CN111793207B - Preparation method of high-modulus high-thermal-conductivity polyimide film - Google Patents

Preparation method of high-modulus high-thermal-conductivity polyimide film Download PDF

Info

Publication number
CN111793207B
CN111793207B CN202010590725.6A CN202010590725A CN111793207B CN 111793207 B CN111793207 B CN 111793207B CN 202010590725 A CN202010590725 A CN 202010590725A CN 111793207 B CN111793207 B CN 111793207B
Authority
CN
China
Prior art keywords
oligomer
solution
film
polyimide film
polymerization reaction
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
Application number
CN202010590725.6A
Other languages
Chinese (zh)
Other versions
CN111793207A (en
Inventor
张清华
董杰
赵昕
郑森森
甘锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donghua University
Original Assignee
Donghua University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Donghua University filed Critical Donghua University
Priority to CN202010590725.6A priority Critical patent/CN111793207B/en
Publication of CN111793207A publication Critical patent/CN111793207A/en
Application granted granted Critical
Publication of CN111793207B publication Critical patent/CN111793207B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Optics & Photonics (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a preparation method of a high-modulus high-thermal conductivity polyimide film, which comprises the following steps: mixing diamine containing anthryl or anthraquinone unit and dianhydride monomer with a solvent, and carrying out polymerization reaction to obtain an oligomer-I solution with an end capped by an anhydride structure; mixing diamine and dianhydride monomers containing benzimidazole or benzoxazole units with a solvent, and carrying out polymerization reaction to obtain a diamine-terminated oligomer-II solution; mixing oligomer-I solution and oligomer-II solution, carrying out polymerization reaction, casting the obtained polyamide acid solution with a block structure into a film, and then carrying out thermal cyclization and bidirectional drafting. The method can be used for continuous preparation, is simple to operate, is environment-friendly in process, is beneficial to large-scale preparation of the intrinsic high-modulus high-thermal conductivity polyimide film, and has good industrial prospect.

