WO2022142320A1 - 聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备 - Google Patents

聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备 Download PDF

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WO2022142320A1
WO2022142320A1 PCT/CN2021/109459 CN2021109459W WO2022142320A1 WO 2022142320 A1 WO2022142320 A1 WO 2022142320A1 CN 2021109459 W CN2021109459 W CN 2021109459W WO 2022142320 A1 WO2022142320 A1 WO 2022142320A1
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Prior art keywords
polyimide film
dianhydride
diamine
slurry
artificial graphite
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PCT/CN2021/109459
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English (en)
French (fr)
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金亚东
张远豪
祝炬烨
杨承翰
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宁波长阳科技股份有限公司
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Priority claimed from CN202011628295.9A external-priority patent/CN112778551B/zh
Priority claimed from CN202011628354.2A external-priority patent/CN112831182A/zh
Application filed by 宁波长阳科技股份有限公司 filed Critical 宁波长阳科技股份有限公司
Publication of WO2022142320A1 publication Critical patent/WO2022142320A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating

Definitions

  • the present disclosure relates to the technical field of thin films, and in particular, to a polyimide thin film and a preparation method thereof, an artificial graphite film and an electronic device.
  • the present disclosure provides a polyimide film with a thickness of 25-100 ⁇ m, an elongation at break of 70-130%, an elastic modulus of 2.7-4.0 GPa, and a thermal expansion coefficient of 16-32 ppm /K;
  • the polyimide film is mainly made of the following raw materials: dianhydride, diamine, dehydrating agent, catalyst and filler;
  • the dianhydride includes dianhydride I
  • the dianhydride I includes pyromellitic dianhydride
  • the diamine includes diamine I
  • the diamine I includes 4,4'-diaminodiphenyl ether
  • the fillers include unmodified inorganic fillers and/or modified inorganic fillers, and the mass of the fillers accounts for 0.2-5.0% of the total mass of the polyimide film.
  • the difference between the refractive index of the polyimide film along the plane direction and the refractive index along the thickness direction is 0.095- 0.15.
  • the average particle size of the inorganic filler is 1.0-6.0 ⁇ m.
  • the unmodified inorganic filler includes any one or a combination of at least two of calcium carbonate, calcium bicarbonate, or calcium hydrogen phosphate.
  • the modified inorganic filler includes an inorganic filler surface-modified with a coupling agent.
  • the amount of the coupling agent is 1-5% of the total mass of the inorganic filler.
  • the coupling agent includes a silane coupling agent, for example including ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ aminopropyl Any of gamma-glycidoxypropyltrimethoxysilane or gamma-glycidyloxypropyltrimethoxysilane.
  • the inorganic filler includes any one or a combination of at least two of calcium carbonate, calcium bicarbonate, or calcium hydrogen phosphate.
  • the dianhydride includes dianhydride I and dianhydride II, and the molar percentage of dianhydride I and dianhydride II is (50 -100 mol%): (0-50 mol%).
  • the dianhydride II includes 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4-biphenyl Tetracarboxylic dianhydride.
  • the diamines include diamine I and diamine II, and the molar percentages of diamine I and diamine II are (50-100 mol %): (0-50 mol %) .
  • the diamine II comprises 1,4-diaminobenzene, 1,3-diaminobenzene, or 1,3-bis(4-aminophenoxy)benzene any one or a combination of at least two.
  • the dehydrating agent includes an acid anhydride.
  • the catalyst includes a tertiary organic amine.
  • the acid anhydride includes any one or a combination of at least two of formic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, or valeric anhydride.
  • the organic tertiary amine includes any one or a combination of at least two of pyridine, 3-picoline, triethylamine, or isoquinoline.
  • the dehydrating agent includes any one or a combination of at least two of acetic anhydride, propionic anhydride, or butyric anhydride.
  • the catalyst includes any one or a combination of at least two of pyridine, 3-picoline, triethylamine, or isoquinoline.
  • the molar ratio of the dianhydride and diamine is 1:(0.9-1.1).
  • the molar ratio of the dianhydride to the dehydrating agent is 1:(0-2).
  • the molar ratio of the dianhydride and catalyst is 1:(0.5-2).
  • the present disclosure also provides a method for preparing the above-mentioned polyimide film, comprising the following steps:
  • slurry I formed by dianhydride, diamine and organic solvent provide slurry II formed by filler and organic solvent, provide catalyst liquid formed by dehydrating agent, catalyst and organic solvent;
  • the composite slurry is mixed with the catalytic liquid to form a film to obtain a polyimide film.
  • the organic solvent includes N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylpyrrolidone Any one or a combination of at least two of methylacetamide.
  • the preparation method of the polyimide film includes the following steps:
  • the filler is added into the organic solvent to obtain slurry II;
  • the temperature of the imidization treatment is 380-450°C.
  • the present disclosure also provides an artificial graphite film, which is made of the polyimide film prepared by the above-mentioned polyimide film or the above-mentioned preparation method of the polyimide film.
  • the present disclosure provides a method for preparing the artificial graphite film, the method comprising: carbonizing the polyimide film, and then performing graphitization treatment to obtain the artificial graphite film.
  • the temperature of the carbonization treatment is 1000-1500° C.
  • the time of the carbonization treatment is 4-8 h.
  • the present disclosure provides the use of the artificial graphite film as a heat dissipation material.
  • the present disclosure also provides an electronic device comprising the above-mentioned artificial graphite film.
  • the electronic devices include chips, mobile phones, tablet computers, notebook computers, televisions, outdoor advertising screens, video recorders, camcorders, cameras, DVD players, CD players, stereos, One of the tape recorders, projectors, copiers, scanners, and fax machines.
  • polyimide films are directly related to the chemical structure of polyimide, and polyimides with different structures can be obtained through the selection of monomers, so that polyimide films exhibit different properties. .
  • the difference in the properties of the polyimide films will also cause the artificial graphite films prepared by using these polyimide films to show obvious performance differences, so the present disclosure is proposed.
  • the term "electronic device” refers to a device that is composed of electronic components such as integrated circuits, transistors, and electronic tubes, and that uses electronic technology (including software) to function.
  • imidization refers to dehydration condensation of carboxyl groups and amide bonds of polyamic acid to form an imide five-membered ring structure.
  • anisotropic refers to that all or part of the chemical, physical and other properties of a substance change with the change of direction, and show different properties in different directions.
  • anisotropy is used to characterize the orientation of polyimide films.
  • An embodiment of the present disclosure provides a polyimide film, the thickness of the polyimide film is 25-100 ⁇ m, the elongation at break is 70-130%, the elastic modulus is 2.7-4.0 GPa, and the thermal expansion coefficient is 16-32ppm/K;
  • Polyimide film is mainly made of the following raw materials: dianhydride, diamine, dehydrating agent, catalyst and filler;
  • the dianhydride includes dianhydride I
  • the dianhydride I includes pyromellitic dianhydride
  • the diamine includes diamine I
  • the diamine I includes 4,4'-diaminodiphenyl ether
  • the fillers include unmodified inorganic fillers and/or modified inorganic fillers, and the mass of the fillers accounts for 0.2-5.0% of the total mass of the polyimide film.
  • the polyimide film provided by the present disclosure can improve the technical problem that the polyimide film in the prior art cannot meet application requirements.
  • the polyimide film provided by the present disclosure is mainly made of dianhydrides, diamines, dehydrating agents, catalysts and fillers, wherein by selecting specific types of dianhydrides and diamines and a specific amount of fillers, the prepared polyimide film is made of Imide films have excellent mechanical properties and film orientation.
  • the thickness of the artificial graphite film prepared by using it is within a suitable range.
  • Typical but non-limiting thicknesses of polyimide films are 25 ⁇ m-90 ⁇ m, 30 ⁇ m-100 ⁇ m or 25 ⁇ m-70 ⁇ m, such as 25 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m or 100 ⁇ m.
  • the mechanical properties of polyimide films are mainly reflected in elongation at break and elastic modulus.
  • its elongation at break and elastic modulus are in a trade-off relationship, that is, the elongation at break is high, the elastic modulus is low, the elongation at break is low, and the elastic modulus is low. low volume.
  • the molecular arrangement is made regular by selecting monomers with no branch and rigid structure, so that the elongation at break and elastic modulus of the prepared polyimide are both at suitable levels, thereby ensuring that the polyimide is Amine films have good mechanical properties.
  • Typical but non-limiting elongation at break of polyimide film is 70%-120%, 80%-130% or 85%-110%, such as 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, 125% or 130%.
  • Typical but non-limiting elastic moduli are 2.7GPa-3.9GPa, 3.0GPa-4.0GPa, or 2.7GPa-3.7GPa, such as 2.7GPa, 2.8GPa, 3.0GPa, 3.2GPa, 3.4GPa, 3.5GPa, 3.6GPa, 3.8GPa or 4.0GPa.
  • the thermal expansion coefficient is mainly affected by the difference of molecular monomers and the arrangement of molecules. Typical but non-limiting coefficients of thermal expansion are 16 ppm/K, 18 ppm/K, 20 ppm/K, 22 ppm/K, 24 ppm/K, 25 ppm/K, 26 ppm/K, 28 ppm/K, 30 ppm/K or 32 ppm/K.
  • fillers can effectively improve the degree of graphitization of the artificial graphite film.
  • "and/or" means that the fillers may include only unmodified inorganic fillers, may only include modified inorganic fillers, or may include both unmodified inorganic fillers and modified inorganic fillers.
  • the unmodified inorganic filler is relative to the modified inorganic filler, and the difference between the unmodified inorganic filler and the modified inorganic filler is whether the inorganic filler has undergone surface modification treatment.
  • the modified inorganic filler obtained after surface modification has better compatibility with polyimide, and is more conducive to becoming a nucleation center and improving the degree of graphitization.
