chains is broken, the melt viscosity of the polyimide resin is reduced, and meanwhile, the introduction of the fluorine-containing group or an alicyclic structure can effectively inhibit charge transfer in the molecular chains and among the chains, so that the fluorine-containing thermoplastic polyimide resin has good thermoplastic processability and high transmittance.
Further, in the invention, by controlling the molar ratio of the structural unit M to the structural unit N, the dianhydride monomer residue Ar in the polyimide resin is subjected to 1 With dianhydride monomer residue Ar 2 And when the molar ratio of the structural unit M to the structural unit N satisfies the above range, the fluorine-containing thermoplastic polyimide resin can be made to have good thermoplastic processability, high transmittance and low yellowness index in combination. The fluorine-containing thermoplastic polyimide resin is suitable for the fields of optical waveguide devices, photorefractive materials, resin lenses, precision lenses, transparent films, optical fibers and the like.
Further, ar 1 Is composed of
Further, the molar ratio of the structural unit M to the structural unit N is 1:0.1-0.25.
According to the invention, B is selected from at least one of the group consisting of:
in the present invention, when B is selected from at least one of the above groups, a flexible group and/or a bulky side group can be introduced into the molecular main chain of the polyimide, thereby further reducing the rigidity of the molecular main chain and breaking the close packing between the molecular chains, so that the melt viscosity of the polyimide resin is further reduced and the processability is further improved.
According to the present invention, B is at least one selected from the group consisting of;
in a preferred embodiment of the present invention, ar 1 Is composed of
Ar 2 Is composed of
B is at least one selected from the group consisting of:
in a preferred embodiment of the present invention, ar 1 Is composed of
Ar 2 Is composed of
B is at least one selected from the group consisting of:
according to the present invention, the theoretical molecular weight of the polyimide resin is 25,000 to 100,000g/mol.
According to the present invention, the polyimide resin has a minimum melt viscosity of 100 to 10 4 Pa · s, preferably from 500 to 10 4 Pa·s。
According to the present invention, the polyimide has a transmittance of 70% or more, preferably 75% or more at a wavelength of 450 nm.
According to the invention, the transmittance at a wavelength of 650nm is 80% or higher, preferably 85% or higher. According to the present invention, the polyimide resin has a yellowness index of 10 or less, preferably 8 or less;
according to the present invention, the glass transition temperature of the polyimide resin is 210 ℃ or higher, preferably 220 ℃ or higher.
According to the present invention, the 5wt% thermal weight loss temperature of the polyimide resin is equal to or higher than 520 ℃, preferably equal to or higher than 530 ℃.
The second aspect of the present invention provides a method for producing a fluorine-containing thermoplastic polyimide resin, characterized in that the method comprises:
(1) Dissolving a dianhydride monomer I, a dianhydride monomer II and a diamine monomer in a polar solvent, and carrying out copolymerization reaction to obtain a polyamic acid solution;
(2) Mixing the polyamic acid solution, a dehydrating agent and a catalyst, and then carrying out chemical imidization reaction;
(3) Mixing a precipitator and the product obtained in the step (2) to separate out polyimide resin;
(4) Vacuum drying the polyimide resin to obtain the fluorine-containing thermoplastic polyimide resin;
the dianhydride monomer I is selected from at least one of the following compounds:
the dianhydride monomer II is selected from at least one of the following compounds:
the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.1-0.4.
In the method for preparing the fluorine-containing thermoplastic polyimide resin, provided by the invention, chemical imidization is adopted to replace thermal imidization, so that the heat treatment temperature can be obviously reduced, the influence of the traditional high-temperature oxidation reaction on the optical performance of the fluorine-containing thermoplastic polyimide resin is further reduced, the prepared polyimide resin has high light transmittance, and the fluorine-containing thermoplastic polyimide resin prepared by the method is suitable for the fields of optical waveguide devices, photorefractive materials, resin lenses, precision lenses, transparent films, optical fibers and the like.
Furthermore, in the invention, a specific dianhydride monomer I and a dianhydride monomer II are adopted to react with a diamine monomer together to prepare polyimide, so that flexible ether bonds, bulky side groups and the like are introduced into a polyimide molecular main chain, the rigidity of the molecular main chain is reduced, the close packing among molecular chains is broken, and the melt viscosity of the polyimide resin is reduced.
Further, in the invention, by controlling the molar ratio of the dianhydride monomer I to the dianhydride monomer II, the dianhydride monomer residue Ar in the polyimide resin is realized 1 With dianhydride monomer residue Ar 2 And when the molar ratio of the dianhydride monomer I to the dianhydride monomer II satisfies the above range, the fluorine-containing thermoplastic polyimide resin can combine good thermoplastic processability, high transmittance and low yellowness index. The fluorine-containing thermoplastic polyimide resin is suitable for the fields of optical waveguide devices, photorefractive materials, resin lenses, precision lenses, transparent films, optical fibers and the like.
