CN113088076B - High-performance polyimide molding powder, preparation method and application thereof - Google Patents
High-performance polyimide molding powder, preparation method and application thereof Download PDFInfo
- Publication number
- CN113088076B CN113088076B CN201911341996.1A CN201911341996A CN113088076B CN 113088076 B CN113088076 B CN 113088076B CN 201911341996 A CN201911341996 A CN 201911341996A CN 113088076 B CN113088076 B CN 113088076B
- Authority
- CN
- China
- Prior art keywords
- polyimide
- hours
- formula
- temperature
- polyamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- 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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
-
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses high-performance polyimide molding powder and a preparation method thereof. The preparation method comprises the following steps: two different polyamic acids are capped with benzoic anhydride, blended and then thermally imidized with a boiling dehydrating agent to obtain polyimide molding powder. The polyimide molding powder prepared by the invention has good molding property, excellent heat resistance and impact resistance, for example, the polyimide molding powder can be molded by compression, the molding pressure is 20-200MPa, the molding temperature is 370-460 ℃, the 5 wt% thermal weight loss temperature of the corresponding polyimide molding compound is 540-560 ℃, the glass transition temperature is 360-490 ℃, and the impact strength is 50-200KJ/m 2 。
Description
Technical Field
The invention relates to a polyimide material, in particular to polyimide molding powder, and belongs to the technical field of preparation of high polymer materials.
Background
The polyimide engineering plastic has the highest heat-resistant grade in all thermoplastic resins, has the advantages of high temperature resistance, low temperature resistance, solvent resistance, radiation resistance, outstanding mechanical property, dielectric property and the like, and is widely applied to various fields.
The polyimide molding material is a very important class of polyimide engineering plastics, generally adopts a rigid main chain structure, has no melting point or softening point below the decomposition temperature, and needs to be molded by adopting a special isostatic pressing-sintering mode. The high-temperature-resistant alloy has extremely high temperature-resistant grade, continuous use temperature of more than 350 ℃, excellent wear resistance, low creep, good electrical insulation performance and chemical resistance, so that the high-temperature-resistant alloy has wide application in the military and civil fields, wherein the military field mainly comprises airplanes and aerospace products, such as self-lubricating bushings of aircraft engines, and the like, and the civil field comprises automobiles, electronic and electrical appliances, machinery, semiconductors and the like.
Many studies have been made at home and abroad to improve the processability of polyimide molding powder, wherein a typical representative of polyimide molding materials and profiles is Vespel from dupont, pyromellitic dianhydride and diaminodiphenyl ether are used as monomers, which are widely regarded as having excellent properties, but a molecular chain of the polyimide molding materials is a strong rigid and highly symmetrical structure, so that the polyimide molding materials are insoluble, infusible, low in thermal property and poor in processability, and special high-temperature and high-pressure molding conditions are required, thereby limiting the application range of the polyimide molding materials. Therefore, in order to further improve the processability of the imide molding powder and to improve the processability thereof, research and improvement of imidization process of polyimide are required.
Disclosure of Invention
The invention provides high-performance polyimide molding powder and a preparation method thereof, which are used for solving the problems of low thermal performance and low processing performance of the polyimide molding powder in the prior art.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the embodiment of the invention provides a preparation method of high-performance polyimide molding powder, which comprises the following steps: respectively sealing polyimide A and polyimide B with benzoic anhydride, wherein the sealing group has a structure shown in formula III, then blending, carrying out imidization reaction with a boiling dehydrating agent, and then carrying out post-treatment to obtain the polyimide molding powder.
Wherein the polyimide A and the polyimide B respectively have a structure represented by formula I, II.
In the formula I, n is an integer between 20 and 1000, AR1 is selected from one or two of the formulas I and ii, and Ar1 is selected from one or two of the formulas iii and iv.
In formula II, m is an integer from 20 to 1000 and AR2 is selected from one or more members of formula v-x.
