CN114181391A - Thermoplastic polyimide resin and preparation method thereof - Google Patents
Thermoplastic polyimide resin and preparation method thereof Download PDFInfo
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- CN114181391A CN114181391A CN202010962688.7A CN202010962688A CN114181391A CN 114181391 A CN114181391 A CN 114181391A CN 202010962688 A CN202010962688 A CN 202010962688A CN 114181391 A CN114181391 A CN 114181391A
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- polyimide resin
- polyimide
- thermoplastic polyimide
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- 239000009719 polyimide resin Substances 0.000 title claims abstract description 58
- 229920006259 thermoplastic polyimide Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920001721 polyimide Polymers 0.000 claims abstract description 109
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004642 Polyimide Substances 0.000 claims description 85
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 42
- 229920005575 poly(amic acid) Polymers 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 239000008188 pellet Substances 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 12
- 239000012716 precipitator Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- -1 tertiary amine compound Chemical class 0.000 claims description 5
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 43
- 239000000843 powder Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000012545 processing Methods 0.000 description 10
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- YIHKILSPWGDWPR-UHFFFAOYSA-N 6708-37-8 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C=C2 YIHKILSPWGDWPR-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- WWKSSCSHSWQOAT-UHFFFAOYSA-N 4-phenylcyclohexa-1,5-diene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)=C(C(O)=O)C=CC1(C(O)=O)C1=CC=CC=C1 WWKSSCSHSWQOAT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- 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
- C08G73/1042—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
- C08G73/1067—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
Landscapes
- 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 thermoplastic polyimide materials, and discloses a thermoplastic polyimide resin and a preparation method thereof. The polyimide resin has a structure represented by formula (1):
wherein Ar is the residue of a primary diamine monomer; ar is selected from one or more than two of the following groups:
x is 0.45-0.9; EG is an end-capping agent residue selected from one of the following groups:
Description
Technical Field
The invention relates to the field of thermoplastic polyimide materials, in particular to thermoplastic polyimide resin and a preparation method thereof.
Background
Polyimide is a resin material with excellent comprehensive performance, has the advantages of good thermal stability, excellent mechanical performance, good dimensional stability, excellent chemical stability, high breakdown voltage, low dielectric constant, high flame retardance, low expansion coefficient and the like, and is widely applied to the high-tech fields of electronic and electrical products, aerospace, automobiles, chemical machinery and the like. On the other hand, due to the extremely strong interaction force between the rigid molecular chains and molecules of polyimide, the polymer is difficult to melt, and the processing and application range of polyimide is limited, so that a plurality of methods are developed to improve the thermoplastic processability of polyimide. For example, flexible groups such as-O-, -S-, -CH-may be introduced into the main chain molecule2And the like, the rigidity of molecular chains is reduced, and intermolecular forces are reduced, but the glass transition temperature of polyimide is lowered. CN102634021A discloses a thermoplastic polyimide resin and a preparation method thereof. The thermoplastic polyimide resin is prepared by reacting mixed dianhydride consisting of 1,2,3, 4-pyromellitic dianhydride and other common tetracarboxylic dianhydride, diamine and phthalic anhydride or aniline, polymerizing the mixed dianhydride and the diamine, and controlling the molecular weight by using the phthalic anhydride or aniline as an end capping agent, so that the thermoplastic polyimide resin with good thermal stability and excellent thermoplastic processability is obtained, the inherent viscosity can reach 0.22-0.90dL/g, and the glass transition temperature is 220-420 ℃, so that the thermoplastic polyimide resin can be widely applied to the preparation of materials such as high-temperature-resistant engineering plastics, films, adhesives and the like.
However, the thermoplastic polyimide resin provided by the above patent has disadvantages of low melt index and high extrusion temperature required for extrusion injection molding.
Disclosure of Invention
The invention aims to solve the problems of difficulty in controlling the viscosity, low melt index and high extrusion temperature of polyimide resin in the prior art, and provides the polyimide resin and the preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a thermoplastic polyimide resin, characterized in that the polyimide resin has a structure represented by formula (1):
wherein Ar is the residue of a primary diamine monomer; ar is selected from one or more than two of the following groups:
x is 0.45-0.9;
EG is an end-capping agent residue selected from one of the following groups:
the viscosity of the thermoplastic polyimide resin at 30 ℃ is 0.35-0.55 dL/g.