Description

Preparation method of high-modulus high-thermal-conductivity polyimide film
Technical Field
The invention belongs to the field of polyimide film preparation, and particularly relates to a preparation method of a high-modulus high-thermal-conductivity polyimide film.
Background
In recent years, with the rapid development of flexible photoelectric technology, polyimide films are widely used as flexible polymer substrates and dielectric insulating materials in the fields of flexible photoelectric devices, flexible printed circuit boards and the like. Polyimide films are typically required to bond or composite to the surface of other metal sheets (e.g., copper sheets) or inorganic materials (e.g., silicon wafers) during the fabrication of electronic devices or circuit boards. In order to ensure the quality of the optoelectronic device, the polyimide film is generally required to have the characteristic of high modulus, so as to avoid serious problems such as deformation and warping in the processing process. In addition, with the continuous improvement of the integration level of microelectronic devices, polyimide materials are generally required to have higher thermal conductivity, so that heat generated during the operation of the microelectronic devices can be timely transmitted out, and the safe use of the devices is ensured. Therefore, the polyimide film with high modulus and high thermal conductivity is one of the key materials in urgent need in the present microelectronic technical field, and the development of the materials can meet the increasingly urgent technical requirements in the advanced electronic and flexible display field.
In order to improve the modulus and the thermal conductivity of the polyimide film, researches at home and abroad mostly focus on the aspects of modification through nano particle doping and the like. Inorganic fillers with high rigidity and high thermal conductivity, such as graphene, boron nitride nanosheets, mica sheets and the like, are doped in a polyimide matrix through direct doping or chemical modification, and the modulus and the thermal conductivity of the film are improved. However, since the addition amount of the inorganic filler is limited by factors such as the processability of the film and the dispersibility of the nanoparticles, the method has poor effect of improving the final mechanical properties and the heat conduction behavior of the polyimide film, and is difficult to realize large-scale development. A large number of researches show that the mechanical property and the heat conduction property of the polymer material are closely related to the conformation and the aggregation state structure of a molecular chain, and the high coplanar orientation and the close packing of the molecular chain are beneficial to inhibiting the local chain motion, so that the material is ensured to have the characteristic of high modulus. For example, poly-p-phenylene benzobisoxazole (AS-Zylon) fibers developed by Toyobo, Japan, have a high molecular chain orientation regulated by high-temperature heat treatment and form an ordered close packing, and the material modulus can be increased by 100% (Polymer Reviews,2008,48, 230-. Furthermore, Wang et al found that the highly coplanar orientation and close packing of polymer molecular chains also helped to reduce the scattering effect of phonons inside the material, forming efficient heat conducting channels (Macromolecules,2013,46, 4937-. For example, the axial thermal conductivity of spider silk fibers subjected to cold drawing treatment is as high as 416W/mK, and mainly benefits from the relationship of high orientation of crystalline regions in the fibers.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-modulus high-thermal conductivity polyimide film, so as to overcome the defects that the modulus and the thermal conductivity of the polyimide film prepared by adopting a blending modification technology in the prior art are improved to a limited extent and are difficult to develop on a large scale.
The invention provides a polyimide film, which is characterized in that a dianhydride monomer and diamine containing anthryl or anthraquinone unit are subjected to polymerization reaction to obtain oligomer-I solution with an end capped by an anhydride structure; a dianhydride monomer and diamine containing benzimidazole or benzoxazole units are subjected to polymerization reaction to obtain diamine-terminated oligomer-II solution; mixing oligomer-I solution and oligomer-II solution, carrying out polymerization reaction, casting the obtained polyamide acid solution with a block structure to form a film, and then carrying out thermal cyclization and bidirectional thermal drafting treatment to obtain the polyimide film with the block structure and the highly coplanar molecular chain.
The dianhydride monomer comprises:
Figure BDA0002555399210000021
the diamine containing anthracene units is
Figure BDA0002555399210000022
Containing anthraquinone units of diamines
Figure BDA0002555399210000023
The diamine containing benzimidazole units is