Further, the preparation method of the high-performance polyimide molding powder provided by the embodiment of the invention comprises the following steps:
s1, adding tetracarboxylic dianhydride and diamine required for preparing polyimide A into an aprotic polar solvent at room temperature in a protective atmosphere, stirring and reacting for 4-20 hours, and then adding phthalic anhydride to react for 1-10 hours to obtain a polyamic acid solution a;
s2, adding tetracarboxylic dianhydride and diamine required by polyimide B preparation into an aprotic polar solvent at room temperature in a protective atmosphere, stirring for reaction for 4-20 hours, and then adding phthalic anhydride for reaction for 1-10 hours to obtain a polyamic acid solution B;
s3, mixing and stirring the polyamic acid solution a and the polyamic acid solution b for 0-0.5 hour at room temperature in a protective atmosphere to blend the two polyamic acids uniformly;
s4, adding the blended polyamic acid obtained in the step S3 into a boiling dehydrating agent for reaction at the reaction temperature of 150 ℃ and 220 ℃ for refluxing with water for 2-20 hours, and then carrying out post-treatment to obtain the polyimide molding powder.
Preferably, the molar ratio of the polyimide A to the polyimide B is 5-9.5: 5-0.5.
Preferably, the aprotic polar solvent includes any one of N, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and m-cresol, without being limited thereto.
Preferably, the dehydrating solvent includes any one of toluene, xylene, chloro-o-xylene, and m-cresol, without being limited thereto.
Preferably, the molar ratio of the tetracarboxylic dianhydride, the diamine and the phthalic anhydride is 0.9995-0.95: 1: 0.001-0.1.
preferably, the protective atmosphere is a nitrogen atmosphere.
Further, the polyamic acid solution a and the polyamic acid solution b may be yellow viscous.
Preferably, the post-processing in step S4 includes: after the reaction is carried out until light yellow powder is precipitated in a reaction system, cooling and filtering are carried out, filter cakes are fully washed, then the mixture is baked at 100 ℃ for 10 to 36 hours and then is heat treated at 300-380 ℃ for 1 to 20 hours in vacuum, and the mixture is crushed after cooling to obtain the polyimide molding powder.
The embodiment of the invention also provides the high-performance polyimide molding powder prepared by the method, wherein the compression molding pressure of the high-performance polyimide molding powder is 20-200MPa, and the molding temperature is 370-460 ℃.
Correspondingly, the embodiment of the invention also provides a compression molding method of the high-performance polyimide molding powder, which comprises the following steps: the compression molding pressure is 20-200MPa, and the molding temperature is 370-460 ℃.
Further, the embodiment of the invention also provides application of the high-performance polyimide molding powder in the field of engineering plastics.
Further, the embodiment of the invention also provides application of the preparation method of the high-performance polyimide molding powder in the field of preparation of high polymer materials.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the polyimide molding powder prepared by the method of the embodiment of the invention has good molding performance, excellent heat resistance and impact resistance, for example, the polyimide molding powder can be molded by compression, the molding pressure is 20-200MPa, the molding temperature is 370-460 ℃, the corresponding 5 wt% thermal weight loss temperature of the polyimide molding compound is 540-560 ℃, the glass transition temperature is 360-490 ℃, and the impact strength is 50-200KJ/m 2 。
(2) The embodiment of the invention blends two different polyamic acids, terminates the polyamic acids by benzoic anhydride, and then drops the polyamic acids into a boiling dehydrating agent, so that polyimide molding powder is obtained by thermal imidization, and the polyimide A prepared by the method has a molecular chain structure with strong rigidity and good symmetry, so that the material has excellent thermal property and mechanical property; the prepared polyimide B molecular chain has a nonlinear, non-coplanar, asymmetric and twisted chain structure, intermolecular acting force is reduced, chain accumulation is weakened, the material has better plasticity, the molding pressure required by the molding powder is relatively low, and various structural functional parts can be prepared by mold pressing, curing and molding and machining.
Drawings
FIG. 1 shows the IR spectra of the polyimide molding powders prepared in examples 1 and 2 of the present invention, wherein A represents the data of example 1 and B represents the data of example 2.
Detailed Description
Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The reagents and materials used in the following examples of the invention are commercially available from public sources, and the equipment and instruments used in the process are conventional in the art.