The second aspect of the present invention provides a method for producing the above polyimide resin, characterized in that the method comprises the steps of:
(1) preparation of polyimide solution: in the presence of a solvent and an inert atmosphere, carrying out a first reaction on a diamine monomer and a dianhydride monomer to obtain a polyamic acid solution; adding an end-capping reagent when the viscosity of the polyamic acid solution reaches 0.35-0.55dL/g, performing a second reaction, and adding an imidization reagent to perform a third reaction to obtain a polyimide solution;
(2) preparation of polyimide resin: and (2) diluting the polyimide solution obtained in the step (1), separating out the polyimide solution in a precipitator, washing and drying to obtain the thermoplastic polyimide resin.
The third aspect of the present invention provides a polyimide resin obtained by the above-mentioned process.
By the technical scheme, the polyimide resin and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the polyimide resin provided by the invention can improve the melt index and reduce the extrusion temperature on the premise of not influencing the mechanical property of the resin;
(2) in the invention, the reaction stability is greatly improved by changing the feeding mode, particularly adding the end-capping reagent after the viscosity of the polyimide is measured to reach a certain value, rather than adding all the raw materials into the reaction vessel at one time.
(3) The reaction temperature after the imidization reagent is added is controlled to be 60-90 ℃, the reaction time is controlled to be 1-3 hours, the imidization reaction time is greatly shortened under the condition of controlling the polyamic acid not to be degraded, and the reaction stability is also improved.
(4) The polyimide solution is diluted to a certain concentration and then precipitated in a precipitator, so that the particle size of the precipitated polyimide powder can be effectively controlled, and meanwhile, the polyimide powder is further crushed by a crusher after being dried, so that the particle size of the polyimide powder before processing is ensured.
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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
A first aspect of the present invention provides a thermoplastic polyimide resin, characterized in that the polyimide resin has a structure represented by formula (1):
wherein Ar is the residue of a primary diamine monomer; ar is selected from one or more than two of the following groups:
x is 0.45-0.9;
EG is an end-capping agent residue selected from one of the following groups:
the viscosity of the thermoplastic polyimide resin at 30 ℃ is 0.35-0.55 dL/g.
In the polyimide resin with the specific structure, due to the fact that the polyimide resin has the isomeric structural unit of the biphenyldianhydride, molecular chains are distorted, and the specific end capping agent structure is introduced, the polyimide resin has the performance characteristics of high melt index and low extrusion temperature.
In the present invention, x represents the weight percentage of the structural unit in the polyimide resin. x can be measured by FI-IR or calculated according to the feeding and the residual amount.
According to the invention, Ar is selected from one or more than two of the following groups:
according to the invention, the blocking agent is selected from at least one of the structures shown below:
according to the invention, x is from 0.5 to 0.8.
According to the present invention, the thermoplastic polyimide resin has a melt index of 0.5 to 5g/10min at 360 ℃ and a load of 12.5 kg; the extrusion temperature of the thermoplastic polyimide resin is 300-360 ℃.
In the invention, the viscosity of the polyimide resin is measured by a national standard GB/T10247-2008 method, and the melt index is measured by a national standard GB/T3682.1-2018 method.
In one embodiment of the present invention, the polyimide has a structure represented by formula (2):
formula (2);
wherein x is 0.5-0.8 and Ar is as described above.
The second aspect of the present invention provides a method for producing the above polyimide resin, characterized in that the method comprises the steps of:
(1) preparation of polyimide solution: in the presence of a solvent and an inert atmosphere, carrying out a first reaction on a diamine monomer and a dianhydride monomer to obtain a polyamic acid solution; adding an end-capping reagent when the viscosity of the polyamic acid solution reaches 0.3-0.6dL/g, performing a second reaction, and adding an imidization reagent to perform a third reaction to obtain a polyimide solution;
(2) preparation of polyimide resin: and (2) diluting the polyimide solution obtained in the step (1), separating out the polyimide solution in a precipitator, washing and drying to obtain the thermoplastic polyimide resin.