Wherein the content of the first and second substances,
is 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride);
Further, the dianhydride monomer I is
Further, the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.1-0.25.
According to the present invention, the diamine monomer is at least one selected from the group consisting of:
in particular, the amount of the solvent to be used,
is 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl;
In the invention, the diamine monomer of the specific kind is selected, so that a flexible group or a bulky side group can be introduced into a molecular main chain of the polyimide, the rigidity of the molecular main chain is further reduced, the close packing among the molecular chains is damaged, the melt viscosity of the polyimide resin is further reduced, and the processability is further improved.
Further, the diamine monomer is selected from at least one of the group consisting of:
according to the present invention, the ratio of the molar amount of the diamine monomer to the total molar amount of the dianhydride monomer I and the dianhydride monomer II is 1:1.02-1.1.
In the present invention, the kind of the polar solvent is not particularly limited, and may be N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, or the like.
According to the invention, the dehydrating agent is an anhydride, preferably acetic anhydride.
According to the invention, the catalyst is a tertiary amine, preferably selected from triethylamine and/or pyridine.
According to the invention, the precipitating agent is selected from water and/or ethanol.
According to the present invention, the dehydrating agent is used in an amount of 120 to 300mol% based on the total molar amount of the dianhydride monomer I and the dianhydride monomer II.
Further, the amount of the dehydrating agent is 150 to 200mol% based on the total molar amount of the dianhydride monomer I and the dianhydride monomer II.
According to the invention, the amount of catalyst used is 30 to 50mol%, based on the amount of dehydrating agent used.
According to the invention, the conditions of the copolymerization reaction include: the reaction temperature is 0-25 ℃, and the reaction time is 6-12h.
Further, the copolymerization reaction conditions include: the reaction temperature is 0-10 ℃, and the reaction time is 8-12h.
According to the invention, the conditions of the chemical imidization reaction comprise: the reaction temperature is 30-90 ℃ and the reaction time is 0.5-2h.
In the present invention, under the above conditions, the polyamic acid solution is chemically imidized under the action of the dehydrating agent and the catalyst, and the polyamic acid can undergo dehydrating cyclization in the molecular structure at a relatively low temperature to produce polyimide. Compared with thermal imidization, the chemical imidization can effectively reduce the influence of high-temperature oxidation reaction on the optical performance of the polyimide resin and improve the transmittance of the resin.
Further, the conditions of the chemical imidization reaction include: the reaction temperature is 70-90 ℃ and the reaction time is 1-1.5h.
According to the present invention, the vacuum drying conditions include: the drying temperature is 200-250 deg.C, and the drying time is 0.5-3h.
Further, the vacuum drying conditions include: the drying temperature is 200-220 deg.C, and the drying time is 1-2h.
The third aspect of the present invention provides a fluorine-containing thermoplastic polyimide resin obtained by the above method.
The fourth aspect of the present invention provides an application of the above fluorine-containing thermoplastic polyimide resin in at least one of an optical waveguide device, a photorefractive material, a resin lens, a precision lens, a transparent film and an optical fiber.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the glass transition temperature of the polyimide resin is measured by DSC;
the 5wt% thermal weight loss temperature of the polyimide resin is measured by TGA, the test temperature range is 30-800 ℃, and the test atmosphere is nitrogen;
the lowest melt viscosity of the polyimide resin is measured by a rotational rheometer (DHR-2, TA of America) and the test temperature ranges from 280 ℃ to 400 ℃;
the transmittance of the polyimide resin is measured by an ultraviolet-visible spectrophotometer;
the yellowness index of the polyimide resin is measured by a spectrocolorimeter;
the raw materials used in the examples and comparative examples are all commercially available products.
Example 1
(1) Dissolving a diamine monomer (2, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) in a three-necked flask containing N, N-dimethylacetamide, mechanically stirring, adding in portions after complete dissolution in a molar ratio of 1:0.11 dianhydride monomer I (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride)) and dianhydride monomer II cyclobutane tetracarboxylic dianhydride were reacted at 25 ℃ with stirring for 8 hours to obtain a polyamic acid solution; wherein the ratio of the molar amount of diamine monomer to the total molar amount of dianhydride monomer I and dianhydride monomer II is 1:1.03.
(2) Adding acetic anhydride and pyridine into the polyamic acid solution, and stirring to react for chemical imidization; wherein, the total molar weight of the dianhydride monomer I and the dianhydride monomer II is taken as a reference, the usage amount of acetic anhydride is 120mol%, and the usage amount of pyridine is 40mol%; the imidization conditions were: the temperature is 30 ℃, and the time is 1.5h;
(3) Slowly adding the product obtained in the step (2) into water, stirring at a high speed, and precipitating to separate out the polyimide resin;
(4) And (4) drying the polyimide resin obtained in the step (3) in a vacuum oven at 220 ℃ for 1h to finally obtain the fluorine-containing thermoplastic polyimide resin A1.
The glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A1 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, with the results shown in table 1.
Example 2
A fluorine-containing thermoplastic polyimide resin A2 was prepared by following the procedure of example 1, except that:
in the step (1), the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.25.
the glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A2 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, and the results are shown in table 1.
Example 3
A fluorine-containing thermoplastic polyimide resin A3 was prepared by following the procedure of example 1, except that:
in the step (1), the dianhydride monomer II is 4,4' - (hexafluoroisopropylidene) diphthalic anhydride.
The glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A3 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, and the results are shown in table 1.
Example 4
A fluorine-containing thermoplastic polyimide resin A4 was produced by following the procedure of example 1, except that:
in the step (1), the dianhydride monomer II is 4,4' - (hexafluoro-isopropyl-propylene) diphthalic anhydride, and the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.25.
the glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A4 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, with the results shown in table 1.
Example 5
A fluorine-containing thermoplastic polyimide resin A5 was prepared by following the procedure of example 1, except that:
in the step (1), the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.35.
the glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A5 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, with the results shown in table 1.
Example 6
A fluorine-containing thermoplastic polyimide resin A6 was prepared by following the procedure of example 1, except that:
in the step (1), the dianhydride monomer II is 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, and the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.35.
the glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A6 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index of 4 were measured, with the results shown in table 1.
Example 7
A fluorine-containing thermoplastic polyimide resin A7 was prepared by following the procedure of example 1, except that:
in the step (1), two diamine monomers are adopted, specifically, a diamine monomer is prepared by mixing the diamine monomers in a molar ratio of 1:0.11 of (2, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) and (1, 3-bis (4-aminophenoxy) benzene) in place of (2, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) in example 1.
The glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A7 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, with the results shown in table 1.
Example 8
A fluorine-containing thermoplastic polyimide resin A8 was prepared by following the procedure of example 1, except that:
in the step (1), diamine monomer III and diamine monomer IV (1, 3-bis (4-aminophenoxy) benzene) are mixed in a molar ratio of 1:0.25 reaction with dianhydride monomer after mixing.
The glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin A8 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, and the results are shown in table 1.
Comparative example 1
A fluorine-containing thermoplastic polyimide resin D1 was prepared by following the procedure of example 1, except that:
in the step (1), the dianhydride monomer II is replaced by an equimolar amount of the dianhydride monomer I.
The glass transition temperature, 5wt% thermal weight loss temperature, and lowest melt viscosity of the polyimide resin D1 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, and the results are shown in table 1.
Comparative example 2
A fluorine-containing thermoplastic polyimide resin D2 was prepared by following the procedure of example 1, except that:
in the step (1), the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.5.
the glass transition temperature and 5wt% weight loss on heat temperature of the polyimide resin D2 were measured, and the results are shown in table 1. The polyimide resin prepared by the comparative example has no melting plasticizing phenomenon below 400 ℃, and cannot be molded by a thermoplastic process.
Comparative example 3
A fluorine-containing thermoplastic polyimide resin D3 was prepared by following the procedure of example 1, except that: in the step (2), without chemical imidization, adding a polyamic acid solution into water to precipitate out resin, and then performing heat treatment for 1.5h in a vacuum oven at 350 ℃ to obtain the fluorine-containing thermoplastic polyimide resin D3.
The glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin D3 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index were measured, and the results are shown in table 1.
Comparative example 4
A fluorine-containing thermoplastic polyimide resin D4 was produced by following the procedure of example 1, except that:
in the step (1), the diamine monomer III is p-phenylenediamine, and the dianhydride monomer II is replaced by the dianhydride monomer I with the same molar amount.
The glass transition temperature, 5wt% thermal weight loss temperature and lowest melt viscosity of the polyimide resin D4 were measured, and a sample sheet having a thickness of about 0.11mm was prepared by hot press molding, and the transmittance at 450nm and 650nm and the yellowness index thereof were measured, and the results are shown in table 1.
TABLE 1
Note that the fluorine-containing thermoplastic polyimide resin prepared in comparative example 2 does not have a melt plasticizing phenomenon below 400 ℃, cannot be molded by a thermoplastic process to prepare a test sample piece, and cannot obtain transmittance and a yellowing index;
* It is shown that the fluorine-containing thermoplastic polyimide resin prepared in comparative example 2 could not be melted at the test temperature of melt viscosity ranging from 280 to 400 c, and the lowest viscosity value could not be read.
According to the comparison of the properties of the resins of examples and comparative examples, it is known that the introduction of a flexible ether bond and a certain amount of a fluorine-containing group or an alicyclic structure into the molecular structure of polyimide is effective in improving the thermoplastic processability and optical properties of the polyimide resin.