Example 1
At room temperature, 0.7mol (140.17g) of 4,4 '-diaminodiphenyl ether and 0.6965mol (151.92g) of pyromellitic dianhydride were added to 2500ml of N, N' -dimethylacetamide with nitrogen protection, stirred and reacted for 20 hours, after complete dissolution, 0.007mol (1.036g) of benzoic anhydride was added, and reacted for 10 hours to obtain a polyamic acid solution a in a pale yellow viscous state.
At room temperature, 0.3mol (32.44g) of p-phenylenediamine and 0.2985mol (87.82g) of 3,4 '-biphenyl dianhydride are added into 490ml of N, N' -dimethylacetamide with nitrogen protection, stirred and reacted for 20 hours, after complete dissolution, 0.003mol (0.444g) of benzoic anhydride is added, and reacted for 10 hours to obtain a polyamic acid solution b in a light yellow viscous state.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 30 minutes in a nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. Dripping the blended polyamic acid into 900ml of boiling dehydrating agent xylene, controlling the temperature at 170 ℃, refluxing and carrying water for 18 hours under the protection of nitrogen, separating out light yellow powder, cooling and filtering, fully washing a filter cake, drying for 36 hours at 100 ℃, carrying out heat treatment for 1 hour at 360 ℃ in vacuum, cooling and crushing to obtain the polyimide molding powder, wherein an infrared spectrogram of the polyimide molding powder is shown in figure 1.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.78, and was molded by compression at a temperature of 440 ℃ under a pressure of 80 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 549 ℃, the glass transition temperature is 436 ℃, and the impact strength is 96KJ/m 2 。
Comparative example 1
Adding 0.7mol (140.17g) of 4,4 '-diaminodiphenyl ether and 0.6965mol (151.92g) of pyromellitic dianhydride into 2500ml of N, N' -dimethylacetamide with nitrogen protection at room temperature, stirring for reaction for 20 hours, adding 0.007mol (1.036g) of benzoic anhydride after complete dissolution, reacting for 10 hours to obtain a polyamic acid solution, dripping the polyamic acid solution into 900ml of boiling dehydrating agent xylene at the temperature of 170 ℃, refluxing with water under nitrogen protection for 18 hours to precipitate light yellow powder, cooling, filtering, fully washing a filter cake, drying at 100 ℃ for 36 hours, carrying out heat treatment at 360 ℃ for 1 hour in vacuum, cooling and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in comparative example 1 was found to have a Ubbelohde viscosity of 0.85, and was molded by compression at a molding temperature of 440 ℃ under a pressure of 80 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 550 ℃, the glass transition temperature is 380 ℃, and the impact strength is only 25KJ/m 2 。
Example 2
At room temperature, 0.5mol (100.12g) of 4,4 '-diaminodiphenyl ether and 0.4998mol (109.01g) of pyromellitic dianhydride were added to 2500ml of N, N' -dimethylformamide with nitrogen protection, stirred and reacted for 12 hours, after complete dissolution, 0.0005mol (0.074g) of benzoic anhydride was added, and reacted for 6 hours to obtain a polyamic acid solution a in the form of pale yellow viscous.
0.5mol (54.07g) of p-phenylenediamine and 0.4998mol (147.04g) of 3,3 '-biphenyl dianhydride were added to 490ml of N, N' -dimethylformamide protected with nitrogen at room temperature, stirred and reacted for 12 hours, after complete dissolution, 0.0005mol (0.074g) of benzoic anhydride was added, and reacted for 6 hours to obtain a polyamic acid solution b in a pale yellow viscous state.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 20 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. Dripping the blended polyamic acid into 1000ml of boiling dehydrating agent m-cresol at 220 ℃, refluxing for 20 hours with water under the protection of nitrogen, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying for 30 hours at 100 ℃, carrying out vacuum heat treatment for 20 hours at 380 ℃, cooling and crushing to obtain polyimide molding powder, wherein an infrared spectrogram of the polyimide molding powder is shown in figure 1.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.75, and was molded by compression at a temperature of 450 ℃ under a pressure of 90 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 543 ℃, the glass transition temperature is 446 ℃, and the impact strength is 72KJ/m 2 。
Example 3
At room temperature, 0.95mol (190.23g) of 4,4 '-diaminodiphenyl ether and 0.9025mol (265.53g) of 4, 4' -biphenyl dianhydride are added into 3000ml of N-methyl-2-pyrrolidone with nitrogen protection to be stirred and reacted for 15 hours, after the components are completely dissolved, 0.095mol (14.06g) of benzoic anhydride is added to be reacted for 5 hours, and a viscous light yellow polyamic acid solution a is obtained.