In the invention, the end-capping reagent is added instead of adding all the raw materials into the reaction vessel at one time by changing the feeding mode, particularly after the viscosity of the polyimide is measured to reach a certain value and particularly when the viscosity of the polyamic acid solution reaches 0.3-0.6dL/g, so that the stability of the reaction is greatly improved.
In the invention, the viscosity of the polyamic acid solution is measured by using the national standard GB/T10247-2008.
According to the invention, the conditions of the first reaction comprise: the reaction temperature is 0-35 ℃, and the reaction time is 8-14 h.
According to the invention, the conditions of the second reaction comprise: the reaction temperature is 0-35 ℃, and the reaction time is 1-2 h.
According to the invention, the conditions of the third reaction comprise: the reaction temperature is 60-90 ℃, and the reaction time is 1-3 h.
In the invention, the inventor researches and discovers that the reaction temperature is controlled to be 60-90 ℃ and the reaction time is controlled to be 1-3 hours after the imidizing agent is added, so that the imidizing time is greatly shortened and the reaction stability is improved under the condition that the polyamic acid is not degraded.
According to the present invention, it is preferable that when the viscosity of the polyamic acid solution reaches 0.35 to 0.55dL/g, preferably 0.35 to 0.45dL/g, and the end-capping agent is added, the polyimide resin thus obtained has the characteristics of high melt index and low extrusion temperature.
According to the present invention, the end-capping agent is selected from at least one of phthalic anhydride, aniline, p-toluidine and acetic anhydride.
According to the invention, the molar ratio of dianhydride to capping agent is 1:0.02-0.2, preferably 1:0.02-0.1, more preferably 1: 0.05-0.2.
According to the present invention, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
According to the invention, the polyimide solution has a solids content of 15 to 35 wt.%, preferably 20 to 30 wt.%.
According to the invention, the molar ratio of dianhydride to diamine is from 1:0.95 to 0.995, preferably from 1:0.95 to 0.985, more preferably from 1:0.955 to 0.985.
According to the invention, the diamine monomer is selected from one or more than two of the following monomers:
according to the invention, the diamine monomer is selected from one or more than two of the following monomers:
in the present invention, the diamine monomer may be specifically 4, 4' -bis (3-aminophenoxy) diphenylsulfone.
According to the invention, the imidizing agent is acetic anhydride and a tertiary amine compound, and the volume ratio of the acetic anhydride to the tertiary amine compound is 1:0.5-1, preferably 1: 0.5-0.8.
According to the invention, the tertiary amine compound is selected from triethylamine and/or pyridine.
According to the invention, the molar ratio of the diamine to the acetic anhydride is between 1:2.5 and 3, preferably between 1:2.5 and 2.8.
According to the present invention, in step (2), the polyimide solution is diluted to 5 to 10 wt% solid content.
According to the invention, the method also comprises the steps of crushing, drying, extruding and cutting the thermoplastic polyimide resin into polyimide resin granules.
According to the present invention, the drying conditions include: the drying temperature is 150-.
According to the invention, the conditions of the extrusion include: the extrusion temperature is 300 ℃ and 360 ℃, and the rotating speed is 10-50 rpm.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the viscosity of the polyamic acid solution is measured by adopting a national standard GB/T10247-2008 method;
the viscosity of the polyimide powder is measured by adopting a national standard GB/T10247-2008 method;
the melt index of the polyimide powder is measured by adopting a national standard GB/T3682.1-2018 method;
the mechanical property of the polyimide sample is measured by GB/T1040-;
1,2,3, 4-benzenetetracarboxylic dianhydride was synthesized in the laboratory by the following method (see 2018 university of shanghai university, university of china, preparation of highly soluble phenylacetylene-terminated thermosetting polyimide resin and performance research, written in lufunuo):
adding 100g of cyclohexene, 200mL of carbon tetrachloride and 10mL of absolute ethanol into a 1000mL three-neck flask, then placing the flask in an ice water bath at 0 ℃, dissolving 160g of liquid bromine in 100mL of carbon tetrachloride and dropwise adding the solution into the flask, controlling the solution to be completely dripped within 10 hours, after the reaction is finished, spirally distilling off redundant carbon tetrachloride and cyclohexene, and obtaining 188g of 1, 2' -dibromocyclohexane through reduced pressure distillation.