Figure BDA0002555399210000024
Diamines containing benzoxazole units are
Figure BDA0002555399210000025
The invention also provides a preparation method of the polyimide film, which comprises the following steps:
(1) mixing diamine containing anthryl or anthraquinone unit and dianhydride monomer with a solvent, and carrying out polymerization reaction to obtain an oligomer-I solution with an end capped by an anhydride structure;
(2) mixing diamine and dianhydride monomers containing benzimidazole or benzoxazole units with a solvent, and carrying out polymerization reaction to obtain diamine-terminated oligomer-II solution;
(3) mixing the oligomer-I solution obtained in the step (1) with the oligomer-II solution obtained in the step (2), and carrying out polymerization reaction to obtain a polyamide acid solution with a block structure, wherein the molar ratio of the oligomer-I to the oligomer-II is 1: 1;
(4) and (4) filtering, defoaming and casting the polyamic acid solution with the block structure in the step (3) to form a film, and then performing thermal cyclization and bidirectional thermal drafting treatment and rolling to obtain the polyimide film with the block structure and the highly coplanar molecular chain.
In the step (1), the molar ratio of the diamine containing the anthracene group or anthraquinone unit to the dianhydride monomer is n (n +1), wherein n is 3-20.
The mass fraction of the oligomer-I solution in the step (1) is 10-20 wt%.
The solvent in the steps (1) and (2) is N-methyl-pyrrolidone NMP.
In the steps (1) and (2), the polymerization reaction temperature is 0-10 ℃, the polymerization reaction time is 10-12 h, and the polymerization degree is 2-20.
The molar ratio of the diamine containing benzimidazole or benzoxazole units to the dianhydride monomer in the step (2) is (n +1): n, wherein n is 3-20.
The mass fraction of the oligomer-II solution in the step (2) is 10-20 wt%.
The polymerization degree of the oligomer-I and the polymerization degree of the oligomer-II in the step (3) are the same; the mass fraction of the oligomer-I solution is the same as that of the oligomer-II solution.
The polymerization reaction in the step (3) is as follows: reacting at 5-10 deg.C for 12-24h, and controlling apparent viscosity of the solution to 5000cP s.
The steps (1), (2) and (3) are carried out under the protection of nitrogen.
The casting film in the step (4) is as follows: extruding from a casting die head, flowing into a solidified and formed steel plate, removing a solvent, drying, and solidifying the solution to form a film, wherein the extrusion rate of the casting die head is 2-5cm3The curing and forming conditions of the polyamic acid film are 100, 150 and 200 ℃ for 5min respectively.
The thermal cyclization and bidirectional thermal drafting treatment process parameters in the step (4) are as follows: the temperature is 350-500 ℃, the drafting is 1.5-3.5 times in the direction parallel to the moving direction of the film, and the drafting is 1.5-2.5 times in the direction perpendicular to the moving direction of the film.
The invention also provides a polyimide film prepared by the method.
The invention also provides an application of the polyimide film.
The invention provides a preparation method of a novel polyimide film with high modulus and high heat conduction property, which is characterized in that anthracene or anthraquinone units and benzimidazole or benzoxazole units with high coplanarity are introduced into a polyimide macromolecular chain, so that a high-efficiency channel for phonon propagation is favorably formed; and by regulating and controlling a molecular sequence structure (block polymerization) and subsequent heat treatment, a highly ordered orientation structure is formed by macromolecular chains in the film, and the intrinsic high-modulus high-heat-conductivity polyimide film is developed. The design of the block structure is favorable for regulating and controlling the ordered arrangement of polymer macromolecular chains to form a highly oriented crystalline condensed structure, is favorable for weakening interface scattering of phonon propagation, and simultaneously endows the film with outstanding mechanical properties.
According to the invention, by designing a highly coplanar molecular structure, introducing a heterocyclic unit and regulating a molecular sequence structure, the formation of macromolecular chain coplanar orientation and close packing arrangement in the material is facilitated, so that the double-effect improvement of the modulus and the heat conductivity of the film is realized, the intrinsic polyimide film with high modulus and high heat conductivity is prepared, and the requirements of future flexible OLED and flexible wearable equipment on polyimide substrates are hopefully met.
Advantageous effects