According to the comparison of the results of the optical property tests of examples 1 to 6 with those of comparative examples 1 and 4, it is understood that when the content of the fluorine-containing dianhydride monomer 4,4' - (hexafluoroisopropylene) diphthalic anhydride or the alicyclic dianhydride-containing monomer cyclobutanetetracarboxylic dianhydride is low, the optical property improvement effect on the polyimide resin is remarkable, and when the content of the fluorine-containing dianhydride monomer or the alicyclic structure-containing dianhydride monomer is too high, the transmittance is rather decreased because the rigidity of the molecular main chain is increased, the melt viscosity is increased, the molding process needs to be performed at a higher temperature, the oxidation reaction is accelerated, and the transmittance is decreased; comparison of the results of the optical property tests according to example 1 and comparative example 3 also shows that chemical imidization can perform dehydrocyclization reaction at a lower temperature than thermal imidization, thereby reducing the effect of high temperature treatment on the optical properties of polyimide resin.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A fluorine-containing thermoplastic polyimide resin characterized by comprising a structural unit M represented by the formula I and a structural unit N represented by the formula II;
wherein Ar is 1 And Ar 2 Is dianhydride monomer residue, B is diamine monomer residue;
Ar 1 at least one selected from the group consisting of:
Ar 2 at least one selected from the group consisting of:
the molar ratio of the structural unit M to the structural unit N is 1:0.1-0.4.
2. The fluorine-containing thermoplastic polyimide resin according to claim 1, wherein B is at least one selected from the group consisting of:
preferably, B is selected from at least one of the group consisting of;
3. the fluorine-containing thermoplastic polyimide resin according to claim 1 or 2, wherein the polyimide resin has a theoretical molecular weight of 25,000 to 100,000g/mol;
preferably, the polyimide resin has a minimum melt viscosity of 100 to 10 4 Pa·s；
Preferably, the polyimide has a transmittance of 70% or more at a wavelength of 450 nm;
preferably, the polyimide has a transmittance of 80% or more at a wavelength of 650 nm;
preferably, the polyimide resin has a yellowness index of 10 or less;
preferably, the glass transition temperature of the polyimide resin is greater than or equal to 210 ℃;
preferably, the 5wt% thermal weight loss temperature of the polyimide resin is 520 ℃ or higher.
4. A method for producing a fluorine-containing thermoplastic polyimide resin, characterized by comprising:
(1) Dissolving a dianhydride monomer I, a dianhydride monomer II and a diamine monomer in a polar solvent, and carrying out copolymerization reaction to obtain a polyamic acid solution;
(2) Mixing the polyamic acid solution, a dehydrating agent and a catalyst, and then carrying out chemical imidization reaction;
(3) Mixing a precipitator and the product obtained in the step (2) to separate out polyimide resin;
(4) Vacuum drying the polyimide resin to obtain the fluorine-containing thermoplastic polyimide resin;
the dianhydride monomer I is selected from at least one of the following compounds:
the dianhydride monomer II is selected from at least one of the following compounds:
the molar ratio of the dianhydride monomer I to the dianhydride monomer II is 1:0.1-0.4.
5. The production method according to claim 4, wherein the diamine monomer is at least one selected from the group consisting of:
preferably, the diamine monomer is selected from at least one of the group consisting of:
6. the method of claim 4 or 5, wherein the ratio of the molar amount of diamine monomer to the total molar amount of dianhydride monomer I and dianhydride monomer II is 1:1.02-1.1.
7. The process according to any one of claims 4 to 6, wherein the dehydrating agent is an anhydride, preferably acetic anhydride;
preferably, the catalyst is a tertiary amine, preferably triethylamine and/or pyridine;
preferably, the precipitating agent is selected from water and/or ethanol;
preferably, the amount of the dehydrating agent is 120 to 300mol% based on the total molar amount of the dianhydride monomer I and the dianhydride monomer II;
preferably, the catalyst is used in an amount of 30 to 50mol% based on the amount of the dehydrating solvent.
8. The process of any one of claims 4-7, wherein the copolymerization reaction conditions include: the reaction temperature is 0-25 ℃, and the reaction time is 6-12h;
preferably, the conditions of the chemical imidization reaction include: the reaction temperature is 30-90 ℃, and the reaction time is 0.5-2h;
preferably, the vacuum drying conditions include: the drying temperature is 200-250 deg.C, and the drying time is 0.5-3h.
9. A fluorine-containing thermoplastic polyimide resin obtained by the method according to any one of claims 4 to 8.
10. Use of the fluorine-containing thermoplastic polyimide resin according to any one of claims 1 to 3 and 9 in at least one of an optical waveguide device, a photorefractive material, a resin lens, a precision lens, a transparent film and an optical fiber.
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