  • filler When the amount of filler is too low (less than 0.2%), it is easy to cause the artificial graphite film to be brittle; when the amount of filler is too high (higher than 5.0%), it is easy to cause the mechanical properties of polyimide to decline, and the artificial graphite film graphite The structure is incomplete, so the amount of filler should be limited to a specific value range.
  • typical but non-limiting amounts of fillers are 0.2%-4.8%, 0.5%-5.0%, or 0.5%-4.5%, such as 0.2%, 0.5%, 0.8%, 1.0%, 1.5%, 2.0% , 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0%.
  • mainly made of means that in addition to the above-mentioned raw materials, it may also include other raw materials acceptable in the field of polyimide films, and these other raw materials can impart different properties to the polyimide films. characteristic.
  • "mainly made of” in the present disclosure can also be replaced with closed “is” or "made of”.
  • the difference between the refractive index n (TE) along the plane direction and the refractive index n (TM) along the thickness direction of the polyimide film is between 0.095 and 0.15, that is, 0.095 ⁇ n (TE)-n(TM) ⁇ 0.15.
  • n(TE)-n(TM) represents the difference (difference) between the refractive index in the plane direction of the polyimide film and the refractive index in the thickness direction, that is, the anisotropy of molecular orientation.
  • the above parameters directly affect the molecular orientation, which in turn affects the anisotropy of the polyimide film.
  • the larger the difference the larger the anisotropy and the better the molecular orientation.
  • a typical but non-limiting difference in n(TE)-n(TM) is 0.010-0.15, 0.095-0.13 or 0.010-0.14, such as 0.095, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15.
  • the average particle size of the filler is 1.0-6.0 ⁇ m; the typical but non-limiting average particle size of the filler is 1.0 ⁇ m-5.0 ⁇ m, 2.0 ⁇ m-6.0 ⁇ m or 3.0 ⁇ m-5.0 ⁇ m, For example 1.0 ⁇ m, 1.5 ⁇ m, 2.0 ⁇ m, 2.5 ⁇ m, 3.0 ⁇ m, 3.5 ⁇ m, 4.0 ⁇ m, 4.5 ⁇ m, 5.0 ⁇ m, 5.5 ⁇ m or 6.0 ⁇ m.
  • the unmodified inorganic fillers include calcium salts, sodium salts, magnesium salts, and aluminum salts.
  • the unmodified inorganic filler includes any one or a combination of at least two of calcium carbonate, calcium bicarbonate or calcium hydrogen phosphate.
  • the modified inorganic filler includes an inorganic filler whose surface is modified by a coupling agent
  • the amount of the coupling agent is 1-5% of the total mass of the inorganic filler; the typical but non-limiting amount of the coupling agent is 1%-4%, 1.5%-4.5%, 2.0%-4.0%, for example 1.0 %, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0%.
  • the coupling agent includes a silane coupling agent, such as ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ aminopropyltrimethoxysilane or ⁇ -glycidyl ether any one of oxypropyltrimethoxysilane;
  • a silane coupling agent such as ⁇ -aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ aminopropyltrimethoxysilane or ⁇ -glycidyl ether any one of oxypropyltrimethoxysilane;
  • the inorganic fillers include calcium salts, sodium salts, magnesium salts, and aluminum salts.
  • the inorganic filler includes any one or a combination of at least two of calcium carbonate, calcium bicarbonate or calcium hydrogen phosphate.
  • the coupling agent can fully modify the surface of the inorganic filler, so that the modified inorganic filler has a good compatibility with the polyimide resin. Capacitance.
  • dianhydrides there are many types of dianhydrides, and the dianhydrides in the present disclosure are, for example, compounded by using a specific type of dianhydride I and other dianhydrides.
  • the dianhydride includes dianhydride I and dianhydride II, and the molar percentage of dianhydride I and dianhydride II is (50-100 mol%): (0-50 mol%);
  • the dianhydride II includes 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or 2,3,3',4-biphenyltetracarboxylic dianhydride.
  • Typical but non-limiting mole percentages of dianhydride I and dianhydride II are (60-100 mol %): (10-50 mol %), (60-90 mol %): (10-40 mol %) or (50-85 mol %) : (0-45mol%), such as 50mol%: 50mol%, 55mol%: 45mol%, 60mol%: 40mol%, 65mol%: 35mol%, 70mol%: 30mol%, 75mol%: 25mol%, 80mol%: 20mol% , 85 mol%: 15 mol%, 90 mol%: 10 mol%, 95 mol%: 5 mol% or 100 mol%: 0 mol%. It should be noted that, when the mole percentage of dianhydride I and dianhydride II is 100 mol%: 0 mol%, it means that the dianhydride only includes dianhydride I and does not include dianhydride II.
  • diamines matching with dianhydrides there are many types of diamines matching with dianhydrides, and the diamines in the present disclosure are, for example, compounded by using specific types of diamines (ie, diamine I and diamine II).
  • the diamine includes diamine I and diamine II, and the molar percentage of diamine I and diamine II is (50-100 mol%): (0-50 mol%);
  • the diamine II includes any one or a combination of at least two of 1,4-diaminobenzene, 1,3-diaminobenzene or 1,3-bis(4-aminophenoxy)benzene.
  • Typical but non-limiting mole percentages of diamine I and diamine II are (50-90 mol %): (0-40 mol %), (60-100 mol %): (10-50 mol %) or (60-80 mol %) : (10-45mol%), such as 50mol%: 50mol%, 55mol%: 45mol%, 60mol%: 40mol%, 65mol%: 35mol%, 70mol%: 30mol%, 75mol%: 25mol%, 80mol%: 20mol% , 85 mol%: 15 mol%, 90 mol%: 10 mol%, 95 mol%: 5 mol% or 100 mol%: 0 mol%. It should be noted that when the molar percentage of diamine I and diamine II is 100 mol%: 0 mol%, it means that the diamine only includes diamine I and does not include diamine II.
  • the molar ratio of dianhydride and diamine is 1:(0.9-1.1).
  • Typical but non-limiting molar ratios of dianhydride and diamine are 1:(0.9-1.0), 1:(1.0-1.1) or 1:(0.9-1.05), eg 1:0.9, 1:0.95, 1:1 , 1:1.05, 1:1.1.
  • dehydrating agent and catalyst directly affects the progress of the polycondensation reaction.
  • the dehydrating agent includes an acid anhydride.
  • the acid anhydride includes any one or a combination of at least two of formic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, or valeric anhydride.
  • the dehydrating agent includes any one or a combination of at least two of acetic anhydride, propionic anhydride or butyric anhydride.
  • the catalyst includes an organic tertiary amine.
  • the organic tertiary amine includes any one or a combination of at least two of pyridine, 3-picoline, triethylamine or isoquinoline.
  • the catalyst includes any one or a combination of at least two of pyridine, 3-picoline, triethylamine or isoquinoline.
  • the molar ratio of dianhydride and dehydrating agent is 1:(0-2); the typical but non-limiting molar ratio of dianhydride and dehydrating agent is 1:(0-1.5), 1 :(0.5-2) or 1:(0.5-1.8), eg 1:0, 1:0.2, 1:0.4, 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.4, 1: 1.5, 1:1.6, 1:1.8 or 1:2.0.
  • the molar ratio of the dianhydride and the catalyst is 1:(0.5-2).
  • Typical but non-limiting molar ratios of dianhydride and catalyst are 1:(0.5-1.8), 1:(1-2) or 1:(0.6-1.5), eg 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8 or 1:2.0.
  • the polyimide resin prepared by using the above raw materials has better orientation, so that the polyimide film has Regular graphite structure.
  • a method for preparing the above polyimide film includes the following steps:
  • slurry I formed by dianhydride, diamine and organic solvent provide slurry II formed by filler and organic solvent, provide catalyst liquid formed by dehydrating agent, catalyst and organic solvent;
  • the composite slurry and the catalyst liquid are mixed at low temperature to form a film to obtain a polyimide film.
  • the preparation method of the above polyimide film provided by the present disclosure has the advantages of simple operation, stable process, suitable for large-scale industrial production, and the polyimide film prepared by the above preparation method has good orientation.
  • the type of the organic solvent is not particularly limited, as long as it is ensured that it has good dissolving ability for fillers, dianhydrides and diamines.
  • the organic solvent includes any one or a combination of at least two of N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.
  • the preparation method of the polyimide film includes the following steps:
  • the filler is added into the organic solvent to obtain slurry II;
  • the orientation of the polyimide film is better.
  • the temperature of the imidization treatment is 380-450°C.
  • the temperature of the imidization treatment is higher than the glass transition temperature, and the molecular chain can be rearranged, which is beneficial to the molecular orientation, so it should be limited within a specific numerical range.
  • an artificial graphite film is also provided, which is made of the polyimide film prepared by the above-mentioned polyimide film or the above-mentioned preparation method of the polyimide film.
  • the artificial graphite film applied with it has good heat dissipation performance and excellent mechanical properties, and can be processed into various styles according to actual needs to meet the needs of different application scenarios.
  • the application of the above artificial graphite film in electronic equipment can prevent heat accumulation and prevent heat accumulation from affecting product performance and life.
  • An embodiment of the present disclosure provides a method for preparing an artificial graphite film.
  • the artificial graphite film can be prepared by conventional preparation methods in the art.
  • the preparation method of the artificial graphite film includes the following steps:
  • the temperature of the carbonization treatment is 1000-1500° C.
  • the time of the carbonization treatment is 4-8 h.
  • Typical but non-limiting carbonization temperatures are 1000°C, 1100°C, 1200°C, 1300°C, 1400°C or 1500°C.
  • a typical but non-limiting carbonization treatment time is 4h, 5h, 6h, 7h or 8h.
  • the temperature of the graphitization treatment is 2600-3300° C.
  • the time of the graphitization treatment is 4-12 h.
  • Typical but non-limiting temperatures for the graphitization process are 2600°C, 2700°C, 2800°C, 2900°C, 3000°C, 3100°C, 3200°C or 3300°C.