Adding 200g of sodium hydroxide into 400mL of ethylene glycol, heating to 210 ℃, evaporating about 80mL of water, then starting to dropwise add 188g of 1, 2' -dibromocyclohexane, heating to 230 ℃, continuing to introduce nitrogen after dropwise addition, continuing to collect fractions for 1h, separating a water layer of the product by using a separating funnel, and drying by using anhydrous calcium chloride to finally obtain 72g of cyclohexadiene.
Taking 72g of cyclohexadiene, adding 80g of maleic anhydride, starting mechanical stirring, reacting in a water bath at 45 ℃, wherein the exothermic reaction is observed, putting the mixture into a cold water bath for cooling when the reaction is observed to be started, stirring for 12 hours after the reaction is cooled, filtering to obtain a crude product, concentrating the filtrate, collecting the crude product, and boiling and washing the obtained crude product with water to obtain 124g of bicyclo [2,2,2] -5-octene-2, 3-dicarboxylic anhydride.
Adding 80mL of 60% concentrated nitric acid into a 500mL flask, then adding 60mg of ammonium metavanadate and 20mg of ammonium molybdate, controlling the reaction temperature at 60 ℃, adding 20g of bicyclo [2,2,2] -5-octene-2, 3-dicarboxylic anhydride in batches in 4 hours, simultaneously dropwise adding 30mL of fuming nitric acid, cooling and filtering after the reaction is finished, and recrystallizing by using water to obtain 25g of cis-1,2,3, 4-cyclohexanetetracarboxylic acid.
Adding 10g of cis-1,2,3, 4-cyclohexanetetracarboxylic acid into 120mL of glacial acetic acid, heating and refluxing, dropwise adding 95mL of glacial acetic acid dissolved with 16g of bromine, continuously refluxing for 3 hours after dropwise adding, cooling, recrystallizing with water, filtering and drying to obtain 5g of 1,2,3, 4-biphenyltetracarboxylic acid.
Finally, the obtained 1,2,3, 4-pyromellitic acid is recrystallized in acetic anhydride, and the filter cake is dried and then put into a sublimation tube to be sublimated to obtain the 1,2,3, 4-pyromellitic dianhydride.
4, 4' -bis (3-aminophenoxy) diphenyl sulfone available from Nanjing Yuetui chemical Co., Ltd;
1,2,4, 5-pyromellitic dianhydride was purchased from pharmaceutical industry, Inc., national drug group;
examples and comparative examples all other materials were commercially available.
Example 1
The thermoplastic polyimide resin pellet is prepared as follows:
(1) adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (64.8735g, 150.0mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,3, 4-benzenetetracarboxylic dianhydride (6.4454g, 29.55mmol) and 1,2,4, 5-benzenetetracarboxylic dianhydride (25.7818g, 118.2mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding phthalic anhydride (1.3330g, 9mmol) after the viscosity of the polyamic acid is measured to be 0.45dL/g, stirring at room temperature for 1 hour, then adding 36mL of chemical imidization reagent acetic anhydride and 18mL of pyridine, and reacting at 80 ℃ for 2 hours to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 10% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and then crushing for 3 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.40dL/g, and the melt index is 3g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 340 ℃ by using a high-temperature desktop extruder, extruding and granulating at the screw rotation speed of 20rpm to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
example 2
The thermoplastic polyimide resin pellet is prepared as follows:
(1) adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (64.8769g,150.0mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,3, 4-benzenetetracarboxylic dianhydride (12.8255g,58.8mmol) and 1,2,4, 5-benzenetetracarboxylic dianhydride (19.2380g,88.2mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding phthalic anhydride (1.7773g,12mmol) after the viscosity of the polyamic acid is measured to be 0.37dL/g, stirring at room temperature for 1 hour, then adding 36mL of acetic anhydride and 18mL of pyridine, and reacting at 80 ℃ for 1.5 hours to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 10% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and then crushing for 3 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.36dL/g, and the melt index is 1.8g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 320 ℃ by using a high-temperature desktop extruder at the screw rotation speed of 20rpm, and extruding and granulating to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
example 3
(1) Adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (64.8735g, 150.0mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,3, 4-benzenetetracarboxylic dianhydride (3.2220g, 14.78mmol) and 1,2,4, 5-benzenetetracarboxylic dianhydride (29.0050g, 118.2mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding phthalic anhydride (1.3330g, 9mmol) after the viscosity of the polyamic acid is measured to be 0.53dL/g, stirring at room temperature for 2 hours, then adding 36mL of chemical imidization reagent acetic anhydride and 18mL of pyridine, and reacting at the temperature of 90 ℃ for 1 hour to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 8% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and then crushing for 5 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.49dL/g, and the melt index is 1g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 350 ℃ by using a high-temperature desktop extruder at the screw rotation speed of 10rpm, and extruding and granulating to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