(1) According to the invention, through the design of a macromolecular chemical structure and a sequence structure, effective regulation and control of a molecular orientation structure and a stacking state in a material are realized, the mechanical property and the heat conduction behavior of a film are improved, the problem of poor film modulus and heat conductivity improvement effect in the existing blending modification technology is solved, a beneficial material solution can be provided for an advanced microelectronic technology, an advanced composite material and a flexible wearable technology, and the material has good commercial development potential.
(2) The method can be used for continuous preparation, is simple to operate, has an environment-friendly process, is beneficial to large-scale preparation of the intrinsic high-modulus high-thermal conductivity polyimide film, and has a good industrial prospect.
Drawings
FIG. 1(A) is a graph comparing the thermal conductivity of the block structures and corresponding random copolyimide films of examples 1-3; (B) the mechanical properties of the block polyimide film in example 3 are compared with those of the commercial Kapton film, and the insets are high thermal conductivity film samples prepared in example 3.
FIG. 2 is a diagram showing the synthesis of a block structured polyamic acid precursor in example 1.
FIG. 3 is a diagram showing the synthesis of a block structured polyamic acid precursor in example 2.
FIG. 4 is a diagram showing the synthesis of a block structured polyamic acid precursor in example 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The film performance test conditions in the embodiment of the invention are as follows:
wide angle X-ray scattering (WAXS) was tested at the line station of the shanghai synchrotron radiation source 16B1 at a test distance of 178 mm;
mechanical properties: testing by using an Instron3300, wherein the stretching speed is 5cm/min, and the distance between clamps is 2 cm;
and (3) testing thermal conductivity: testing the thermal diffusion coefficient alpha of the film by NETZSCH and LFA 467Nano-Flash equipment, and testing the specific heat capacity C of the film by DSCpBy the formula K ═ α × CpThe thermal conductivity of the film was calculated by x ρ (ρ is the density of the film).
Example 1
(1) In a three-neck flask, 50mL of NMP, 2.76g (0.0133mol) of anthracene-2, 6-diamine (Beijing Dingsheng brother science and technology Co., Ltd., purity 99%) and 4.12g (0.014mol) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA) (99.5% in Changzhou sunshine pharmaceutical industry) are sequentially added under the protection of nitrogen, and fully stirred and reacted for 12 hours, the reaction temperature is controlled to be 2 ℃, and the acid anhydride end-capped polyamic acid oligomer-I solution is obtained. In a three-neck flask, 50mL of NMP, 2.98g (0.0133mol) of 5-amino 2- (4-aminophenyl) -Benzimidazole (BIA) (purity 99% by Henzhou sunshine pharmaceutical industry Co., Ltd.) and 3.70g (0.0126mol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) (Henzhou sunshine pharmaceutical industry, 99.5%) were sequentially added under nitrogen protection, and the mixture was stirred sufficiently to react for 12 hours, the reaction temperature was controlled at 2 ℃, and an amino-terminated polyamic acid oligomer-II solution was obtained. Stirring and mixing the oligomer-I solution and the oligomer-II solution in nitrogen atmosphere, and reacting at 10 ℃ for 12h to obtain a polyamide acid precursor solution with a block structure, wherein the apparent viscosity of the polyamide acid precursor solution is 4800cP & s (25 ℃), and the molecular structure of the polyamide acid precursor solution is shown in figure 2.
(2) Taking the polyamic acid solution prepared in the step (1) as a raw material, adopting tape casting equipment and taking 3cm3Extruding at a speed of/min, heating the steel plate at three stages at 100, 150 and 200 ℃, and keeping the temperature for 5min at each stage to obtain the cured polyamic acid precursor film. And (3) continuously carrying out thermal cyclization and bidirectional thermal drafting treatment on the cured precursor film, wherein the thermal treatment temperature is 400 ℃, the longitudinal drafting multiplying factor is 2.0 times, the transverse drafting multiplying factor is 1.5 times, and rolling to obtain the polyimide film with the bidirectional drafting block structure, wherein the molecular structure is shown as follows. The molecular chain orientation factor f in the film surface can be measured to be approximately equal to 0.81 by wide-angle X-ray scattering (WAXS), the tensile strength of the obtained polyimide film is 220MPa, the initial modulus reaches 3.5GPa, and the in-plane thermal conductivity of the film is 3.2W/mK.
Figure BDA0002555399210000051
Example 2
(1) The preparation of the anhydride-terminated polyamic acid oligomer-I solution was the same as in example 1. According to example 1, "2.98 g (0.0133mol) of 5-amino 2- (4-aminophenyl) -Benzimidazole (BIA)" was changed to "2.99 g (0.0133mol) of 5-amino 2- (4-aminophenyl) -Benzoxazole (BOA) (Hitachi sunshine pharmaceutical Co., Ltd., Henzhou, purity 99%)", and the rest was the same as in example 1, to obtain an amino-terminated polyamic acid oligomer-II solution. Stirring and mixing the oligomer-I solution and the oligomer-II solution in nitrogen atmosphere, and reacting at 5 ℃ for 12h to obtain a polyamide acid precursor solution with a block structure, wherein the apparent viscosity of the polyamide acid precursor solution is 4980cP & s (25 ℃), and the molecular structure of the polyamide acid precursor solution is shown in figure 3.