  • Typical but non-limiting times for the graphitization treatment are 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
  • An embodiment is disclosed to provide the use of an artificial graphite film as a heat dissipation material.
  • an electronic device comprising the above artificial graphite film.
  • the electronic devices including it also have the same advantages.
  • the electronic device here is not limited to one type, for example, it can be a chip, a mobile phone, a tablet computer, a notebook computer, a TV, an outdoor advertising screen, a video recorder, a camcorder, a camera, a DVD player, a CD player, a stereo, tape recorders, projectors, copiers, scanners, fax machines, etc.
  • a polyimide film provided by the present disclosure is made of dianhydride, diamine, dehydrating agent, catalyst and filler, wherein, by selecting a specific type of dianhydride and diamine and a specific amount of filler, so that The prepared polyimide film has excellent mechanical properties and film orientation, and the artificial graphite film prepared by using the above polyimide film has a more complete graphite structure and excellent thermal conductivity.
  • the present disclosure provides a method for preparing the above-mentioned polyimide film, which is easy to operate, has a stable process, and is suitable for large-scale industrial production.
  • the present disclosure provides an artificial graphite film, which is made of the polyimide film prepared by the above-mentioned polyimide film or the preparation method of the polyimide film.
  • the artificial graphite film applied with it has good thermal conductivity and excellent mechanical properties. It can be processed into various types according to actual needs to meet the needs of different application scenarios. .
  • the present disclosure provides an electronic device comprising the above-mentioned artificial graphite film.
  • the electronic devices including it also have the same advantages.
  • This embodiment provides a polyimide film, which is mainly made of the following raw materials: dianhydride, diamine, dehydrating agent, catalyst and filler;
  • dianhydride includes dianhydride 1
  • dianhydride 1 includes pyromellitic dianhydride (PMDA)
  • diamine includes diamine 1
  • diamine 1 includes 4,4'-diaminodiphenyl ether (ODA);
  • dianhydride The molar ratio to diamine is 1:1; the catalyst is 3-picoline, the molar ratio of dianhydride and catalyst is 1:2; the dehydrating agent is acetic anhydride, and the molar ratio of dianhydride and dehydrating agent is 1:2;
  • the filler is a modified inorganic filler, namely calcium hydrogen phosphate modified by ⁇ -aminopropyl triethoxy silane, (the amount of ⁇ -aminopropyl triethoxy silane is 1.5% of the total mass of calcium hydrogen phosphate), hydrogen phosphate
  • the average particle size of calcium is 4 ⁇ m, and the mass of the filler accounts for 1.5% of the total mass of the polyimide film.
  • This embodiment provides a polyimide film, except that the mass of the filler accounts for 0.2% of the total mass of the polyimide film, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.
  • This embodiment provides a polyimide film, except that the mass of the filler accounts for 5% of the total mass of the polyimide film, and other raw materials, dosages and preparation methods are the same as those in Embodiment 1.
  • This embodiment provides a polyimide film, except that the imidization temperature in the preparation method is replaced from 420° C. to 380° C., the remaining raw materials, dosage and preparation method are the same as those in Embodiment 1.
  • This embodiment provides a polyimide film, except that the imidization temperature in the preparation method is replaced from 420° C. to 450° C., the remaining raw materials, dosage and preparation method are the same as those in Embodiment 1.
  • This embodiment provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing dianhydride I 100mol% with dianhydride I 90mol% and dianhydride II 10mol%, dianhydride II is 3,3', 4,4' -Biphenyltetracarboxylic dianhydride, the remaining raw materials, dosage and preparation method are the same as those in Example 5.
  • This embodiment provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing dianhydride I 100mol% with dianhydride I 70mol% and dianhydride II 30mol%, dianhydride II is 3,3', 4,4' -Biphenyltetracarboxylic dianhydride, the remaining raw materials, dosage and preparation method are the same as those in Example 5.
  • This embodiment provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing dianhydride I 100mol% with dianhydride I 50mol% and dianhydride II 50mol%, dianhydride II is 3,3', 4,4' -Biphenyltetracarboxylic dianhydride, the remaining raw materials, dosage and preparation method are the same as those in Example 5.
  • This embodiment provides a polyimide film.
  • 100 mol% of diamine I is replaced by 90 mol% of diamine I and 10 mol% of diamine II, and diamine II is 1,4-diaminobenzene (PDA). ), the remaining raw materials, consumption and preparation method are the same as in Example 5.
  • PDA 1,4-diaminobenzene
  • This embodiment provides a polyimide film.
  • 100 mol% of diamine I is replaced by 70 mol% of diamine I and 30 mol% of diamine II, and diamine II is 1,4-diaminobenzene (PDA). ), the remaining raw materials, consumption and preparation method are the same as in Example 5.
  • PDA 1,4-diaminobenzene
  • This embodiment provides a polyimide film, in addition to changing the type of diamine, that is, replacing 100 mol% of diamine I with 50 mol% of diamine I and 50 mol% of diamine II, and diamine II is 1,4-diaminobenzene (PDA) ), the remaining raw materials, consumption and preparation method are the same as in Example 5.
  • PDA 1,4-diaminobenzene
  • This embodiment provides a polyimide film, except that the filler is replaced by a modified inorganic filler ( ⁇ -aminopropyltriethoxysilane-modified calcium hydrogen phosphate) with an unmodified inorganic filler calcium hydrogen phosphate, That is, the surface of calcium hydrogen phosphate is not modified, and the remaining raw materials and consumption are the same as those in Example 5.
  • a modified inorganic filler ⁇ -aminopropyltriethoxysilane-modified calcium hydrogen phosphate
  • the preparation method of the above polyimide film provided in this embodiment is the same as that of Embodiment 5 except that the silane coupling agent ⁇ -aminopropyltriethoxysilane is not added in the preparation process of the slurry II.
  • This embodiment provides a polyimide film, which is mainly made of the following raw materials: dianhydride, diamine, dehydrating agent, catalyst and filler;
  • dianhydride includes dianhydride I and dianhydride II
  • dianhydride I is pyromellitic dianhydride (PMDA)
  • dianhydride II is 2,3,3',4-biphenyltetracarboxylic dianhydride
  • Diamines include diamine I and diamine II, diamine I is 4,4'-diaminodiphenyl ether (ODA), and diamine II is 1,3-bis(4-aminophenoxy)benzene; dianhydride
  • ODA 4,4'-diaminodiphenyl ether
  • diamine II is 1,3-bis(4-aminophenoxy)benzene
  • dianhydride The molar ratio to diamine is 1.02:1; the catalyst is isoquinoline, the molar ratio of dianhydride and catalyst is 1:2; the dehydrating agent is butyric anhydride, and the molar ratio of dianhydride and dehydrating agent is 1:2;
  • the filler is a modified inorganic filler, namely ⁇ -N-( ⁇ -aminoethyl)- ⁇ aminopropyltrimethoxysilane modified calcium carbonate, (N-( ⁇ -aminoethyl)- ⁇ aminopropyltrimethyl)
  • the dosage of oxysilane is 3.0% of the total mass of calcium carbonate)
  • the average particle size of calcium carbonate is 1.0 ⁇ m
  • the mass of the filler accounts for 5.0% of the total mass of the polyimide film.
  • Embodiments 14-26 respectively provide an artificial graphite film, which is made by using the polyimide films provided in Embodiments 1-13, respectively.
  • the preparation method of artificial graphite film comprises the following steps:
  • the polyimide film was carbonized at 1300°C for 4 hours, and then graphitized at 3000°C for 8 hours to obtain an artificial graphite film.
  • the operation of the carbonization treatment is as follows: sandwich the polyimide film between the artificial graphite films, raise the temperature to 1300°C at a speed of 5°C/min in the vacuum environment of the carbonization furnace, and then keep the temperature for 1 hour; the operation of the graphitization treatment The steps are: heating the polyimide carbonized film to 3000°C at a rate of 5°C/min under an argon atmosphere in a graphitization furnace, and then maintaining the temperature for 0.5 hours.
  • Examples 27-39 respectively provide an artificial graphite film, which is made by using the polyimide films provided in Examples 1-13, respectively.
  • the preparation method of artificial graphite film comprises the following steps:
  • the polyimide film was carbonized at 1200 °C for 5 h, and then graphitized at 2900 °C for 9 h to obtain an artificial graphite film.
  • the operation of carbonization treatment is as follows: the polyimide film is sandwiched between artificial graphite films, and the temperature is raised to 1200°C at a speed of 5°C/min in the vacuum environment of the carbonization furnace, and then kept for 1 hour; the operation of the graphitization treatment For: heating the polyimide carbonized film to 2900°C at a rate of 5°C/min in a graphitization furnace under argon atmosphere, and then keeping the temperature for 0.5 hours.
  • This comparative example provides a polyimide film, except that in the preparation method, the imidization temperature is replaced from 420° C. to 350° C., the other raw material types, amounts and preparation methods are the same as those in Example 1.
  • This comparative example provides a polyimide film, except that no filler is added to the raw materials, and the types, amounts and preparation methods of other raw materials are the same as those in Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing dianhydride 1 pyromellitic dianhydride with dianhydride II 3,3',4,4'-biphenyltetracarboxylic acid bis Anhydride, other raw materials, dosage and preparation method are the same as in Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing dianhydride I pyromellitic dianhydride with dianhydride II 2,3,3',4-biphenyltetracarboxylic dianhydride , the remaining raw materials, dosage and preparation method are the same as in Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of dianhydride, that is, replacing dianhydride I pyromellitic dianhydride with dianhydride II 2,3,3',4-biphenyltetracarboxylic dianhydride 50mol% and 50mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride, the remaining raw materials, dosage and preparation method are the same as those in Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of diamine, that is, replacing diamine I4,4'-diaminodiphenyl ether with diamine II 1,4-diaminobenzene, the remaining raw materials, dosage and
  • the preparation method is the same as that of Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of diamine, that is, replacing diamine I4,4'-diaminodiphenyl ether with diamine II 1,3-bis(4-aminophenoxy) Benzene, other raw materials, dosage and preparation method are the same as in Example 1.