0.05mol (5.41g) of p-phenylenediamine and 0.0475mol (14.74g) of 3, 4' -oxygen ether dianhydride are added into 500ml of N-methyl-2-pyrrolidone with nitrogen protection at room temperature, stirred and reacted for 15 hours, after complete dissolution, 0.005mol (0.74g) of benzoic anhydride is added, and then reacted for 5 hours, thus obtaining a light yellow viscous polyamic acid solution b.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 15 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And dripping the blended polyamic acid into 1000ml of a boiling dehydrating agent chloro-o-xylene, carrying out reflux for 10 hours with water at the temperature of 200 ℃, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying at 100 ℃ for 20 hours, carrying out heat treatment at 360 ℃ for 4 hours in vacuum, cooling and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.82, and was molded by compression at a temperature of 450 ℃ under a pressure of 80 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 542 ℃, the glass transition temperature is 392 ℃, and the impact strength is 85KJ/m 2 。
Example 4
0.6mol (64.88g) of p-phenylenediamine and 0.594mol (174.77g) of 4,4 '-biphenyl dianhydride are added into 1800ml of N, N' -dimethylformamide with nitrogen protection at room temperature, stirred and reacted for 4 hours, after complete dissolution, 0.012mol (1.777g) of benzoic anhydride is added, and then reacted for 1 hour, so that a light yellow viscous polyamic acid solution a is obtained.
0.4mol (43.26g) of p-phenylenediamine and 0.392mol (126.31g) of 3,4 '-benzophenone dianhydride are added into 490ml of N, N' -dimethylacetamide with nitrogen protection at room temperature, stirred and reacted for 4 hours, after complete dissolution, 0.008mol (0.185g) of benzoic anhydride is added, and then reacted for 1 hour, so that a polyamic acid solution b with a light yellow viscous shape is obtained.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 5 minutes in a nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And dripping the blended polyamic acid into 1000ml of boiling dehydrating agent toluene, carrying out reflux with water for 2 hours at the temperature of 150 ℃, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying for 10 hours at the temperature of 100 ℃, carrying out heat treatment for 1 hour at the temperature of 300 ℃ in vacuum, cooling and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.89, and was molded by compression at a temperature of 460 ℃ under a pressure of 200 MPa. The resulting polyimide moldingThe 5 wt% thermal weight loss temperature of the material is 545 ℃, the glass transition temperature is 438 ℃, and the impact strength is 50KJ/m 2 。
Example 5
0.6mol (64.88g) of p-phenylenediamine, 0.297mol (87.39g) of 4, 4' -biphenyl dianhydride and 0.297mol (64.78) of pyromellitic dianhydride were added to 1800ml of dimethyl sulfoxide with nitrogen protection at room temperature, stirred and reacted for 18 hours, and after complete dissolution, 0.012mol (1.777g) of benzoic anhydride was added and reacted for 5 hours to obtain a pale yellow viscous polyamic acid solution a.
At room temperature, 0.4mol (43.26g) of p-phenylenediamine and 0.392mol (126.31g) of 3,3 '-benzophenone dianhydride are added into 500ml of dimethyl sulfoxide with nitrogen protection to be stirred and reacted for 20 hours, after the p-phenylenediamine and the 3, 3' -benzophenone dianhydride are completely dissolved, 0.008mol (0.185g) of benzoic anhydride is added to be reacted for 5 hours, and the polyamic acid solution b with light yellow viscous state is obtained.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 15 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And dripping the blended polyamic acid into 1000ml of boiling dehydrating agent m-cresol, carrying out reflux with water for 18 hours at the temperature of 220 ℃, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying for 36 hours at the temperature of 100 ℃, carrying out heat treatment for 6 hours at the temperature of 360 ℃ in vacuum, cooling and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in the example was tested to have a Ubbelohde viscosity of 0.91, and was molded by compression at 460 ℃ under a pressure of 200 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 545 ℃, the glass transition temperature is 490 ℃, and the impact strength is 60KJ/m 2 。
Example 6
At room temperature, 0.8mol (160.19g) of 4,4 '-diaminodiphenyl ether and 0.798mol (174.06g) of pyromellitic dianhydride were added to 2600ml of N, N' -dimethylacetamide under nitrogen protection, stirred and reacted for 15 hours, after complete dissolution, 0.004mol (0.5925g) of benzoic anhydride was added, and reacted for 4 hours to obtain a polyamic acid solution a in a pale yellow viscous state.