(2) And (3) casting the polyamic acid precursor solution in the step (1) into a film under the same conditions as in the example 1 to obtain a cured polyamic acid precursor film. And (3) continuously carrying out thermal cyclization and bidirectional thermal drafting treatment on the cured precursor film, wherein the thermal treatment temperature is 450 ℃, the longitudinal drafting multiplying factor is 2.2 times, the transverse drafting multiplying factor is 1.8 times, and rolling to obtain the polyimide film with the bidirectional drafting block structure, wherein the molecular structure is shown as follows. The molecular chain orientation factor f in the film surface can be measured to be approximately equal to 0.88 by wide-angle X-ray scattering (WAXS), the tensile strength of the obtained polyimide film is 240MPa, the initial modulus reaches 4.12GPa, and the in-plane thermal conductivity of the film is 3.12W/mK.
Figure BDA0002555399210000052
Example 3
(1) According to example 1, "2.76 g (0.0133mol) of anthracene-2, 6-diamine" was changed to "3.16 g (0.0133mol) of 2, 6-diamino-anthraquinone (Kobon specialty Chemicals, Ltd., purity 99%)" and the rest was the same as in example 1 to obtain an acid anhydride-terminated polyamic acid oligomer-I solution. According to example 1, "2.98 g (0.0133mol) of 5-amino 2- (4-aminophenyl) -Benzimidazole (BIA)" was changed to "2.99 g (0.0133mol) of 5-amino 2- (4-aminophenyl) -Benzoxazole (BOA) (Hitachi sunshine pharmaceutical Co., Ltd., Henzhou, purity 99%)", and the rest was the same as in example 1, to obtain an amino-terminated polyamic acid oligomer-II solution. Stirring and mixing the oligomer-I solution and the oligomer-II solution in nitrogen atmosphere, and reacting at 5 ℃ for 12h to obtain a polyamide acid precursor solution with a block structure, wherein the apparent viscosity of the polyamide acid precursor solution is 4280cP & s (25 ℃), and the molecular structure of the polyamide acid precursor solution is shown in figure 4.
(2) And (3) casting the polyamic acid precursor solution in the step (1) into a film under the same conditions as in the example 1 to obtain a cured polyamic acid precursor film. And (3) continuously carrying out thermal cyclization and bidirectional thermal drafting treatment on the cured precursor film, wherein the thermal treatment temperature is 430 ℃, the longitudinal drafting multiplying factor is 2.5 times, the transverse drafting multiplying factor is 2.0 times, and rolling to obtain the polyimide film with the bidirectional drafting block structure, wherein the molecular structure is shown as follows. The molecular chain orientation factor f in the film surface can be measured to be approximately equal to 0.89 by wide-angle X-ray scattering (WAXS), the tensile strength of the obtained polyimide film is 268MPa, the initial modulus reaches 3.8GPa, and the in-plane thermal conductivity of the film is 2.8W/mK.
Figure BDA0002555399210000061
Compared with the commercially available Kapton polyimide film, the mechanical properties of the polyimide film with the block structure prepared in the embodiment are shown in fig. 1(B), and the polyimide film with the highly coplanar alignment structure prepared in the embodiment has higher tensile strength.
Comparative example 1
By using the polymerization process conditions (same temperature, same reaction mass fraction, etc.) in examples 1, 2, and 3, the polymerization mode was changed to random copolymerization, i.e., two diamine monomers were added into the solvent at the same time, after completely dissolving, equimolar amount of dianhydride monomer was added, after the polymerization reaction was completed, the random copolymerization polyimide film was obtained by tape casting and hot drawing under the same conditions, and the thermal conductivity of the random copolymerization polyimide film was not as good as the thermal conductivity of the block structure polyimide film, as shown in fig. 1A.
In the disclosed preparation methods (ZL 201810427843.8, CN 201911070735.0), methods (such as boron nitride and the like) of adding a heat-conducting filler into polyimide resin are adopted to improve the problem of low heat conductivity of polyimide, however, the methods always face the problems of easy agglomeration of the filler, unobvious improvement effect of the low-content filler and the like. In the invention, the intrinsic high-thermal-conductivity polyimide film is prepared by introducing the coplanar structure, the thermal conductivity can reach more than 3.0W/mK, and the intrinsic high-thermal-conductivity polyimide film has excellent mechanical properties, has the potential of large-scale development and has good application prospect in the field of microelectronics.