  • This comparative example provides a polyimide film, in addition to changing the type of diamine, that is, replacing diamine I4,4'-diaminodiphenyl ether with diamine II 1,3-bis(4-aminophenoxy) 50 mol% of benzene and 50 mol% of 1,3-diaminobenzene, and other raw materials, dosages and preparation methods are the same as in Example 1.
  • This comparative example provides a polyimide film, except that the mass of the filler accounts for 0.1% of the total mass of the polyimide film, and other raw materials, dosages and preparation methods are the same as those in Example 1.
  • This comparative example provides a polyimide film, except that the mass of the filler accounts for 6% of the total mass of the polyimide film, and other raw materials, dosages and preparation methods are the same as those in Example 1.
  • Comparative Examples 11-20 respectively provide an artificial graphite film, which is made of the polyimide films provided in Comparative Examples 1-10, respectively.
  • the preparation method of the artificial graphite film is the same as that of Examples 14-26.
  • the thickness of polyimide film is measured by a micrometer, and the detection method is based on GB/T 6672-2001; the elongation at break and elastic modulus are measured by a universal tensile testing machine, and the detection method is based on GBT1040.3-2006; thermal expansion
  • the coefficient was measured by a thermomechanical analyzer (TMA), the detection method was in accordance with ISO 11359-2; the anisotropy (n(TE) and n(TM)) were measured using a refractive index-film thickness measurement system (Model: 2010) manufactured by Metricon Corporation ; prism coupler) to measure the birefringence of polyimide film, the measuring method is as follows: use a light source with a wavelength of 594 nm under the environment of 25 ° C, respectively in TE mode (Transverse Electric mode, transverse electrical mode) and TM mode (Transverse Magnetic mode) mode, transverse magnetic mode), the refractive index was measured, and the value of n(TE)-n(
  • the thermal conductivity is measured by the laser thermal conductivity meter LFA 467 in the horizontal direction of the artificial graphite film.
  • the polyimide film provided in the present disclosure has excellent mechanical properties, and when the prepared films have the same thickness, the films prepared by the embodiments of the present disclosure A balance is achieved in elongation at break and elastic modulus while having a relatively low coefficient of thermal expansion compared to the comparative example.
  • the larger the birefringence (n(TE)-n(TM)) value the better the orientation of the polyimide film, the better the thermal conductivity and the better bending resistance of the prepared artificial graphite film.
  • Comparative Example 6 due to the reaction between diamine II 1,4-diaminobenzene and dianhydride I pyromellitic dianhydride, the rigidity of the molecular chain formed by the reaction between the two is too strong, and it will be broken as soon as the film is formed. , it is basically impossible to form a film, so it cannot be made into a polyimide film, so the data of Comparative Example 6 in Table 1 and Comparative Example 16 in Table 2 cannot be given.
  • the present disclosure provides a polyimide film and a preparation method thereof, an artificial graphite film and an electronic device.
  • the polyimide film has excellent mechanical properties and film orientation, and the artificial graphite film prepared by using the above polyimide film has a more complete graphite structure, excellent thermal conductivity, and excellent mechanical properties. It actually needs to be processed into various kinds to meet the needs of different application scenarios, and the electronic equipment that includes it also has the same advantages, with broad application prospects and high market value.

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Abstract

本公开提供了一种聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备，涉及薄膜技术领域。该聚酰亚胺薄膜采用二酐、二胺、脱水剂、催化剂和填料制成，其中，通过选用特定种类的二酐和二胺以及特定用量的填料，使得所制得的聚酰亚胺薄膜具有优异的力学性能和薄膜取向，采用上述聚酰亚胺薄膜制备的人工石墨膜具有更加完整的石墨结构，具有优异的导热性能。本公开还提供了一种人工石墨膜，采用上述聚酰亚胺薄膜制成，鉴于上述聚酰亚胺薄膜所具有的优势，使得应用其的人工石墨膜具有良好的导热性能，同时还具有优异的力学性能，可根据实际需要加工成各式各样，满足不同应用场景的需求。

Description

聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备
相关申请的交叉引用