0.2mol (21.63g) of p-phenylenediamine and 0.1995mol (61.89g) of 3,3 '-oxyether dianhydride are added into 720ml of N, N' -dimethylacetamide with nitrogen protection at room temperature, stirred and reacted for 20 hours, after complete dissolution, 0.001mol (0.1481g) of benzoic anhydride is added, and then reacted for 8 hours, so that a light yellow viscous polyamic acid solution b is obtained.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 20 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And (2) dropwise adding the blended polyamic acid into 1200ml of boiling dehydrating agent xylene, carrying out reflux with water at the temperature of 170 ℃ for 20 hours, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying at the temperature of 100 ℃ for 36 hours, carrying out vacuum heat treatment at the temperature of 350 ℃ for 4 hours, cooling, and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.79, and was molded by compression at a temperature of 440 ℃ under a pressure of 80 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 542 ℃, the glass transition temperature is 390 ℃, and the impact strength is 91KJ/m 2 。
Example 7
At room temperature, 0.3mol (60.07g) of 4,4 '-diaminodiphenyl ether, 0.4mol (43.26g) of p-phenylenediamine and 0.6965mol (151.92g) of pyromellitic dianhydride were added to 2500ml of N, N' -dimethylformamide with nitrogen protection, stirred and reacted for 20 hours, and after complete dissolution, 0.007mol (1.036g) of benzoic anhydride was added and reacted for 10 hours to obtain a polyamic acid solution a in a pale yellow viscous state.
0.3mol (32.44g) of p-phenylenediamine, 0.147mol (43.25g) of 3,4 ' -biphenyldianhydride and 0.147mol (43.25g) of 3,3 ' -biphenyldianhydride were added to 520ml of N, N ' -dimethylformamide with nitrogen protection at room temperature, stirred and reacted for 20 hours, and after complete dissolution, 0.012mol (1.777g) of benzoic anhydride was added and reacted for 10 hours to obtain polyamic acid solution b in a pale yellow viscous state.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 20 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And (2) dropwise adding the blended polyamic acid into 1100ml of boiling dehydrating agent chloro-o-xylene, carrying out reflux with water at the temperature of 210 ℃ for 18 hours, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying at the temperature of 100 ℃ for 30 hours, carrying out heat treatment at the temperature of 380 ℃ for 1 hour in vacuum, cooling, and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.76, and was molded by compression at a temperature of 450 ℃ under a pressure of 150 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 550 ℃, the glass transition temperature is 400 ℃, and the impact strength is 122KJ/m 2 。
Example 8
At room temperature, 0.5mol (100.12g) of 4,4 '-diaminodiphenyl ether and 0.49875mol (108.79g) of pyromellitic dianhydride were added to 1800ml of N, N' -dimethylacetamide with nitrogen protection, stirred and reacted for 20 hours, after complete dissolution, 0.0025mol (0.3703g) of benzoic anhydride was added, and reacted for 6 hours to obtain a polyamic acid solution a.