Claims (10)

1. A polyimide film is characterized in that dianhydride monomers and diamine containing anthryl or anthraquinone units are subjected to polymerization reaction to obtain oligomer-I solution with an end capped by an anhydride structure; a dianhydride monomer and diamine containing benzimidazole or benzoxazole units are subjected to polymerization reaction to obtain diamine-terminated oligomer-II solution; mixing oligomer-I solution and oligomer-II solution, carrying out polymerization reaction, casting the obtained polyamide acid solution with a block structure to form a film, and then carrying out thermal cyclization and bidirectional thermal drafting treatment to obtain the polyimide film with the block structure and the highly coplanar molecular chain.
2. The film of claim 1, wherein the dianhydride monomer comprises:
Figure DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE004
or
Figure DEST_PATH_IMAGE006
(ii) a The diamine containing an anthracene unit is
Figure DEST_PATH_IMAGE008
(ii) a Containing anthraquinone units of diamines
Figure DEST_PATH_IMAGE010
。
3. The film of claim 1, wherein said diamine containing benzimidazole units is
Figure DEST_PATH_IMAGE012
(ii) a Diamines containing benzoxazole units are
Figure DEST_PATH_IMAGE014
。
4. A method for preparing a polyimide film, comprising:
(1) mixing diamine containing anthryl or anthraquinone unit and dianhydride monomer with a solvent, and carrying out polymerization reaction to obtain an oligomer-I solution with an end capped by an anhydride structure;
(2) mixing diamine and dianhydride monomers containing benzimidazole or benzoxazole units with a solvent, and carrying out polymerization reaction to obtain diamine-terminated oligomer-II solution;
(3) mixing the oligomer-I solution obtained in the step (1) with the oligomer-II solution obtained in the step (2), and carrying out polymerization reaction to obtain a polyamide acid solution with a block structure, wherein the molar ratio of the oligomer-I to the oligomer-II is 1: 1;
(4) and (4) filtering and defoaming the polyamic acid solution with the block structure in the step (3), casting to form a film, then performing thermal cyclization and bidirectional thermal drafting treatment, and rolling to obtain the polyimide film with the block structure and the highly coplanar molecular chain.
5. The method according to claim 4, wherein the solvent in steps (1) and (2) is N-methylpyrrolidone (NMP); the polymerization temperature is 0-10 ℃, the polymerization time is 10-12 h, and the polymerization degree is 2-20.
6. The method of claim 4, wherein in step (3), the degree of polymerization of oligomer-I and oligomer-II is the same; the mass fractions of the oligomer-I solution and the oligomer-II solution are the same; the polymerization reaction is as follows: reacting at 5-10 deg.C for 12-24 h.
7. The method according to claim 4, wherein the step (4) of casting the film is: extruding from a casting die head, flowing into a solidified and formed steel plate, removing a solvent, drying, and solidifying the solution to form a film, wherein the extrusion rate of the casting die head is 2-5cm3And/min, the procedures of the solidification film-forming conditions of the polyamic acid solution are respectively 5min at 100, 150 and 200 ℃.
8. The method according to claim 4, wherein the parameters of the thermocycling and bi-directional hot-drawing treatment process in the step (4) are as follows: the temperature is 350-500 ℃, the drafting is 1.5-3.5 times in the direction parallel to the moving direction of the film, and the drafting is 1.5-2.5 times in the direction perpendicular to the moving direction of the film.
9. A polyimide film prepared according to the method of claim 4.
10. Use of the polyimide film of claim 1 in microelectronics.
CN202010590725.6A 2020-06-24 2020-06-24 Preparation method of high-modulus high-thermal-conductivity polyimide film Active CN111793207B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010590725.6A CN111793207B (en) 2020-06-24 2020-06-24 Preparation method of high-modulus high-thermal-conductivity polyimide film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010590725.6A CN111793207B (en) 2020-06-24 2020-06-24 Preparation method of high-modulus high-thermal-conductivity polyimide film