本公开要求于2020年12月31日提交中国专利局的申请号为“202011628295.9”名称为“聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备”以及于2020年12月31日提交中国专利局的申请号为“202011628354.2”名称为“无色透明聚酰亚胺薄膜及其制备方法和LED贴膜屏”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及薄膜技术领域，尤其是涉及一种聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备。
背景技术
在摩尔定律的推动下，芯片集成度越来越高，芯片散热成了电子设备持续高效运行的基本需求。目前，通常采用由聚酰亚胺薄膜烧结的人工石墨膜作为各类电子设备内部的散热材料，以满足电子设备内部狭小空间的散热设计要求。
随着科技快速发展，电子设备逐渐向轻薄化及小型化的方向发展，电子设备的产热量也随之明显增大，这就使得对于人工石墨膜的散热性能要求越来越高；同时，由于电子设备越来越轻薄化及小型化，人工石墨膜需要加工成各式各样，也对人工石墨膜的力学特性提出了更高的要求。由于人工石墨膜的各项性能取决于作为原料的聚酰亚胺薄膜，因此，开发优异导热性能人工石墨膜用的聚酰亚胺薄膜就显得尤为重要。
发明内容
本公开提供一种聚酰亚胺薄膜，所述聚酰亚胺薄膜的厚度为25-100μm，断裂伸长率为70-130％，弹性模量为2.7-4.0GPa，热膨胀系数为16-32ppm/K；
所述聚酰亚胺薄膜主要由以下原料制成：二酐、二胺、脱水剂、催化剂和填料；
其中，二酐包括二酐Ι，所述二酐Ι包括均苯四甲酸二酐，二胺包括二胺Ι，所述二胺Ι包括4,4'-二氨基二苯醚；
所述填料包括未改性无机填料和/或改性无机填料，所述填料的质量占聚酰亚胺薄膜总质量的0.2-5.0％。
在一种或多种示例性的实施方式中，在本公开上述技术方案的基础之上，所述聚酰亚胺薄膜沿平面方向的折射率与沿厚度方向的折射率的差值为0.095-0.15。
在一种或多种示例性的实施方式中，在本公开上述技术方案的基础之上，所述无机填料的平均粒径为1.0-6.0μm。
在一种或多种示例性的实施方式中，所述未改性无机填料包括碳酸钙、碳酸氢钙或磷酸氢钙中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，所述改性无机填料包括经过偶联剂进行表面改性的无机填料。
在一种或多种示例性的实施方式中，所述偶联剂的用量为所述无机填料总质量的1-5％。
在一种或多种示例性的实施方式中，所述偶联剂包括硅烷偶联剂，例如包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-α氨丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷中的任意一种。
在一种或多种示例性的实施方式中，所述无机填料包括碳酸钙、碳酸氢钙或磷酸氢钙中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，在本公开上述技术方案的基础之上，所述二酐包括二酐Ι和二酐Ⅱ，二酐Ι和二酐Ⅱ的摩尔百分比为(50-100mol％)：(0-50mol％)。
在一种或多种示例性的实施方式中，所述二酐Ⅱ包括3,3',4,4'-联苯四羧酸二酐和/或2,3,3',4-联苯四羧酸二酐。
在一种或多种示例性的实施方式中，所述二胺包括二胺Ι和二胺Ⅱ，二胺Ι和二胺Ⅱ的摩尔百分比为(50-100mol％)：(0-50mol％)。
在一种或多种示例性的实施方式中，所述二胺Ⅱ包括1,4-二氨基苯、1,3-二氨基苯或1,3-双(4-氨基苯氧基)苯中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，所述脱水剂包括酸酐。在一种或多种示例性的实施方式中，所述催化剂包括有机叔胺。
在一种或多种示例性的实施方式中，所述酸酐包括甲酸酐、乙酸酐、丙酸酐、丁酸酐或戊酸酐任意一种或至少两种的组合。在一种或多种示例性的实施方式中，所述有机叔胺包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，所述脱水剂包括乙酸酐、丙酸酐或丁酸酐中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，所述催化剂包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，在本公开上述技术方案的基础之上，所述二酐和二胺的摩尔比为1：(0.9-1.1)。
在一种或多种示例性的实施方式中，所述二酐和脱水剂的摩尔比为1：(0-2)。
在一种或多种示例性的实施方式中，所述二酐和催化剂的摩尔比为1：(0.5-2)。
本公开还提供了上述聚酰亚胺薄膜的制备方法，包括以下步骤：
提供二酐、二胺和有机溶剂形成的浆料Ι，提供填料和有机溶剂形成的浆料Ⅱ，提供脱水剂、催化剂和有机溶剂形成的催化液；
将浆料Ι和浆料Ⅱ混合，得到复合浆料；
将复合浆料与催化液混合后制膜，得到聚酰亚胺薄膜。
在一种或多种示例性的实施方式中，在本公开上述技术方案的基础之上，所述有机溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的任意一种或至少两种的组合。
在一种或多种示例性的实施方式中，所述聚酰亚胺薄膜的制备方法包括以下步骤：
(a)将二酐、二胺加入到有机溶剂中，于-25-0℃搅拌，得到浆料Ι；其中，浆料Ι的粘度不小于100000厘泊；
将填料加入到有机溶剂中，得到浆料Ⅱ；
将脱水剂、催化剂加入到有机溶剂中，并保持-25-0℃，得到催化液；
(b)将浆料Ι和浆料Ⅱ于-25-0℃混合，得到复合浆料；
(c)将复合浆料和催化液混合后，再经流延、干燥、拉伸和亚胺化处理，得到聚酰亚胺薄膜。
在一种或多种示例性的实施方式中，亚胺化处理的温度为380-450℃。
本公开还提供了一种人工石墨膜，采用上述聚酰亚胺薄膜或上述聚酰亚胺薄膜的制备方法制得的聚酰亚胺薄膜制成。
本公开提供了制备所述人工石墨膜的方法，所述方法包括：将所述聚酰亚胺薄膜碳化处理后，再进行石墨化处理，得到所述人工石墨膜。
在一种或多种示例性的实施方式中，所述碳化处理的温度为1000-1500℃，所述碳化处理的时间为4-8h。
本公开提供所述人工石墨膜用于散热材料的用途。
本公开还提供了一种电子设备，包含上述人工石墨膜。在一种或多种示例性的实施方式中，所述电子设备包括芯片、手机、平板电脑、笔记本电脑、电视、户外广告屏、录像机、摄录机、照相机、影碟机、激光唱机、音响、收录机、投影仪、复印机、扫描仪、传真机中的一种。
实施方式
下面将结合实施对本公开的技术方案进行清楚、完整地描述，显然，所描述的实施例是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。
发明人发现，聚酰亚胺薄膜的性能与聚酰亚胺的化学结构有直接关系，可通过单体的选择得到不同结构的聚酰亚胺，从而使得聚酰亚胺薄膜表现出不同的性能。聚酰亚胺薄膜性能的差异，也会使得采用这些聚酰亚胺薄膜制备的人工石墨膜会表现出明显的性能差异，故提出本公开。
术语定义
如本文所用，术语“电子设备”，是指由集成电路、晶体管、电子管等电子元器件组成，应用电子技术(包括软件)发挥作用的设备。
如本文所用，术语“亚胺化”是指将聚酰胺酸的羧基和酰胺键经脱水缩合形成酰亚胺五元环结构。
如本文所用，术语“各项异性”是指是指物质的全部或部分化学、物理等性质随着方向的改变而有所变化，在不同的方向上呈现出差异的性质。在本文中，利用“各项异性”来表征聚酰亚胺薄膜的取向性。
本公开一实施方式，提供了一种聚酰亚胺薄膜，聚酰亚胺薄膜的厚度为25-100μm，断裂伸长率为70-130％，弹性模量为2.7-4.0GPa，热膨胀系数为16-32ppm/K；
聚酰亚胺薄膜主要由以下原料制成：二酐、二胺、脱水剂、催化剂和填料；
其中，二酐包括二酐Ι，所述二酐Ι包括均苯四甲酸二酐，二胺包括二胺Ι，二胺Ι包括4,4'-二氨基二苯醚；
填料包括未改性无机填料和/或改性无机填料，填料的质量占聚酰亚胺薄膜总质量的0.2-5.0％。
本公开提供的一种聚酰亚胺薄膜，可以改善现有技术中存在的聚酰亚胺薄膜无法满足应用要求的技术问题。
本公开提供的聚酰亚胺薄膜主要采用二酐、二胺、脱水剂、催化剂和填料制成，其中，通过选用特定种类的二酐和二胺以及特定用量的填料，使得所制得的聚酰亚胺薄膜具有优异的力学性能和薄膜取向。
通过对聚酰亚胺薄膜的厚度的限定，以使得采用其制得的人工石墨膜的厚度处于适宜的范围内。聚酰亚胺薄膜典型但非限制性的厚度为25μm-90μm、30μm-100μm或25μm-70μm，例如25μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm或100μm。
聚酰亚胺薄膜的力学性能主要体现在断裂伸长率和弹性模量。对于聚酰亚胺薄膜而言，其断裂伸长率和弹性模量呈此消彼长的关系，也就是断裂伸长率高，其弹性模量低，其断裂伸长率低，其弹性模量低。本公开通过选用没有支链且具有刚性结构的单体使得分子排列规整，从而使得所制得的聚酰亚胺的断裂伸长率和弹性模量均处于较适宜的水平，进而保证聚酰亚胺薄膜具有良好的力学性能。聚酰亚胺薄膜典型但非限制性的断裂伸长率为70％-120％、80％-130％或85％-110％，例如70％、75％、80％、85％、90％、95％、100％、105％、110％、115％、120％、125％或130％。典型但非限制性的弹性模量为2.7GPa-3.9GPa、3.0GPa-4.0GPa或2.7GPa-3.7GPa，例如2.7GPa、2.8GPa、3.0GPa、3.2GPa、3.4GPa、3.5GPa、3.6GPa、3.8GPa或4.0GPa。
热膨胀系数主要受分子单体的不同及分子排列情况影响。典型但非限制性的热膨胀系数为16ppm/K、18ppm/K、20ppm/K、22ppm/K、24ppm/K、25ppm/K、26ppm/K、28ppm/K、30ppm/K或32ppm/K。
填料的加入，可有效提高人工石墨膜的石墨化度。本公开中的“和/或”是指，填料可以只包括未改性无机填料，可以只包括改性无机填料，亦或可以同时包括未改性无机填料和改性无机填料。其中，未改性无机填料是相对于改性无机填料而言的，未改性无机填料和改性无机填料的区别在于无机填料是否经过表面改性处理。经过表面改性后得到的改性无机填料与聚酰亚胺的相容性更好，更有利于成为成核中心，提高石墨化度。