example 4
(1) Adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (57.5125g, 132.98mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,3, 4-benzenetetracarboxylic dianhydride (3.6361g, 16.67mmol) and 1,2,4, 5-benzenetetracarboxylic dianhydride (29.0819g, 133.33mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding aniline (0.8383g, 9mmol) after the viscosity of the polyamic acid is measured to be 0.5dL/g, stirring at room temperature for 2 hours, then adding 36mL of a chemical imidizing reagent and 18mL of pyridine, and reacting at 90 ℃ for 1 hour to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 8 wt% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and crushing for 5 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.44dL/g, and the melt index is 0.6g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 350 ℃ by using a high-temperature desktop extruder at the screw rotation speed of 10rpm, and extruding and granulating to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
example 5
The thermoplastic polyimide resin pellet is prepared as follows:
(1) adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (64.8735g, 150.0mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,3, 4-benzenetetracarboxylic dianhydride (9.6682g, 44.33mmol) and 1,2,4, 5-benzenetetracarboxylic dianhydride (22.5591g, 103.43mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding phthalic anhydride (1.3330g, 9mmol) after the viscosity of the polyamic acid is measured to be 0.45dL/g, stirring at room temperature for 1 hour, then adding 36mL of acetic anhydride and 18mL of pyridine as chemical imidization reagents, and reacting at 80 ℃ for 2 hours to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 10% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and then crushing for 3 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.41dL/g, and the melt index is 2.7g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 340 ℃ by using a high-temperature desktop extruder, extruding and granulating at the screw rotation speed of 20rpm to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
example 6
The thermoplastic polyimide resin pellet is prepared as follows:
(1) adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (64.8735g, 150.0mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,3, 4-benzenetetracarboxylic dianhydride (16.1137g, 73.88mmol) and 1,2,4, 5-benzenetetracarboxylic dianhydride (16.1139g, 73.88mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding phthalic anhydride (1.3330g, 9mmol) after the viscosity of the polyamic acid is measured to be 0.46dL/g, stirring at room temperature for 1 hour, then adding 36mL of acetic anhydride and 18mL of pyridine, and reacting at 80 ℃ for 2 hours to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 10% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and then crushing for 3 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.43dL/g, and the melt index is 2.0g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 320 ℃ by using a high-temperature desktop extruder at the screw rotation speed of 30rpm, and extruding and granulating to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
comparative example 1
The thermoplastic polyimide resin pellet is prepared as follows:
(1) adding 4, 4' -bis (3-aminophenoxy) diphenyl sulfone (64.8735g, 150.0mmol) into a reaction bottle under the protection of nitrogen, adding 415mL of N, N-dimethylacetamide, stirring to completely dissolve the N, N-dimethylacetamide, then adding 1,2,4, 5-pyromellitic dianhydride (32.2272g, 147.75mmol), stirring at room temperature for 10 hours to obtain a polyamic acid solution, adding 1.3330g, 9mmol of phthalic anhydride after measuring the viscosity of the polyamic acid to be 0.50dL/g, stirring at room temperature for 1 hour, then adding 36mL of chemical imidization reagent acetic anhydride and 18mL of pyridine, and reacting at the temperature of 80 ℃ for 2 hours to obtain a polyimide solution;
(2) preparing polyimide powder: diluting the polyimide solution to 10% of solid content, precipitating in a precipitator, collecting precipitates, fully washing, drying, and then crushing for 3 minutes by a crusher to obtain thermoplastic polyimide powder, wherein the measured viscosity is 0.44dL/g, and the melt index is 0.4g/10 min;
(3) preparation of polyimide pellets: and (3) drying the polyimide powder in a common oven at 170 ℃ for 4 hours, processing at 370 ℃ by using a high-temperature desktop extruder at the screw rotation speed of 20rpm, and extruding and granulating to obtain granules.