Publications (2)

Publication Number Publication Date
CN111793207A CN111793207A (en) 2020-10-20
CN111793207B true CN111793207B (en) 2021-07-20

Family

ID=72803100

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010590725.6A Active CN111793207B (en) 2020-06-24 2020-06-24 Preparation method of high-modulus high-thermal-conductivity polyimide film

Country Status (1)

Country Link
CN (1) CN111793207B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114479450A (en) * 2020-10-26 2022-05-13 中国石油化工股份有限公司 Homogeneous heterogeneous polyimide film and preparation method and application thereof
CN112876680B (en) * 2021-02-04 2022-09-23 武汉柔显科技股份有限公司 Polyamide acid slurry, preparation method thereof and polyimide film
CN115197082B (en) * 2022-05-31 2023-09-22 上海交通大学 Anthraquinone diamine monomer, magenta intrinsic polyimide derived from anthraquinone diamine monomer and preparation method of magenta intrinsic polyimide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63112623A (en) * 1986-10-30 1988-05-17 Toshiba Corp Light-screening polyimide, polyimide composition and its use
US8741998B2 (en) * 2011-02-25 2014-06-03 Sabic Innovative Plastics Ip B.V. Thermally conductive and electrically insulative polymer compositions containing a thermally insulative filler and uses thereof
CN111040159A (en) * 2019-12-15 2020-04-21 湖南工业大学 High-barrier polyimide containing high-planarity structure and preparation method and application thereof

Also Published As

Publication number Publication date
CN111793207A (en) 2020-10-20

Similar Documents

Publication Publication Date Title
CN111793207B (en) Preparation method of high-modulus high-thermal-conductivity polyimide film
KR101744009B1 (en) Polyimide resin
CN109438735B (en) High-thermal-conductivity polyimide-based composite film and preparation method thereof
CN113621234B (en) Ultrahigh-modulus high-transmittance polyimide film and preparation method and application thereof
CN106543720B (en) A kind of Kapton of low thermal coefficient of expansion and preparation method thereof
CN108864454B (en) High-transparency and high-flexibility polyimide film for electronic device and preparation method
CN103524767A (en) Novel electronic-grade polyimide film with low linear expansion coefficient and manufacturing method thereof
CN106893121B (en) High-dimensional stable polyimide film and preparation method thereof
CN106496611A (en) A kind of preparation method of high heat conduction Kapton
CN110885466B (en) Polyimide film with high orientation stability and preparation method thereof
CN110304625A (en) Graphene induces the preparation method of the high thermal conductivity graphite film of orientation of polyimide crystallization
Ou et al. Thermal conductive hybrid polyimide with ultrahigh heat resistance, excellent mechanical properties and low coefficient of thermal expansion
Wang et al. Effect of pre-imidization on the aggregation structure and properties of polyimide films
CN108384235A (en) A kind of high heat conduction Kapton and preparation method thereof
CN111286195A (en) Polyimide film containing bisbenzoxazole unit and preparation method and application thereof
CN105019047A (en) Low dielectric polyimide fiber and preparation method thereof
CN114479084A (en) Intrinsic high-flexibility and high-thermal-conductivity liquid crystal elastomer material and preparation and application thereof
Zheng et al. Soluble polyimides containing bulky rigid terphenyl groups with low dielectric constant and high thermal stability
CN111592669B (en) Multi-crosslinked carbon nanotube grafted polyimide heat-conducting film and preparation method and application thereof
CN109054018B (en) Polyamide acid solution and preparation method thereof
CN102942310B (en) Organosilicon polyimide benzimidazole photoconductive fiber coating layer and preparation method thereof
CN113105658B (en) Intrinsic high-thermal-conductivity liquid crystal polyimide film and preparation method thereof
CN113402883B (en) High-thermal-conductivity polyimide film and production process thereof
Chen et al. Polyimides containing a novel bisbenzoxazole with high T g and low CTE
CN102910840A (en) High-temperature resistant benzimidazole optical fiber coating and preparation method of coating

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