当填料的用量过低(低于0.2％)，则容易导致人工石墨膜比较脆；当填料的用量过高(高于5.0％)，则容易导致聚酰亚胺力学性能下降，人工石墨膜石墨结构不完整，故填料用量应该限定在特定的数值范围内。在本公开中，填料典型但非限制性的用量为 0.2％-4.8％、0.5％-5.0％或0.5％-4.5％，例如0.2％、0.5％、0.8％、1.0％、1.5％、2.0％、2.5％、3.0％、3.5％、4.0％、4.5％或5.0％。
本公开所述的“主要由……制成”，意指其除所述原料外，还可以包括聚酰亚胺薄膜领域可接受的其他原料，这些其他原料可赋予聚酰亚胺薄膜不同的特性。除此之外，本公开所述的“主要由……制成”，还可以替换为封闭式的“为”或“由……制成”。
作为本公开一种可选实施方式，聚酰亚胺薄膜沿平面方向的折射率n(TE)与沿厚度方向的折射率n(TM)的差值在0.095-0.15之间，即0.095≤n(TE)-n(TM)≤0.15。
n(TE)-n(TM)表示聚酰亚胺薄膜平面方向的折射率和厚度方向的折射率的差异(差值)，即分子取向的各向异性。上述参数直接影响到分子取向，进而影响聚酰亚胺薄膜的各向异性。差值越大表示各向异性越大，分子取向性越好。n(TE)-n(TM)典型但非限制性的差值为0.010-0.15、0.095-0.13或0.010-0.14，例如0.095、0.10、0.11、0.12、0.13、0.14或0.15。
作为本公开一种可选实施方式，填料的平均粒径为1.0-6.0μm；填料典型但非限制性的平均粒径为1.0μm-5.0μm、2.0μm-6.0μm或3.0μm-5.0μm，例如1.0μm、1.5μm、2.0μm、2.5μm、3.0μm、3.5μm、4.0μm、4.5μm、5.0μm、5.5μm或6.0μm。
作为本公开一种可选实施方式，未改性无机填料包括钙盐、钠盐、镁盐、铝盐。
作为本公开一种可选实施方式，未改性无机填料包括碳酸钙、碳酸氢钙或磷酸氢钙中的任意一种或至少两种的组合。
作为本公开一种可选实施方式，改性无机填料包括经过偶联剂进行表面改性的无机填料；
可选的，偶联剂的用量为无机填料总质量的1-5％；偶联剂典型但非限制性的用量1％-4％、1.5％-4.5％、2.0％-4.0％，例如1.0％、1.5％、2.0％、2.5％、3.0％、3.5％、4.0％、4.5％或5.0％。
可选的，偶联剂包括硅烷偶联剂，例如包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-α氨丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷中的任意一种；
可选的，无机填料包括钙盐、钠盐、镁盐、铝盐。
可选的，无机填料包括碳酸钙、碳酸氢钙或磷酸氢钙中的任意一种或至少两种的组合。
通过对改性无机填料中偶联剂种类、用量以及无机填料种类的限定，使得偶联剂对无机填料的表面进行充分改性，从而使得改性无机填料与聚酰亚胺树脂有良好的相容性。
二酐的种类有很多，本公开中的二酐例如采用特定种类的二酐Ι和其他二酐复合而成。
作为本公开一种可选实施方式，二酐包括二酐Ι和二酐Ⅱ，二酐Ι和二酐Ⅱ的摩尔百分比为(50-100mol％)：(0-50mol％)；
可选的，二酐Ⅱ包括3,3',4,4'-联苯四羧酸二酐和/或2,3,3',4-联苯四羧酸二酐。
二酐Ι和二酐Ⅱ典型但非限制性的摩尔百分比为(60-100mol％)：(10-50mol％)、(60-90mol％)：(10-40mol％)或(50-85mol％)：(0-45mol％)，例如50mol％：50mol％、55mol％：45mol％、60mol％：40mol％、65mol％：35mol％、70mol％：30mol％、75mol％：25mol％、80mol％：20mol％、85mol％：15mol％、90mol％：10mol％、95mol％：5mol％或100mol％：0mol％。需要说明的是，当二酐Ι和二酐Ⅱ的摩尔百分比为100mol％：0mol％，是指二酐只包括二酐Ι，不包括二酐Ⅱ。
与二酐匹配的二胺的种类有很多，本公开中的二胺例如选用特定种类的二胺(即，二胺Ι和二胺Ⅱ)复合而成。
作为本公开一种可选实施方式，二胺包括二胺Ι和二胺Ⅱ，二胺Ι和二胺Ⅱ的摩尔百分比为(50-100mol％)：(0-50mol％)；
可选的，二胺Ⅱ包括1,4-二氨基苯、1,3-二氨基苯或1,3-双(4-氨基苯氧基)苯中的任意一种或至少两种的组合。
二胺Ι和二胺Ⅱ典型但非限制性的摩尔百分比为(50-90mol％)：(0-40mol％)、(60-100mol％)：(10-50mol％)或(60-80mol％)：(10-45mol％)，例如50mol％：50mol％、55mol％：45mol％、60mol％：40mol％、65mol％：35mol％、70mol％：30mol％、75mol％：25mol％、80mol％：20mol％、85mol％：15mol％、90mol％：10mol％、95mol％：5mol％或100mol％：0mol％。需要说明的是，当二胺Ι和二胺Ⅱ的摩尔百分比为100mol％：0mol％，是指二胺只包括二胺Ι，不包括二胺Ⅱ。
作为本公开一种可选实施方式，二酐和二胺的摩尔比为1：(0.9-1.1)。二酐和二胺典型但非限制性的摩尔比为1：(0.9-1.0)、1：(1.0-1.1)或1：(0.9-1.05)，例如1：0.9、1：0.95、1：1、1：1.05、1：1.1。
脱水剂和催化剂的种类直接影响到缩聚反应的进行。
作为本公开一种可选实施方式，脱水剂包括酸酐。可选地，酸酐包括甲酸酐、乙酸酐、丙酸酐、丁酸酐或戊酸酐的任意一种或至少两种的组合。
作为本公开一种可选实施方式，脱水剂包括乙酸酐、丙酸酐或丁酸酐中的任意一种 或至少两种的组合。
作为本公开一种可选实施方式，催化剂包括有机叔胺。可选地，有机叔胺包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。
作为本公开一种可选实施方式，催化剂包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。
作为本公开一种可选实施方式，二酐和脱水剂的摩尔比为1：(0-2)；二酐和脱水剂典型但非限制性的摩尔比为1：(0-1.5)、1：(0.5-2)或1：(0.5-1.8)，例如1：0、1：0.2、1：0.4、1：0.5、1：0.8、1：1.0、1：1.2、1：1.4、1：1.5、1：1.6、1：1.8或1：2.0。
作为本公开一种可选实施方式，二酐和催化剂的摩尔比为1：(0.5-2)。二酐和催化剂典型但非限制性的摩尔比为1：(0.5-1.8)、1：(1-2)或1：(0.6-1.5)，例如1：0.5、1：0.8、1：1.0、1：1.2、1：1.4、1：1.5、1：1.6、1：1.8或1：2.0。
通过对二酐、二胺种类以及摩尔配比、脱水剂和催化剂种类和用量的限定，使得采用上述原料制得的聚酰亚胺树脂具有较好的取向性，从而使得聚酰亚胺薄膜具有规整的石墨结构。
根据本公开一实施方式提供了上述聚酰亚胺薄膜的制备方法，包括以下步骤：
提供二酐、二胺和有机溶剂形成的浆料Ι，提供填料和有机溶剂形成的浆料Ⅱ，提供脱水剂、催化剂和有机溶剂形成的催化液；
将浆料Ι和浆料Ⅱ混合，得到复合浆料；
将复合浆料与催化液低温下混合后制膜，得到聚酰亚胺薄膜。
本公开提供的上述聚酰亚胺薄膜的制备方法，操作简便，工艺稳定，适合规模化工业生产，且通过上述制备方法制得的聚酰亚胺薄膜的取向性好。
有机溶剂的种类不作具体限定，只要确保其对填料、二酐和二胺具有良好的溶解能力即可。作为本公开一种可选实施方式，有机溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的任意一种或至少两种的组合。
作为本公开一种可选的实施方式，聚酰亚胺薄膜的制备方法包括以下步骤：
(a)将二酐和二胺加入到有机溶剂中，于-25-0℃搅拌，得到浆料Ι；其中，浆料Ι的粘度不小于100000厘泊；
将填料加入到有机溶剂中，得到浆料Ⅱ；
将脱水剂、催化剂加入到有机溶剂中，并保持-25-0℃，得到催化液；
(b)将浆料Ι和浆料Ⅱ于-25-0℃混合，得到复合浆料；
(c)将复合浆料和催化液混合后，再经流延、干燥、拉伸和亚胺化处理，得到聚酰亚胺薄膜。
通过对聚酰亚胺薄膜的制备步骤以及工艺参数的进一步限定，使得聚酰亚胺薄膜取向性更好。
作为本公开一种可选的实施方式，亚胺化处理的温度为380-450℃。
亚胺化处理的温度高于玻璃化转变温度，分子链可以重排，有利于分子取向，故应当将其限定在特定的数值范围内。
根据本公开一实施方式还提供了一种人工石墨膜，采用上述聚酰亚胺薄膜或上述聚酰亚胺薄膜的制备方法制得的聚酰亚胺薄膜制成。
鉴于上述聚酰亚胺薄膜所具有的优势，使得应用其的人工石墨膜具有良好的散热性能，同时还具有优异的力学性能，可根据实际需要加工成各种样式，满足不同应用场景的需求。将上述人工石墨膜应用于电子设备中，可防止热量聚集，避免热量聚集影响产品性能及寿命。
本公开一实施方式提供制备人工石墨膜的方法。人工石墨膜可通过本领域的常规制备方法制得。
作为本公开一种可选实施方式，人工石墨膜的制备方法包括以下步骤：
将聚酰亚胺薄膜碳化处理后，再进行石墨化处理，得到人工石墨膜。作为本公开一种可选实施方式，碳化处理的温度为1000-1500℃，碳化处理的时间为4-8h。典型但非限制性的碳化处理的温度为1000℃、1100℃、1200℃、1300℃、1400℃或1500℃。典型但非限制性的碳化处理的时间为4h、5h、6h、7h或8h。
作为本公开一种可选实施方式，石墨化处理的温度为2600-3300℃，石墨化处理的时间为4-12h。典型但非限制性的石墨化处理的温度为2600℃、2700℃、2800℃、2900℃、3000℃、3100℃、3200℃或3300℃。典型但非限制性的石墨化处理的时间为4h、5h、6h、7h、8h、9h、10h、11h或12h。
公开一实施方式提供人工石墨膜用于散热材料的用途。
根据本公开一实施方式还提供了一种电子设备，包含上述人工石墨膜。
鉴于上述人工石墨膜所具有的优势，使得包含其的电子设备也具有同样的优势。需要说明的是，此处的电子设备不限于一种，例如可为芯片、手机、平板电脑、笔记本电脑、电视、户外广告屏、录像机、摄录机、照相机、影碟机、激光唱机、音响、收录机、投影仪、复印机、扫描仪、传真机等。
本公开具有以下有益效果：
(1)本公开提供的一种聚酰亚胺薄膜，采用二酐、二胺、脱水剂、催化剂和填料制成，其中，通过选用特定种类的二酐和二胺以及特定用量的填料，使得所制得的聚酰亚胺薄膜具有优异的力学性能和薄膜取向，采用上述聚酰亚胺薄膜制备的人工石墨膜具有更加完整的石墨结构，具有优异的导热性能。