0.5mol (54.07g) of p-phenylenediamine, 0.4mol (117.69g) of 3,4 ' -biphenyl dianhydride and 0.09975mol (30.94g) of 3,4 ' -oxy-ether dianhydride were added to 1800ml of N, N ' -dimethylacetamide with nitrogen protection and stirred for reaction for 20 hours at room temperature, after complete dissolution, 0.0025mol (0.3703g) of benzoic anhydride was added and the reaction was continued for 10 hours to obtain a polyamic acid solution b.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 30 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And (2) dripping the blended polyamic acid into 5000ml of boiling dehydrating agent m-cresol at the temperature of 200 ℃, refluxing with water for 18 hours to separate out light yellow powder, cooling, filtering, fully washing a filter cake, drying at the temperature of 100 ℃ for 36 hours, performing vacuum heat treatment at the temperature of 370 ℃ for 1.5 hours, cooling and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.93, and was molded by compression at a temperature of 370 ℃ under a pressure of 20 MPa. The resulting polyimide moldingThe 5 wt% thermal weight loss temperature of the material is 540 ℃, the glass transition temperature is 360 ℃, and the impact strength is 200KJ/m 2 。
Example 9
0.2mol (40.05g) of 4,4 '-diaminodiphenyl ether, 0.4mol (43.27g) of p-phenylenediamine, 0.399mol (87.03g) of pyromellitic dianhydride and 0.171mol (50.31g) of 4, 4' -biphenyl dianhydride were added to 2400ml of N-methyl-2-pyrrolidone with nitrogen protection and stirred for reaction for 18 hours at room temperature, after complete dissolution, 0.006mol (0.8887g) of benzoic anhydride was added and reaction was carried out for 10 hours to obtain a polyamic acid solution a.
0.4mol (43.26g) of p-phenylenediamine and 0.396mol (116.51g) of 3,4 '-biphenyl dianhydride were added to 490ml of N, N' -dimethylacetamide with nitrogen protection at room temperature, and stirred for reaction for 20 hours, after complete dissolution, 0.004mol (0.593g) of benzoic anhydride was added and reaction was continued for 10 hours to obtain a polyamic acid solution b.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 5 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And (2) dropwise adding the blended polyamic acid into 3000ml of boiling dehydrating agent xylene, carrying out reflux with water at the temperature of 170 ℃ for 18 hours, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying at the temperature of 100 ℃ for 36 hours, carrying out vacuum heat treatment at the temperature of 380 ℃ for 1 hour, cooling, and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.86, and was molded by compression at a temperature of 450 ℃ under a pressure of 120 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 550 ℃, the glass transition temperature is 426 ℃, and the impact strength is 86KJ/m 2 。
Example 10
At room temperature, 0.95mol (190.23g) of 4,4 ' -diaminodiphenyl ether, 0.6965mol (151.92g) of pyromellitic dianhydride and 0.225mol (66.20g) of 4,4 ' -biphenyl dianhydride were added to 3000ml of N, N ' -dimethylacetamide with nitrogen protection, stirred for reaction for 20 hours, and after complete dissolution, 0.057mol (8.4423g) of benzoic anhydride was added and reacted for 10 hours to obtain a polyamic acid solution a.
0.05mol (5.41g) of p-phenylenediamine and 0.04975mol (14.66g) of 3,4 '-biphenyldianhydride were added to 90ml of N, N' -dimethylacetamide under nitrogen protection at room temperature, and the mixture was stirred and reacted for 20 hours, and after completely dissolving, 0.0005mol (0.074g) of benzoic anhydride was added and reacted for 10 hours to obtain a polyamic acid solution b.
And mixing the polyamic acid solution a and the polyamic acid solution b together at room temperature, and stirring for 15 minutes under the nitrogen atmosphere to uniformly blend the two polyamic acids and avoid chain exchange reaction between the two polyamic acids. And dripping the blended polyamic acid into 5000ml of boiling dehydrating agent m-cresol at the temperature of 180 ℃, refluxing for 16 hours with water, separating out light yellow powder, cooling, filtering, fully washing a filter cake, drying at the temperature of 100 ℃ for 36 hours, carrying out heat treatment at the temperature of 350 ℃ for 6 hours in vacuum, cooling, and crushing to obtain the polyimide molding powder.