The polyimide is obtained by calculation according to the feeding amount and the residual amount, and the structure of the polyimide is shown as the following formula:
ar is:
TABLE 1
| Numbering | x | PAA viscosity (dl/g) | PI viscosity (dl/g) | Melt index (g/10min) | Extrusion temperature (. degree.C.) |
| Example 1 | 0.80 | 0.45 | 0.40 | 3.0 | 340 |
| Example 2 | 0.60 | 0.37 | 0.36 | 1.8 | 320 |
| Example 3 | 0.89 | 0.53 | 0.49 | 1.0 | 350 |
| Example 4 | 0.89 | 0.50 | 0.44 | 0.6 | 360 |
| Example 5 | 0.70 | 0.45 | 0.41 | 2.7 | 340 |
| Example 6 | 0.5 | 0.46 | 0.43 | 2.0 | 320 |
| Comparative example 1 | 0.50 | 0.44 | 0.4 | 370 |
As can be seen from the results in Table 1, the polyimide prepared by using the method of the present invention, in which l,2,3, 4-biphenyldianhydride monomer is added, in examples 1-6, has a higher melt index (0.6-3.0g/10min) under the same conditions (360 ℃/12.5kg), and the temperature of the pellets extruded by the extruder is reduced from 370 ℃ to 360 ℃ and 320 ℃, so that the method has the obvious effect of reducing the extrusion temperature, and greatly improves the thermal stability of resin processing.
Test example
The polyimide pellets of examples 1 to 6 and comparative example 1 were subjected to injection molding and molding at 340 ℃ and 210bar to obtain polyimide samples, and the mechanical properties of the prepared polyimide samples were tested, with the test results shown in table 2.
TABLE 2
| Numbering | Tensile Strength (MPa) | Tensile modulus (GPa) | Elongation at Break (%) |
| Example 1 | 110.6 | 3.0 | 5.0 |
| Example 2 | 112.9 | 2.9 | 4.2 |
| Example 3 | 120.2 | 2.9 | 4.0 |
| Example 4 | 116.4 | 2.9 | 4.1 |
| Example 5 | 115.0 | 2.9 | 4.4 |
| Example 6 | 103.2 | 2.9 | 4.7 |
| Comparative example 1 | 107.7 | 2.9 | 4.2 |
As can be seen from Table 2, the samples prepared by injection molding of the polyimide pellets provided by the invention have equivalent tensile strength, tensile modulus and elongation at break, which shows that the thermoplastic polyimide resin provided by the invention not only has high melt index and low extrusion temperature, but also can not affect the mechanical properties of the 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 thermoplastic polyimide resin, characterized in that the polyimide resin has a structure represented by formula (1):
wherein Ar is the residue of a primary diamine monomer; ar is selected from one or more than two of the following groups:
x is 0.45-0.9;
EG is an end-capping agent residue selected from one of the following groups:
the viscosity of the thermoplastic polyimide resin at 30 ℃ is 0.35-0.55 dL/g.
2. The thermoplastic polyimide resin according to claim 1, wherein Ar is one or two or more selected from the group consisting of:
preferably, x is 0.5 to 0.8;
preferably, the capping agent is selected from at least one of the structures shown below:
3. the thermoplastic polyimide resin according to claim 1 or 2, wherein the thermoplastic polyimide resin has a melt index of 0.5 to 5g/10min at 360 ℃ and a load of 12.5 kg; the extrusion temperature of the thermoplastic polyimide resin is 300-360 ℃.
4. A method for preparing the thermoplastic polyimide resin according to any one of claims 1 to 3, comprising the steps of:
(1) preparation of polyimide solution: in the presence of a solvent and an inert atmosphere, carrying out a first-step reaction on a diamine monomer and a dianhydride monomer to obtain a polyamic acid solution; adding an end-capping reagent when the viscosity of the polyamic acid solution reaches 0.3-0.6dL/g, performing the second-step reaction, and adding an imidization reagent to perform the third-step reaction to obtain a polyimide solution;
(2) preparation of polyimide resin: and (2) diluting the polyimide solution obtained in the step (1), separating out the polyimide solution in a precipitator, washing and drying to obtain the thermoplastic polyimide resin.
5. The method of claim 4, wherein the conditions of the first step reaction comprise: the reaction temperature is 0-35 ℃, and the reaction time is 8-14 h;
preferably, the conditions of the second-step reaction include: the reaction temperature is 0-35 ℃, and the reaction time is 1-2 h;
preferably, the conditions of the third step reaction include: the reaction temperature is 60-90 ℃, and the reaction time is 1-3 h.
6. The process according to claim 4 or 5, wherein the end-capping agent is added when the viscosity of the polyamic acid solution reaches 0.35 to 0.55 dL/g;
preferably, the end-capping agent is selected from at least one of phthalic anhydride, aniline, p-toluidine and acetic anhydride;
preferably, the molar ratio of dianhydride to capping agent is 1:0.02-0.2, preferably 1: 0.02-0.1;
preferably, the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
preferably, the polyimide solution has a solid content of 15 to 35 wt%, preferably 20 to 30 wt%.
7. The process according to any one of claims 4-6, wherein the molar ratio of dianhydride to diamine is from 1:0.95 to 0.995, preferably from 1:0.95 to 0.985;
the dianhydride monomer is selected from 1,2,3, 4-pyromellitic dianhydride and/or 1,2,4, 5-pyromellitic dianhydride;
preferably, the diamine monomer is selected from one or two or more of the following monomers:
more preferably, the diamine monomer is selected from one or two or more of the following monomers:
8. the process according to any one of claims 4 to 7, wherein the imidizing agent is acetic anhydride and a tertiary amine compound in a volume ratio of 1:0.5 to 1, preferably 1:0.5 to 0.8;
preferably, the tertiary amine compound is selected from triethylamine and/or pyridine;
preferably, the molar ratio of the diamine to the acetic anhydride is from 1:2.5 to 3, preferably from 1:2.5 to 2.8.
9. The process of any one of claims 4-8, wherein in step (2), the polyimide solution is diluted to a solids content of 5-10 wt%.
10. The method of any one of claims 4-9, further comprising pulverizing, oven drying, extruding, and pelletizing the thermoplastic polyimide resin to obtain polyimide resin pellets;
preferably, the drying conditions include: the drying temperature is 150-;
preferably, the conditions of the extrusion include: the extrusion temperature is 300 ℃ and 360 ℃, and the rotating speed is 10-50 rpm.
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| US20090263745A1 (en) * | 2008-03-31 | 2009-10-22 | Katsuya Sakayori | Polyimide precursor, resin composition comprising the polyimide precursor, pattern forming method using the resin composition, and articles produced by using the resin composition |
| CN102634021A (en) * | 2012-03-30 | 2012-08-15 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyimide resin and preparation method thereof |
| CN105906809A (en) * | 2016-06-03 | 2016-08-31 | 万华化学集团股份有限公司 | Polyimide preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090263745A1 (en) * | 2008-03-31 | 2009-10-22 | Katsuya Sakayori | Polyimide precursor, resin composition comprising the polyimide precursor, pattern forming method using the resin composition, and articles produced by using the resin composition |
| CN102634021A (en) * | 2012-03-30 | 2012-08-15 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyimide resin and preparation method thereof |
| CN105906809A (en) * | 2016-06-03 | 2016-08-31 | 万华化学集团股份有限公司 | Polyimide preparation method |
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