(2)本公开提供了上述聚酰亚胺薄膜的制备方法，操作简便，工艺稳定，适合规模化工业生产。
(3)本公开提供了一种人工石墨膜，采用上述聚酰亚胺薄膜或聚酰亚胺薄膜的制备方法制得的聚酰亚胺薄膜制成。鉴于上述聚酰亚胺薄膜所具有的优势，使得应用其的人工石墨膜具有良好的导热性能，同时还具有优异的力学性能，可根据实际需要加工成各式各样，满足不同应用场景的需求。
(4)本公开提供了一种电子设备，包含上述人工石墨膜。鉴于上述人工石墨膜所具有的优势，使得包含其的电子设备也具有同样的优势。
下面结合示例性的实施例和对比例，对本公开作进一步说明。
实施例
实施例1
本实施例提供了一种聚酰亚胺薄膜，主要由以下原料制成：二酐、二胺、脱水剂、催化剂和填料；
其中，二酐包括二酐Ι，二酐Ι包括均苯四甲酸二酐(PMDA)，二胺包括二胺Ι，二胺Ι包括4,4'-二氨基二苯醚(ODA)；二酐和二胺的摩尔比为1：1；催化剂为3-甲基吡啶，二酐和催化剂的摩尔比为1：2；脱水剂为乙酸酐，二酐和脱水剂的摩尔比为1：2；
填料为改性无机填料，即γ-氨丙基三乙氧基硅烷改性的磷酸氢钙，(γ-氨丙基三乙氧基硅烷用量为磷酸氢钙总质量的1.5％)，磷酸氢钙的平均粒径为4μm，填料的质量占聚酰亚胺薄膜总质量的1.5％。
本实施例提供的上述聚酰亚胺薄膜的制备方法，包括以下步骤：
(a)提供浆料Ι、浆料Ⅱ和催化液
在氮气气氛下，向反应器中加入8.6154g(0.043mol)4,4'-二氨基二苯醚(二胺Ι)，再加入82g有机溶剂N,N-二甲基乙酰胺搅拌使之溶解，边冷却(温度为-25℃)边加入 9.3846g(0.043mol)均苯四甲酸二酐(二酐Ι)，低温下机械搅拌8h，得到粘度240000厘泊的浆料Ι(含有18wt％的聚酰胺酸溶液)；
在氮气气氛下，将0.2700g填料磷酸氢钙(平均粒径4μm)、0.0041g偶联剂γ-氨丙基三乙氧基硅烷(偶联剂用量为磷酸氢钙总质量的1.5％)溶解在0.6260g有机溶剂N,N-二甲基乙酰胺，搅拌分散均匀，得到浆料Ⅱ；
在氮气气氛下，将8.0092g(0.086mol)催化剂3-甲基吡啶和8.7797g(0.086mol)脱水剂乙酸酐溶解于16.2111g有机溶剂N,N-二甲基乙酰胺中，边冷却(温度为-25℃)边搅拌0.5h，得到催化液并保持处于低温状态(温度为-25℃)；
(b)将浆料Ι和浆料Ⅱ混合，继续搅拌1h，真空消泡，得到复合浆料；
(c)将复合浆料和催化液经混合器混合，然后经狭缝式模头流延到钢带上，钢带温度80-130℃，氮气气氛，除去一部分有机溶剂，接着从钢带上分离薄膜并经纵拉和横拉处理并亚胺化，亚胺化温度为420℃，处理时间为50s，最后收卷，得到聚酰亚胺薄膜。
实施例2
本实施例提供了一种聚酰亚胺薄膜，除了填料的质量占聚酰亚胺薄膜总质量的0.2％，其余原料、用量以及制备方法与实施例1相同。
实施例3
本实施例提供了一种聚酰亚胺薄膜，除了填料的质量占聚酰亚胺薄膜总质量的5％，其余原料、用量以及制备方法与实施例1相同。
实施例4
本实施例提供了一种聚酰亚胺薄膜，除了将制备方法中的亚胺化温度由420℃替换为380℃，其余原料、用量以及制备方法与实施例1相同。
实施例5
本实施例提供了一种聚酰亚胺薄膜，除了将制备方法中的亚胺化温度由420℃替换为450℃，其余原料、用量以及制备方法与实施例1相同。
实施例6
本实施例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将二酐Ι100mol％替换为二酐Ι90mol％和二酐Ⅱ10mol％，二酐Ⅱ为3,3',4,4'-联苯四羧酸二酐，其余原料、用量以及制备方法与实施例5相同。
实施例7
本实施例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将二酐Ι100mol％替换为二酐Ι70mol％和二酐Ⅱ30mol％，二酐Ⅱ为3,3',4,4'-联苯四羧酸二酐，其余原料、用量以及制备方法与实施例5相同。
实施例8
本实施例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将二酐Ι100mol％替换为二酐Ι50mol％和二酐Ⅱ50mol％，二酐Ⅱ为3,3',4,4'-联苯四羧酸二酐，其余原料、用量以及制备方法与实施例5相同。
实施例9
本实施例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将二胺Ι100mol％替换为二胺Ι90mol％和二胺Ⅱ10mol％，二胺Ⅱ为1,4-二氨基苯(PDA)，其余原料、用量以及制备方法与实施例5相同。
实施例10
本实施例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将二胺Ι100mol％替换为二胺Ι70mol％和二胺Ⅱ30mol％，二胺Ⅱ为1,4-二氨基苯(PDA)，其余原料、用量以及制备方法与实施例5相同。
实施例11
本实施例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将二胺Ι100mol％替换为二胺Ι50mol％和二胺Ⅱ50mol％，二胺Ⅱ为1,4-二氨基苯(PDA)，其余原料、用量以及制备方法与实施例5相同。
实施例12
本实施例提供了一种聚酰亚胺薄膜，除了将填料由改性无机填料(γ-氨丙基三乙氧基硅烷改性的磷酸氢钙)替换为未改性无机填料磷酸氢钙，即磷酸氢钙表面未经表面改性，其余原料、用量与实施例5相同。
本实施例提供的上述聚酰亚胺薄膜的制备方法，除了在浆料Ⅱ的制备过程中未添加硅烷偶联剂γ-氨丙基三乙氧基硅烷，其余步骤与实施例5相同。
实施例13
本实施例提供了一种聚酰亚胺薄膜，主要由以下原料制成：二酐、二胺、脱水剂、催化剂和填料；
其中，二酐包括二酐Ι和二酐Ⅱ，二酐Ι为均苯四甲酸二酐(PMDA)，二酐Ⅱ为2,3,3',4-联苯四羧酸二酐；
二胺包括二胺Ι和二胺Ⅱ，二胺Ι为4,4'-二氨基二苯醚(ODA)，二胺Ⅱ为1,3-双(4-氨基苯氧基)苯；二酐和二胺的摩尔比为1.02：1；催化剂为异喹啉，二酐和催化剂的摩尔比为1：2；脱水剂为丁酸酐，二酐和脱水剂的摩尔比为1：2；
填料为改性无机填料，即γ-N-(β-氨乙基)-α氨丙基三甲氧基硅烷改性的碳酸钙，(N-(β-氨乙基)-α氨丙基三甲氧基硅烷用量为碳酸钙总质量的3.0％)，碳酸钙的平均粒径为1.0μm，填料的质量占聚酰亚胺薄膜总质量的5.0％。
本实施例提供的上述聚酰亚胺薄膜的制备方法，包括以下步骤：
(a)提供浆料Ι、浆料Ⅱ和催化液
在氮气气氛下，向反应器中加入7.1085g(0.0355mol)二胺Ι(4,4'-二氨基二苯醚)和10.3777g(0.0355mol)二胺Ⅱ(1,3-双(4-氨基苯氧基)苯)，再加入有机溶剂N,N-二甲基乙酰胺搅拌使之溶解，边冷却(温度为-20℃)边加入7.7433g(0.0355mol)二酐Ι(均苯四甲酸二酐)和10.4448g(0.0355mol)二酐Ⅱ(2,3,3',4-联苯四羧酸二酐)，低温下机械搅拌8h，得到粘度150000厘泊的浆料Ι(含有18wt％的聚酰胺酸溶液)；
在氮气气氛下，将0.9g填料碳酸钙(平均粒径1.0μm)、0.027g偶联剂γ-N-(β-氨乙基)-α氨丙基三甲氧基硅烷(偶联剂用量为磷酸氢钙总质量的3.0％)溶解在2.073g有机溶剂N,N-二甲基乙酰胺，搅拌分散均匀，得到浆料Ⅱ；
在氮气气氛下，将9.1574g(0.0709mol)催化剂异喹啉和11.2164g(0.0709mol)脱水剂丁酸酐溶解于12.6262g有机溶剂N,N-二甲基乙酰胺中，边冷却(温度为-20℃)边搅拌0.5h，得到催化液并保持处于低温状态(温度为-20℃)；
(b)将浆料Ι和浆料Ⅱ混合，继续搅拌1h，真空消泡，得到复合浆料；
(c)将复合浆料和催化液经混合器混合，然后经狭缝式模头流延到钢带上，钢带温度80-130℃，氮气气氛，除去一部分有机溶剂，接着从钢带上分离薄膜并经纵拉和横拉处理并亚胺化，亚胺化温度380℃，处理时间为50s，最后收卷，得到聚酰亚胺薄膜。
实施例14-26
实施例14-26分别提供了一种人工石墨膜，分别采用实施例1-13提供的聚酰亚胺薄膜制成。
人工石墨膜的制备方法，包括以下步骤：
将聚酰亚胺薄膜1300℃碳化处理4h，再3000℃石墨化处理8h，得到人工石墨膜。
其中，碳化处理的操作为：将聚酰亚胺薄膜夹在人造石墨膜之间，在炭化炉真空环境下以5℃/min的速度升温至1300℃，随后保温1小时；石墨化处理的操作为：将聚酰 亚胺炭化膜，在石墨化炉氩气环境下以5℃/min的速度升温至3000℃，随后保温0.5小时。
实施例27-39
实施例27-39分别提供了一种人工石墨膜，分别采用实施例1-13提供的聚酰亚胺薄膜制成。
人工石墨膜的制备方法，包括以下步骤：
将聚酰亚胺薄膜1200℃碳化处理5h，再2900℃石墨化处理9h，得到人工石墨膜。
其中，碳化处理的操作为：将聚酰亚胺薄膜夹在人造石墨膜之间，在炭化炉真空环境下以5℃/min的速度升温至1200℃，随后保温1小时；石墨化处理的操作为：将聚酰亚胺炭化膜，在石墨化炉氩气环境下以5℃/min的速度升温至2900℃，随后保温0.5小时。
对比例1
本对比例提供了一种聚酰亚胺薄膜，除了制备方法中亚胺化温度由420℃替换为350℃，其余原料种类、用量与制备方法与实施例1相同。
对比例2
本对比例提供了一种聚酰亚胺薄膜，除了原料中未添加填料，其余原料种类、用量与制备方法与实施例1相同。
本对比例提供的聚酰亚胺薄膜的制备方法，除了步骤(a)中未提供浆料Ⅱ，且未进行步骤(b)且步骤(c)中直接将浆料Ι与催化液混合后制膜，其余步骤与实施例1相同。
对比例3
本对比例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将二酐Ι均苯四甲酸二酐替换为二酐Ⅱ3,3',4,4'-联苯四羧酸二酐，其余原料、用量以及制备方法与实施例1相同。
对比例4
本对比例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将二酐Ι均苯四甲酸二酐替换为二酐Ⅱ2,3,3',4-联苯四羧酸二酐，其余原料、用量以及制备方法与实施例1相同。
对比例5
本对比例提供了一种聚酰亚胺薄膜，除了改变二酐的种类，即将二酐Ι均苯四甲酸二酐替换为二酐Ⅱ2,3,3',4-联苯四羧酸二酐50mol％和3,3',4,4'-联苯四羧酸二酐50mol％，其余原料、用量以及制备方法与实施例1相同。