The polyimide molding powder obtained in this example was found to have a Ubbelohde viscosity of 0.95, and was molded by compression at a temperature of 460 ℃ under a pressure of 200 MPa. The 5 wt% thermal weight loss temperature of the obtained polyimide molding compound is 560 ℃, the glass transition temperature is 456 ℃, and the impact strength is 50KJ/m 2 。
In addition, the inventors of the present application also refer to examples 1 to 10, and have performed corresponding tests with other raw materials and process conditions listed in the present specification, and obtained polyimide molding powder products all having desirable properties. The high-performance polyimide molding powder can be prepared into polyimide molding compound by a compression molding mode, wherein the molding pressure is 20-200MPa, the molding temperature is 370-460 ℃, the corresponding 5 wt% thermal weight loss temperature of the polyimide molding compound is 540-560 ℃, the glass transition temperature is 360-490 ℃, and the impact strength is 50-200KJ/m 2 。
As described above, the aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of the invention being defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
Claims (7)
1. A preparation method of high-performance polyimide molding powder is characterized by comprising the following steps:
s1, adding tetracarboxylic dianhydride and diamine required by polyimide A preparation into an aprotic polar solvent at room temperature in a protective atmosphere, stirring and reacting for 4-20 hours, and then adding phthalic anhydride to react for 1-10 hours to obtain a polyamic acid solution a;
s2, adding tetracarboxylic dianhydride and diamine required for preparing polyimide B into an aprotic polar solvent at room temperature in a protective atmosphere, stirring and reacting for 4-20 hours, and then adding phthalic anhydride to react for 1-10 hours to obtain a polyamic acid solution B;
s3, mixing and stirring the polyamic acid solution a and the polyamic acid solution b for 0-0.5 hour at room temperature in a protective atmosphere to blend the two polyamic acids uniformly;
s4, adding the blended polyamic acid obtained in the step S3 into a boiling dehydrating agent for imidization reaction at the reaction temperature of 150-220 ℃ for refluxing with water for 2-20 hours, and then carrying out post-treatment to obtain polyimide A and polyimide B molding powder, wherein the polyimide A and the polyimide B have end capping groups with structures shown in the formula III;
the polyimide A and the polyimide B respectively have structures shown in a formula I and a formula II:
formula I
Formula II
In the formula I, n is an integer between 20 and 1000, AR1 is selected from one or two of the formulas I and ii, Ar1 is selected from one or two of the formulas iii and iv;
formula i, formula ii, formula iii, formula iv
Formula II wherein m is an integer from 20 to 1000 and AR2 is selected from one or more members of formula v-x;
formula v formula vi formula vii
(ix) formula viii;
formula III
The molar ratio of the polyimide A to the polyimide B is 5-9.5: 5-0.5.
2. The method of claim 1, wherein: the aprotic polar solvent used in steps S1 and S2 includes any one of N, N '-dimethylformamide, N' -dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and m-cresol.
3. The method of claim 1, wherein: the molar ratio of the tetracarboxylic dianhydride, the diamine and the phthalic anhydride adopted in the steps S1 and S2 is 0.9995-0.95: 1: 0.001-0.1.
4. the method of claim 1, wherein: the dehydrating agent comprises any one of toluene, xylene, chloro-o-xylene and m-cresol.
5. The method of claim 1, wherein the post-processing in step S4 includes: after the reaction is carried out until light yellow powder is separated out in the reaction system, cooling and filtering are carried out, the filter cake is fully washed, then the mixture is dried for 10 to 36 hours at the temperature of 100 ℃, then is subjected to heat treatment for 1 to 20 hours at the temperature of 300-380 ℃ in vacuum, and is crushed after cooling, thus obtaining the polyimide molding powder.