对比例6
本对比例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将二胺Ι4,4'-二氨基二苯醚替换为二胺Ⅱ1,4-二氨基苯，其余原料、用量以及制备方法与实施例1相同。
对比例7
本对比例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将二胺Ι4,4'-二氨基二苯醚替换为二胺Ⅱ1,3-双(4-氨基苯氧基)苯，其余原料、用量以及制备方法与实施例1相同。
对比例8
本对比例提供了一种聚酰亚胺薄膜，除了改变二胺的种类，即将二胺Ι4,4'-二氨基二苯醚替换为二胺Ⅱ1,3-双(4-氨基苯氧基)苯50mol％和1,3-二氨基苯50mol％，其余原料、用量以及制备方法与实施例1相同。
对比例9
本对比例提供了一种聚酰亚胺薄膜，除了填料的质量占聚酰亚胺薄膜总质量的0.1％，其余原料、用量以及制备方法与实施例1相同。
对比例10
本对比例提供了一种聚酰亚胺薄膜，除了填料的质量占聚酰亚胺薄膜总质量的6％，其余原料、用量以及制备方法与实施例1相同。
对比例11-20
对比例11-20分别提供了一种人工石墨膜，分别采用对比例1-10提供的聚酰亚胺薄膜制成。
人工石墨膜的制备方法与实施例14-26的制备方法相同。
为验证各实施例和对比例的技术效果，特进行以下实验。
实验例
实验例1
对实施例1-13和对比例1-10提供的聚酰亚胺薄膜的厚度、断裂伸长率、弹性模量、热膨胀系数(CTE)、各项异性(n(TE)-n(TM))等性能进行检测，结果如表1所示。
其中，聚酰亚胺薄膜厚度通过千分尺进行测定，检测方法依据GB/T 6672-2001；断裂伸长率、弹性模量通过万能拉伸试验机测得，检测方法依据GBT1040.3-2006；热膨胀系数通过热机械分析仪(TMA)测得，检测方法依据ISO 11359-2；各项异性(n(TE)和n(TM))采用Metricon公司制造的折射率-膜厚测定系统(型号：2010；棱镜耦合器)测定聚酰亚胺薄膜的双折射，测定方法如下：在25℃的环境下使用波长594nm的光源，分别在TE模式(Transverse Electric mode，横向电模式)和TM模式(Transverse Magnetic mode，横磁模式)下测定折射率，并测定n(TE)-n(TM)的值作为双折射。
表1
Figure PCTCN2021109459-appb-000001
Figure PCTCN2021109459-appb-000002
实验例2
对实施例14-26和对比例11-20提供的人工石墨膜的耐弯折性能和导热系数等性能进行检测，结果见表2。
其中，耐弯折性能检测方法：取人工石墨膜样品100mm*100mm，将一侧固定，另一侧180°折叠并摊平，折叠半径R＝2mm，记为一次弯折，折叠10000次后，看样品是否破裂或有折痕。
导热系数是通过激光导热仪LFA 467测定人工石墨膜水平方向导热系数。
表2
Figure PCTCN2021109459-appb-000003
Figure PCTCN2021109459-appb-000004
从表1和表2所示的检测结果可以得出，本公开中提供的聚酰亚胺薄膜具有优异的力学性能，在制备的膜具有相同厚度的情况下，本公开实施方式制备得到的膜与对比例相比，在断裂伸长率和弹性模量上实现均衡、同时具有相对较低的热膨胀系数。且双折射(n(TE)-n(TM))数值越大，表明聚酰亚胺薄膜的取向性越好，制备得到的人工石墨膜导热性能越好、耐弯折性能更优良。
需要说明的是，对比例6由于采用二胺Ⅱ1,4-二氨基苯与二酐Ι均苯四甲酸二酐反应，由于两者反应所形成的分子链刚性太强，一成膜就会碎，基本无法成膜，故无法制成聚酰亚胺薄膜，故表1中对比例6以及表2中对比例16的数据无法给出。
同时需要说明的是，实施例27-39具有的耐弯折性能和导热系数具有和实施例14-26相近的技术效果(表2中未示出)。
最后应说明的是：以上各实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述各实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的范围。
工业实用性
本公开提供了聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备。该聚酰亚胺薄膜具有优异的力学性能和薄膜取向，采用上述聚酰亚胺薄膜制备的人工石墨膜具有更加完整的石墨结构，具有优异的导热性能，同时还具有优异的力学性能，可根据实际需要 加工成各式各样，满足不同应用场景的需求，而包含其的电子设备也具有同样的优势，具有广泛的应用前景和较高的市场价值。

Claims (15)

  1. 一种聚酰亚胺薄膜，其特征在于，所述聚酰亚胺薄膜的厚度为25-100μm，断裂伸长率为70-130％，弹性模量为2.7-4.0GPa，热膨胀系数为16-32ppm/K；
    所述聚酰亚胺薄膜主要由以下原料制成：二酐、二胺、脱水剂、催化剂和填料；
    其中，二酐包括二酐Ι，所述二酐Ι包括均苯四甲酸二酐，二胺包括二胺Ι，所述二胺Ι包括4,4'-二氨基二苯醚；
    所述填料包括未改性无机填料和/或改性无机填料，所述填料的质量占聚酰亚胺薄膜总质量的0.2-5.0％。
  2. 根据权利要求1所述的聚酰亚胺薄膜，其特征在于，所述聚酰亚胺薄膜沿平面方向的折射率与沿厚度方向的折射率的差值为0.095-0.15。
  3. 根据权利要求1或2所述的聚酰亚胺薄膜，其特征在于，所述填料的平均粒径为1.0-6.0μm；
    优选的，所述未改性无机填料包括碳酸钙、碳酸氢钙或磷酸氢钙中的任意一种或至少两种的组合；
    优选的，所述改性无机填料包括经过偶联剂进行表面改性的无机填料；
    优选的，所述偶联剂的用量为所述无机填料总质量的1-5％；
    优选的，所述偶联剂包括硅烷偶联剂，优选包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-α氨丙基三甲氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷中的任意一种；
    优选的，所述无机填料包括碳酸钙、碳酸氢钙或磷酸氢钙中的任意一种或至少两种的组合。
  4. 根据权利要求1-3任意一项所述的聚酰亚胺薄膜，其特征在于，所述二酐包括二酐Ι和二酐Ⅱ，二酐Ι和二酐Ⅱ的摩尔百分比为(50-100mol％)：(0-50mol％)；
    优选的，所述二酐Ⅱ包括3,3',4,4'-联苯四羧酸二酐和/或2,3,3',4-联苯四羧酸二酐；
    优选的，所述二胺包括二胺Ι和二胺Ⅱ，二胺Ι和二胺Ⅱ的摩尔百分比为(50-100mol％)：(0-50mol％)；
    优选的，所述二胺Ⅱ包括1,4-二氨基苯、1,3-二氨基苯或1,3-双(4-氨基苯氧基)苯中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任意一项所述的聚酰亚胺薄膜，其特征在于，所述脱水剂包括酸酐；优选的，所述催化剂包括有机叔胺；
    优选的，所述酸酐包括甲酸酐、乙酸酐、丙酸酐、丁酸酐或戊酸酐任意一种或至少两种的组合；
    优选的，所述有机叔胺包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。
  6. 根据权利要求1-5任意一项所述的聚酰亚胺薄膜，其特征在于，所述脱水剂包括乙酸酐、丙酸酐或丁酸酐中的任意一种或至少两种的组合；
    优选的，所述催化剂包括吡啶、3-甲基吡啶、三乙胺或异喹啉中的任意一种或至少两种的组合。
  7. 根据权利要求1-6任意一项所述的聚酰亚胺薄膜，其特征在于，所述二酐和二胺的摩尔比为1：(0.9-1.1)；
    优选的，所述二酐和脱水剂的摩尔比为1：(0-2)；
    优选的，所述二酐和催化剂的摩尔比为1：(0.5-2)。
  8. 权利要求1-7任意一项所述的聚酰亚胺薄膜的制备方法，其特征在于，包括以下步骤：
    提供二酐、二胺和有机溶剂形成的浆料Ι，提供填料和有机溶剂形成的浆料Ⅱ，提供脱水剂、催化剂和有机溶剂形成的催化液；
    将浆料Ι和浆料Ⅱ混合，得到复合浆料；
    将复合浆料与催化液混合后制膜，得到聚酰亚胺薄膜。
  9. 根据权利要求8所述的聚酰亚胺薄膜的制备方法，其特征在于，所述有机溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的任意一种或至少两种的组合；
    优选的，所述聚酰亚胺薄膜的制备方法包括以下步骤：
    (a)将二酐、二胺加入到有机溶剂中，于-25-0℃搅拌，得到浆料Ι；其中，浆料Ι的粘度不小于100000厘泊；
    将填料加入到有机溶剂中，得到浆料Ⅱ；
    将脱水剂、催化剂加入到有机溶剂中，并保持-25-0℃，得到催化液；
    (b)将浆料Ι和浆料Ⅱ于-25-0℃混合，得到复合浆料；
    (c)将复合浆料和催化液混合后，再经流延、干燥、拉伸和亚胺化处理，得到聚酰亚胺薄膜；
    优选的，亚胺化处理的温度为380-450℃。
  10. 一种人工石墨膜，其特征在于，采用权利要求1-7任意一项所述的聚酰亚胺薄膜或权利要求8或9所述的聚酰亚胺薄膜的制备方法制得的聚酰亚胺薄膜制成。
  11. 制备如权利要求10所述的人工石墨膜的方法，其特征在于，所述方法包括：将所述聚酰亚胺薄膜碳化处理后，再进行石墨化处理，得到所述人工石墨膜。
  12. 根据权利要求11所述的方法，其特征在于，所述碳化处理的温度为1000-1500℃，所述碳化处理的时间为4-8h。
  13. 如权利要求10所述的人工石墨膜用于散热材料的用途。
  14. 一种电子设备，其特征在于，包含权利要求10所述的人工石墨膜。
  15. 根据权利要求14所述的电子设备，其特征在于，所述电子设备包括芯片、手机、平板电脑、笔记本电脑、电视、户外广告屏、录像机、摄录机、照相机、影碟机、激光唱机、音响、收录机、投影仪、复印机、扫描仪、传真机中的一种。
PCT/CN2021/109459 2020-12-31 2021-07-30 聚酰亚胺薄膜及其制备方法、人工石墨膜和电子设备 WO2022142320A1 (zh)

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