6. A high-performance polyimide molding powder produced by the method of any one of claims 1 to 5.
7. A molding method for high-performance polyimide molding powder according to claim 6, characterized by comprising: the adopted compression molding pressure is 20-200MPa, and the molding temperature is 370-460 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911341996.1A CN113088076B (en) | 2019-12-23 | 2019-12-23 | High-performance polyimide molding powder, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911341996.1A CN113088076B (en) | 2019-12-23 | 2019-12-23 | High-performance polyimide molding powder, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113088076A CN113088076A (en) | 2021-07-09 |
| CN113088076B true CN113088076B (en) | 2022-09-06 |
Family
ID=76664005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911341996.1A Active CN113088076B (en) | 2019-12-23 | 2019-12-23 | High-performance polyimide molding powder, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113088076B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009091470A (en) * | 2007-10-09 | 2009-04-30 | Ube Ind Ltd | Polyimide film producing method, and aromatic polyimide |
| CN101925633A (en) * | 2007-11-29 | 2010-12-22 | 宇部兴产株式会社 | Method for producing polyamic acid solution and polyamic acid solution |
| CN102219902A (en) * | 2011-05-19 | 2011-10-19 | 中国科学院长春应用化学研究所 | Polymide molding powder and preparation method thereof |
| CN104231269A (en) * | 2014-10-14 | 2014-12-24 | 中国科学院长春应用化学研究所 | Polyimide and preparation method thereof and polyimide molding powder |
| CN105037769A (en) * | 2015-09-16 | 2015-11-11 | 安徽鑫柏格电子股份有限公司 | Preparation method for polymide film with low thermal expansion coefficient |
| WO2016056595A1 (en) * | 2014-10-08 | 2016-04-14 | 宇部興産株式会社 | Polyimide precursor composition and method for producing insulating coating layer using same |
-
2019
- 2019-12-23 CN CN201911341996.1A patent/CN113088076B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009091470A (en) * | 2007-10-09 | 2009-04-30 | Ube Ind Ltd | Polyimide film producing method, and aromatic polyimide |
| CN101925633A (en) * | 2007-11-29 | 2010-12-22 | 宇部兴产株式会社 | Method for producing polyamic acid solution and polyamic acid solution |
| CN102219902A (en) * | 2011-05-19 | 2011-10-19 | 中国科学院长春应用化学研究所 | Polymide molding powder and preparation method thereof |
| WO2016056595A1 (en) * | 2014-10-08 | 2016-04-14 | 宇部興産株式会社 | Polyimide precursor composition and method for producing insulating coating layer using same |
| CN104231269A (en) * | 2014-10-14 | 2014-12-24 | 中国科学院长春应用化学研究所 | Polyimide and preparation method thereof and polyimide molding powder |
| CN105037769A (en) * | 2015-09-16 | 2015-11-11 | 安徽鑫柏格电子股份有限公司 | Preparation method for polymide film with low thermal expansion coefficient |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113088076A (en) | 2021-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108641082B (en) | Thermosetting polyimide prepolymer and preparation method and application thereof | |
| CN101392059A (en) | Colorless transparent aromatic polyimide film and preparation method thereof | |
| CN113968971B (en) | Preparation method of soluble and low-temperature rapid imidization polyimide film | |
| CN101565504B (en) | Preparation method of high-temperature endurable active toughener powder used for epoxy resin | |
| WO2012088759A1 (en) | Meltable polyimide moulding plastic and preparation method therefor | |
| CN105017533A (en) | Preparation method for polyamide imide coating | |
| WO2022126647A1 (en) | High-temperature energy storage hybrid polyetherimide dielectric thin film, preparation method therefor and use thereof | |
| CN115260491B (en) | Alkali-resistant hydrolysis-resistant polyimide engineering plastic and preparation method thereof | |
| CN107892745B (en) | Thermoplastic polybenzoxazole imide and preparation method thereof | |
| CN113088076B (en) | High-performance polyimide molding powder, preparation method and application thereof | |
| CN114605638A (en) | Preparation method of polyimide or polyetherimide | |
| CN110498923B (en) | Ultrahigh-temperature-resistant easy-to-mold polyimide resin and preparation method and application thereof | |
| JP2947094B2 (en) | Method for producing high molecular weight polyamide-imide resin | |
| CN115386085B (en) | Polyester imide copolymer and preparation method and application thereof | |
| CN102199350A (en) | Production method of high-temperature-resistant workable polyimide plastic alloy | |
| CN113402883B (en) | High-thermal-conductivity polyimide film and production process thereof | |
| CN111518277B (en) | Thermoplastic polyether sulfone imide copolymer and preparation method thereof | |
| CN102276834A (en) | Preparation method of thermoplastic polyimide | |
| CN112852154A (en) | High-temperature-resistant easy-to-process thermoplastic transparent polyimide resin material with low thermal expansion coefficient and preparation method thereof | |
| JPH0611798B2 (en) | Manufacturing method of polyimide molding | |
| CN113717384A (en) | Modified polyamide-imide material and preparation method thereof | |
| CN109354683B (en) | Polyimide based on diamine monomer containing naphthalimide group and preparation method thereof | |
| KR101259544B1 (en) | Polyimide film | |
| JP2590213B2 (en) | Spherical polyimide powder | |
| CN117004020A (en) | High-temperature-resistant polyimide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |