CN105820368B - A kind of polyimide nano foam and preparation method thereof - Google Patents
A kind of polyimide nano foam and preparation method thereof Download PDFInfo
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- CN105820368B CN105820368B CN201610352251.5A CN201610352251A CN105820368B CN 105820368 B CN105820368 B CN 105820368B CN 201610352251 A CN201610352251 A CN 201610352251A CN 105820368 B CN105820368 B CN 105820368B
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
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- 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
Abstract
The present invention provides a kind of polyimide nano foams and preparation method thereof, include the following steps：A) diamine compound of the group containing adamantane, the diamine compound without adamantane group and two compound anhydrides are subjected to polymerization reaction in a solvent, obtain polyamic acid solution；B successively pass through evenly dispersed or polymerization reaction, curtain coating, solidification and hot imidization after) mixing heat-labile compound with the polyamic acid solution, obtain Kapton；C the Kapton) is obtained into polyimide nano foam by thermally decomposing.Since adamantane group is bulky group, the molal volume of atomic group is improved, to effectively reduce the dielectric constant of polyimide matrix, thereby reduces the dielectric constant of Polyimide nanofoams materials；On the other hand, the introducing of adamantane group improves the glass transition temperature of polyimides, increases the thermal stability of material.And the polyimide nano foam has excellent mechanical property.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of polyimide nano foam and preparation method thereof.
Background technique
Currently, the number of transistors integrated on chip is more and more with the rapid development of integrated circuit (IC) industry, in
This simultaneously, microelectronic component becomes smaller and smaller.Under this double action, the density of interconnection wiring is increasing on chip, mutually
Even resistance and line capacitance increase, and cause signal transmission time delay that distorted signals even occurs.International Semiconductor Industry Association
Revision in 2009《International technology roadmap for semiconductors》Prediction, for the development for meeting future IC industry, insulating dielectric is normal
Number palpus<2.0.However the dielectric constant values of bulk material are extremely difficult to 2.0 hereinafter, existing insulating materials such as silica etc.,
Have been unable to meet requirement.This becomes the bottleneck of IC industry development.Therefore, insulating dielectric constants are reduced to reduce resistance-capacitance
Delay time becomes the inevitable choice of IC industry.Polyimide material is insulating materials important in microelectronics industry, has heat
The advantages that stability is good, chemical stability is good, water absorption rate is low, good mechanical performance, but traditional polyimide material dielectric is normal
Number is 3.0~3.4, is unable to satisfy requirement of the microelectronics industry to insulating dielectric constants, therefore reduce polyimide material
It is very necessary that dielectric constant is applied to microelectronics industry.
Hedrick etc. obtains thermally labile object grafting/block to polyimide molecule chain poly- after thermal decomposition
Acid imide nanofoam materials, but the product after thermally labile object decomposes is plasticized polyimide matrix, leads to major part
Abscess occurs to collapse (Chem.Mater.1998,10,39-49).Pluronic F-127 (PEO) is added to polyamic acid by Zhang etc.
In solution, Polyimide nanofoams materials, dielectric constant 2.4, aperture are prepared for after imidizate and thermal decomposition
Range is 40~200nm (J.Electron Mater, 2012,41,8,2281-2285).But PEO have it is highly hydrophilic,
Surface enrichment is serious in wet environment, causes System of Detecting Surface Defects For Material serious.Lee etc. is by ethylene oxide graft to hollow poly- sesquialter
On siloxanes (PEO-POSS), and it is distributed in polyamic acid solution as pore-foaming agent and is prepared for nanoporous polyimides
Film, dielectric constant minimum 2.25 (Polymer, 2005,46,23,10056-10065).This method makes hollow poly- sesquialter silicon
Oxygen alkane can be well dispersed in polyimides, but is easy to appear linked hole and preparation process complexity, and introduces hollow poly-
Silsesquioxane higher cost, is unfavorable for industrialized production.Chinese patent 201510225007.8 adds calcium carbonate suspension
Into polyamic acid solution, after mixing evenly, Kapton is made using the tape casting, it is later that Kapton is slow
By dilute hydrochloric acid solution, calcium carbonate etching obtains polyimide porous film after decomposing.Chinese patent CN 1760241 A and CN
102417604 A are prepared for polyimide/nano-silica hybrid films first, then etch silica with HF, obtain
Obtained porous polyimide film.101645497 B of Chinese patent CN 104211980 A and CN is by nanoscale zinc, manganese, alkali
Earth metal hydroxide, aluminium hydroxide or metal phosphate are introduced into polyimides as pore former, are made with after acid etch
Porous polyimide film.103980522 A of Chinese patent CN is first by polystyrene microsphere solution natural sediment to substrate
On, then polyimides is electrodeposited on the substrate containing microballoon, finally etches obtained polyimide composite film, is obtained
Porous polyimide film.The above method is to obtain porous polyimide film using the method for etching, such film material
Expect most of abscess connection, causes the defect of material more.Styrene and oleic acid polymerize by 104157630 A of Chinese patent CN
The pore-foaming agent of preparation is added to polyamic acid saline solution, is prepared for polyamic acid salt/pore by repeatedly " curtain coating, drying "
Agent laminated film, then porous polyimide film is prepared for through removing pore-foaming agent, imidizate technique.But it is preparing film
During, due to being repeatedly cast, causes the uniformity of film of preparation bad, pore-foaming agent furthermore occurs during imidizate
Phenomenon is removed, the abscess of final material is caused to collapse.103467984 A of Chinese patent CN is prepared for polyimide/inorganic first
Laminated film is put into the inert gases autoclave such as carbon dioxide by particle composite film later, and gas is made to be dissolved into polyamides Asia
In amine composite membrane.Wherein, inorganic particulate acts as the effect of nucleating agent, makes being more evenly distributed for hole, but this method obtain it is more
Porous materials are multi-joint through-hole, and in the process, inert gas generates plasticization to polyimide matrix, lead to material TgDrop
It is low.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of polyimide nano foam and its preparation side
Method, polyimide nano foam provided by the invention also have good heat resistance while with lower dielectric constant
Energy and mechanical property.
The present invention provides a kind of preparation methods of polyimide nano foam, include the following steps：
A) by the diamine compound of the group containing adamantane, the diamine compound without adamantane group and two anhydride chemical combination
Object carries out polymerization reaction in a solvent, obtains polyamic acid solution；
B successively by evenly dispersed, curtain coating, solidification after) heat-labile compound is mixed with the polyamic acid solution
And hot imidization, obtain Kapton；
C the Kapton) is obtained into polyimide nano foam by thermally decomposing.
The present invention also provides a kind of preparation methods of polyimide nano foam, include the following steps：
A) by the diamine compound of the group containing adamantane, the diamine compound without adamantane group, two compound anhydrides
And heat-labile compound carries out polymerization reaction in a solvent, obtains polyamic acid solution；
B) polyamic acid solution is obtained into Kapton successively by curtain coating, solidification and hot imidization；
C) Kapton obtains polyimide nano foam by thermal decomposition.
Preferably, the diamine compound of the group containing adamantane is selected from has formula (I-1)~formula (I-7) structure below
One of compound is a variety of：
Preferably, the diamine compound without adamantane group is selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminos
Yl diphenyl ether, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminobenzophenones, 4,4 '-diaminos
Base -3,3 '-dimethyl diphenyl, 4,4' diaminodiphenyl sulfone, 2- (4- aminophenyl) -5- aminopyrimidine, 2,2 '-two (fluoroforms
Base) -4,4 '-benzidine, 2,5- bis- (4- aminophenyl) pyrimidine, 2,5- bis- (4- aminophenyl) pyridine, 2- (4- aminobenzene
Base) one of -5- aminopyridine and 2,6- diamino-pyridine or a variety of.
Preferably, two compound anhydride is selected from the compound with formula (II-1)~formula (II-5) structure below
It is one or more：
Wherein, A be selected from S, O,
Preferably, the heat-labile compound is selected from compound below with formula (III-1)~formula (III-9) structure
One of or it is a variety of：
Wherein, n is the degree of polymerization, and the number-average molecular weight of the heat-labile compound is 500~5000.
Preferably, the heat-labile compound is selected from chemical combination below with formula (III-10)~formula (III-14) structure
One of object is a variety of：
Wherein, n is the degree of polymerization, and the number-average molecular weight of the heat-labile compound is 500~5000.
Preferably, the additional amount of the heat-labile compound accounts for the diamine compound of the group containing adamantane, is free of
3wt%~30wt% of the diamine compound of adamantane group and two compound anhydride gross masses, the polyamic acid solution
Solid content be 9wt%~40wt%.
Preferably, for the cured humidity less than 30%, the cured temperature is 50~150 DEG C, when described cured
Between for 10~for 24 hours；The hot imidization carries out under atmosphere of inert gases, and the temperature of the hot imidization is 280~350 DEG C,
The time of the hot imidization is 20min~60min.
Preferably, the thermal decomposition process is：Under air atmosphere, with the heating rate of 1~10 DEG C/min from 20~50
DEG C ladder-elevating temperature keeps 1~10h to 250~350 DEG C.
The present invention also provides a kind of polyimide nano foams that above-mentioned preparation method is prepared.
Compared with prior art, the present invention provides a kind of preparation methods of polyimide nano foam, including following step
Suddenly：A) diamine compound of the group containing adamantane, the diamine compound without adamantane group and two compound anhydrides are existed
Polymerization reaction is carried out in solvent, obtains polyamic acid solution；B) heat-labile compound is mixed with the polyamic acid solution
Successively pass through evenly dispersed or polymerization reaction, curtain coating, solidification and hot imidization afterwards, obtains Kapton；It C) will be described poly-
Imide membrane obtains polyimide nano foam by thermal decomposition.Thermally labile object is introduced into containing adamantyl by the present invention
In the diamine monomer of group and the polymer solution of dianhydride monomer, film-forming obtains after imidizate, thermal decomposition process
Polyimide nanofoams materials.Since adamantane group is bulky group, the molal volume of atomic group is improved, to have
Effect reduces the dielectric constant of polyimide matrix, thereby reduces the dielectric constant of Polyimide nanofoams materials；It is another
Aspect, the introducing of adamantane group improve the T of polyimidesg, the thermal stability of material is increased, and the polyimides is received
Rice foam has excellent mechanical property.
The result shows that polyimide nano foam dielectric constant provided by the invention is 1.90~2.45, glass transition
Temperature is 312~362 DEG C, and tensile strength is up to 115.8MPa, and it is 8.18% that elongation at break, which is up to,.
Specific embodiment
The present invention provides a kind of preparation methods of polyimide nano foam, which is characterized in that includes the following steps：
A) by the diamine compound of the group containing adamantane, the diamine compound without adamantane group and two anhydride chemical combination
Object carries out polymerization reaction in a solvent, obtains polyamic acid solution；
B successively by evenly dispersed, curtain coating, solidification after) heat-labile compound is mixed with the polyamic acid solution
And hot imidization, obtain Kapton；
C the Kapton) is obtained into polyimide nano foam by thermally decomposing.
The present invention is first by the diamine compound of the group containing adamantane, the diamine compound without adamantane group and two
Compound anhydride carries out polymerization reaction in a solvent, obtains polyamic acid solution.
In the present invention, the temperature of the polymerization reaction is preferably 20~40 DEG C, more preferably under the conditions of 20~30 DEG C into
Row reaction.The solvent is preferably N, N '-dimethylformamide, N, N '-dimethyl acetamide, dimethyl sulfoxide and N- methyl pyrrole
One or more of pyrrolidone.
After obtaining polyamic acid solution, successively by equal after heat-labile compound is mixed with the polyamic acid solution
Even dispersion, curtain coating, solidification and hot imidization, obtain Kapton.
In the present invention, after the heat-labile compound is mixed with the polyamic acid solution, ultrasound is preferably carried out, with
Guarantee that heat-labile compound and the polyamic acid solution are sufficiently mixed uniformly.
The heat-labile compound is preferably selected from the following chemical combination with formula (III-10)~formula (III-14) structure
One of object is a variety of：
The number-average molecular weight of the heat-labile compound is 500~5000.
It will be cast, be solidified and hot imidization by well-mixed heat-labile compound and polyamic acid solution,
Obtain Kapton.
Wherein, the present invention is to the method for the curtain coating there is no specifically limited, and well known to a person skilled in the art curtain coating sides
Method.
In the present invention, the mode mixed solution of heat-labile compound and the polyamic acid solution to be formed a film
Can direct casting film-forming, or curtain coating after biaxial tension form a film.There is no special for mode of the present invention to the biaxial tension
Limitation, well known to a person skilled in the art the methods of biaxial tension.
Condition of cure of the present invention be preferably humidity less than 30% when, 50~150 DEG C keep 10~for 24 hours, it is more excellent
Choosing, the cured humidity is preferably 5%~25%, and the cured temperature is 60~120 DEG C, and the cured time is
12~20h.
After solidification, obtained film is subjected to hot imidization.In the present invention, the hot imidization process conditions are inertia
Under atmosphere, 280~350 DEG C of holding 20min~60min.The temperature of the hot imidization is preferably 290~340 DEG C, described
The time of hot imidization is preferably 30min~50min.
After hot imidization, Kapton is obtained.By the Kapton by thermally decomposing, polyimides is obtained
Nanometer foam.
In the present invention, the thermal decomposition process is：Under air atmosphere, with the heating rate of 1~10 DEG C/min from 20
~50 DEG C of ladder-elevating temperatures keep 1~10h to 250~350 DEG C.
When carrying out the preparation of polyimide nano foam, all raw materials can also be mixed together to carry out polymerization reaction,
Kapton is obtained again, and then obtains polyimide nano foam.
That is, including the following steps the present invention also provides a kind of preparation method of polyimide nano foam：
A) by the diamine compound of the group containing adamantane, the diamine compound without adamantane group, two compound anhydrides
And heat-labile compound carries out polymerization reaction in a solvent, obtains polyamic acid solution；
B) polyamic acid solution is obtained into Kapton successively by curtain coating, solidification and hot imidization；
C) Kapton obtains polyimide nano foam by thermal decomposition.
The present invention is first by the diamine compound of the group containing adamantane, the diamine compound without adamantane group, dianhydride
Class compound and heat-labile compound carry out polymerization reaction in a solvent, obtain polyamic acid solution.
In the present invention, the temperature of the polymerization reaction is preferably 20~40 DEG C, more preferably under the conditions of 20~30 DEG C into
Row reaction.The solvent is preferably N, N '-dimethylformamide, N, N '-dimethyl acetamide, dimethyl sulfoxide and N- methyl pyrrole
One or more of pyrrolidone.The heat-labile compound is preferably selected from following with formula (III-1)~formula (III-9)
One of compound of structure is a variety of：
In structure above, n is the degree of polymerization, and the number-average molecular weight of the heat-labile compound is 500~5000.
Polyimides acid solution obtained above is cast, is solidified and hot imidization, Kapton is obtained.
Wherein, the present invention is to the method for the curtain coating there is no specifically limited, and well known to a person skilled in the art curtain coating sides
Method.
In the present invention, the mode polyamic acid solution to be formed a film can direct casting film-forming, or curtain coating
Biaxial tension forms a film afterwards.The present invention to the mode of the biaxial tension there is no specifically limited, well known to a person skilled in the art
The method of biaxial tension.
Condition of cure of the present invention be preferably humidity less than 30% when, 50~150 DEG C keep 10~for 24 hours, it is more excellent
Choosing, the cured humidity is preferably 5%~25%, and the cured temperature is 60~120 DEG C, and the cured time is
12~20h.
After solidification, obtained film is subjected to hot imidization.In the present invention, the hot imidization process conditions are inertia
Under atmosphere, 280~350 DEG C of holding 20min~60min.The temperature of the hot imidization is preferably 290~340 DEG C, described
The time of hot imidization is preferably 30min~50min.
After hot imidization, Kapton is obtained.By the Kapton by thermally decomposing, polyimides is obtained
Nanometer foam.
In the present invention, the thermal decomposition process is：Under air atmosphere, with the heating rate of 1~10 DEG C/min from 20
~50 DEG C of ladder-elevating temperatures keep 1~10h to 250~350 DEG C.
In the above two preparation method for preparing polyimide nano foam, the diamine compound of the group containing adamantane
Selected from one of compound below with formula (I-1)~formula (I-7) structure or a variety of：
The diamine compound without adamantane group is selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diamino hexichol
Ether, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminobenzophenones, 4,4 '-diamino -3,
3 '-dimethyl diphenyls, 4,4' diaminodiphenyl sulfone, 2- (4- aminophenyl) -5- aminopyrimidine, 2,2 '-two (trifluoromethyls) -
4,4 '-benzidines, 2,5- bis- (4- aminophenyl) pyrimidine, 2,5- bis- (4- aminophenyl) pyridine, 2- (4- aminophenyl)-
One of 5- aminopyridine and 2,6- diamino-pyridine are a variety of.
One of compound below two compound anhydride with formula (II-1)~formula (II-5) structure is a variety of：
Wherein, A be selected from S, O,
In above two preparation method, the additional amount of the heat-labile compound accounts for the two of the group containing adamantane
3wt%~30wt% of amine compounds, the diamine compound without adamantane group and two compound anhydride gross masses, preferably
For 5wt%~25wt%；The solid content of the polyamic acid solution is 9wt%~40wt%, preferably 10wt%~35wt%.
The present invention also provides a kind of polyimide nano foams being prepared using above-mentioned preparation method.
Thermally labile object is introduced into the diamine monomer of the group containing adamantane and the polymer solution of dianhydride monomer by the present invention
In, film-forming obtains Polyimide nanofoams materials after imidizate, thermal decomposition process.Due to adamantane group
For bulky group, the molal volume of atomic group is improved, to effectively reduce the dielectric constant of polyimide matrix, in turn
Reduce the dielectric constant of Polyimide nanofoams materials；On the other hand, the introducing of adamantane group, improves polyimides
Tg, the thermal stability of material is increased, and there is excellent mechanical property.Polyimide nano foam provided by the invention can
It is used as multi-chip module, dielectric layer, integrated circuit substrate etc. applied to fields such as microelectronics.
The result shows that polyimide nano foam dielectric constant provided by the invention is 1.9~2.45, glass transition temperature
Degree is 312~362 DEG C, and tensile strength is up to 115.8MPa, and it is 8.18% that elongation at break, which is up to,.
For a further understanding of the present invention, below with reference to embodiment to polyimide nano foam provided by the invention and its
Preparation method is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
2,2 '-bis- (4- aminophenyl) adamantane (I-1) 15.924g (0.05mol) are added to 340mlN, N '-diformazan
In yl acetamide solution, after stirring and dissolving, 10.01g (0.05mol) 4,4 '-diaminodiphenyl ether is added, is added after stirring and dissolving
3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride of 31.021g (0.1mol) obtains polyamic acid solution after reaction for 24 hours is stirred at room temperature,
Then polyethylene glycol (III-10) 8.543g that average molecular weight is 600 is added, and ultrasonic disperse is uniform, obtaining solid content is
15% mixed solution.By mixed solution curtain coating on matrix, and it is 30% in humidity, solidifies 10h at 80 DEG C of temperature, gathered
Amic acid film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, from room temperature with the heating rate of 3 DEG C/min
300 DEG C are risen to, 1h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 100 DEG C are risen to from 50 DEG C of heating rates with 1 DEG C/min, is protected
3h is held, then rises to 150 DEG C with the heating rate of 1 DEG C/min, 3h is kept, then rise to 260 DEG C with the heating rate of 1 DEG C/min, protects
1h is held, then rises to 300 DEG C with the heating rate of 1 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.37, and glass transition temperature is 320 DEG C, tensile strength 83.2MPa, elongation at break 6.16%.
Embodiment 2
2,2 '-bis- (4- aminophenyl) adamantane (I-1) 15.924g (0.05mol) are added to 350mlN, N '-diformazan
In yl acetamide solution, after stirring and dissolving, 10.01g (0.05mol) 4,4 '-diaminodiphenyl ether is added, after stirring and dissolving, adds
Enter average molecular weight for 750 diaminobenzoic acid macrogol ester (III-1) 2.907g (0.0039mol), after stirring and dissolving
3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride 32.223g (0.1039mol) are added, after reaction for 24 hours is stirred at room temperature, obtain polyamide
Acid solution.Polyamic acid solution is cast on sheet glass, and is 20% in humidity, solidifies 10h at 100 DEG C of temperature, is gathered
Amic acid film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, from room temperature with the heating rate of 5 DEG C/min
300 DEG C are risen to, 0.5h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 250 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min, is protected
4h is held, then rises to 300 DEG C with the heating rate of 1 DEG C/min, 4h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.23, and glass transition temperature is 320 DEG C, tensile strength 85.9MPa, elongation at break 6.06%.
Embodiment 3
(I-2) 13.6195g (0.05mol) is added to 340ml N, in N '-dimethylacetamide solution, stirring and dissolving
Afterwards, 10.612g (0.05mol) 4,4 '-diaminobenzophenone is added, after stirring and dissolving, 2000 (III- of average molecular weight is added
2) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 36g (0.1117mol) are added after stirring and dissolving in 23.4g (0.0117mol),
After reaction for 24 hours is stirred at room temperature, polyamic acid solution is obtained.It by polyamic acid solution curtain coating on matrix, and is 20% in humidity,
Solidify under temperature 50 C for 24 hours, obtains Polyamic Acid Film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas,
300 DEG C are risen to from room temperature with the heating rate of 4 DEG C/min, 0.7h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 250 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, is protected
5h is held, then rises to 300 DEG C with the heating rate of 1 DEG C/min, 5h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.31, and glass transition temperature is 334 DEG C, tensile strength 95.3MPa, elongation at break 7.12%.
Embodiment 4
(I-3) 31.645g (0.1mol) is added to 345ml N, in N '-dimethylacetamide solution, after stirring and dissolving,
Addition average molecular weight is 5000 (III-2) 8.53g (0.0017mol), and 3,3 ', 4,4 '-benzophenone are added after stirring and dissolving
Tetracarboxylic dianhydride 32.77g (0.1017mol) obtains polyamic acid solution after reaction for 24 hours is stirred at room temperature.By polyamic acid solution
Curtain coating is 30% on matrix, and in humidity, solidifies 20h under temperature 60 C, obtains Polyamic Acid Film.By Polyamic Acid Film
It is placed in the heating device under condition of nitrogen gas, rises to 310 DEG C from room temperature with the heating rate of 2 DEG C/min, 1h is kept to obtain polyamides
Imines film.
By above-mentioned Kapton under air atmosphere, 150 DEG C are risen to from room temperature with the heating rate of 5 DEG C/min, is protected
2h is held, then rises to 200 DEG C with the heating rate of 5 DEG C/min, 2h is kept, then rise to 300 DEG C with the heating rate of 5 DEG C/min, protects
2h is held, polyimide nano foam is obtained.After tested, dielectric constant 2.42, glass transition temperature are 347 DEG C, are stretched
Intensity is 92.1MPa, elongation at break 7.24%.
Embodiment 5
(I-4) 17.523g (0.05mol) is added to 385ml N, in N '-dimethylacetamide solution, stirring and dissolving
Afterwards, 11.316g (0.05mol) 4,4 '-diaminodiphenylmethane is added, after stirring and dissolving, it is 500 that average molecular weight, which is added,
(III-3) 4,4 '-(hexafluoro isopropyl is dilute) two anhydride phthalic acid 52.86g are added after stirring and dissolving in 9.535g (0.019mol)
(0.119mol) obtains polyamic acid solution after reaction for 24 hours is stirred at room temperature.By polyamic acid solution curtain coating on matrix, and
Humidity is 15%, solidifies for 24 hours at 80 DEG C of temperature, obtains Polyamic Acid Film.Polyamic Acid Film is placed under condition of nitrogen gas
In heating device, 300 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, 0.5h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 200 DEG C are risen to from room temperature with the heating rate of 1 DEG C/min, is protected
2h is held, then rises to 250 DEG C with the heating rate of 1 DEG C/min, 4h is kept, then rise to 300 DEG C with the heating rate of 1 DEG C/min, protects
4h is held, polyimide nano foam is obtained.After tested, dielectric constant 2.0, glass transition temperature are 327 DEG C, are stretched strong
Degree is 105.7MPa, elongation at break 7.26%.
Embodiment 6
(I-3) 31.645g (0.1mol) is added to 450ml N, in N '-dimethylacetamide solution, after stirring and dissolving,
(III-2) 7.38g (0.0074mol) that average molecular weight is 1000 is added, it is bis- (trifluoromethyl)-that Isosorbide-5-Nitrae-is added after stirring and dissolving
2,3,5,6- benzene tertacarbonic acid's dianhydride 35.66g (0.1007mol) obtain polyamic acid solution after reaction for 24 hours is stirred at room temperature.It will gather
Amic acid solution curtain coating is 20% on matrix, and in humidity, solidifies 10h at 100 DEG C of temperature, obtains Polyamic Acid Film.It will
Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, is risen to 300 DEG C from room temperature with the heating rate of 1 DEG C/min, is protected
It holds 1h and obtains Kapton.
By above-mentioned Kapton under air atmosphere, 250 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, is protected
2h is held, then rises to 340 DEG C with the heating rate of 3 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.45, and glass transition temperature is 362 DEG C, tensile strength 115.8MPa, elongation at break 5.98%.
Embodiment 7
(I-5) 17.722g (0.05mol) is added to 150ml N, in N '-dimethylacetamide solution, stirring and dissolving
Afterwards, 10.612g (0.05mol) 4,4 '-diaminobenzophenone is added, after stirring and dissolving, it is 1000 that average molecular weight, which is added,
(III-5) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 36g are added after stirring and dissolving in 7.38g (0.0074mol)
(0.1117mol) obtains polyamic acid solution after reaction for 24 hours is stirred at room temperature.By polyamic acid solution curtain coating on matrix, and
It is 20% in humidity, solidifies 10h at 100 DEG C of temperature, obtain Polyamic Acid Film.Polyamic Acid Film is placed under condition of nitrogen gas
Heating device in, rise to 300 DEG C from room temperature with the heating rate of 5 DEG C/min, 1h kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 250 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, is protected
2h is held, then rises to 300 DEG C with the heating rate of 3 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.13, and glass transition temperature is 339 DEG C, tensile strength 87.8MPa, elongation at break 6.29%.
Embodiment 8
(I-6) 63.824g (0.1mol) is added to 700ml N, in N '-dimethylacetamide solution, after stirring and dissolving,
(III-4) 45.6g (0.057mol) that average molecular weight is 800 is added, 2,3,6,7- tetracarboxylics -9,9- are added after stirring and dissolving
Bis- (trifluoromethyl) xanthene dianhydride 71.94g (0.157mol) obtain polyamic acid solution after reaction for 24 hours is stirred at room temperature.It will
Polyamic acid solution is cast on matrix, and is 20% in humidity, is solidified 12h at 80 DEG C of temperature, is obtained Polyamic Acid Film.It will
Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, is risen to 300 DEG C from room temperature with the heating rate of 5 DEG C/min, is protected
It holds 0.5h and obtains Kapton.
By above-mentioned Kapton under air atmosphere, 100 DEG C are risen to from room temperature with the heating rate of 2 DEG C/min, is protected
2h is held, then rises to 150 DEG C with the heating rate of 2 DEG C/min, 4h is kept, then rise to 200 DEG C with the heating rate of 2 DEG C/min, protects
4h is held, then rises to 250 DEG C with the heating rate of 2 DEG C/min, 2h is kept, then rise to 300 DEG C with the heating rate of 2 DEG C/min, protects
2h is held, polyimide nano foam is obtained.After tested, dielectric constant 1.9, glass transition temperature are 314 DEG C, are stretched strong
Degree is 101.9MPa, elongation at break 8.18%.
Embodiment 9
(I-7) 50.266g (0.1mol) is added to 750ml N, in N '-dimethylacetamide solution, after stirring and dissolving,
Addition average molecular weight is 3000 (III-8) 3.13g (0.001mol), and pyromellitic acid dianhydride 22.026g is added after stirring and dissolving
(0.101mol) obtains polyamic acid solution after reaction for 24 hours is stirred at room temperature.By polyamic acid solution curtain coating on matrix, and
Humidity is 20%, solidifies 12h at 100 DEG C of temperature, obtains Polyamic Acid Film.Polyamic Acid Film is placed under condition of nitrogen gas
In heating device, 300 DEG C are risen to from room temperature with the heating rate of 5 DEG C/min, 1h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 250 DEG C are risen to from room temperature with the heating rate of 2 DEG C/min, is protected
2h is held, then rises to 300 DEG C with the heating rate of 2 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.2, and glass transition temperature is 319 DEG C, tensile strength 92.7MPa, elongation at break 5.98%.
Embodiment 10
2,2 '-bis- (4- aminophenyl) adamantane (I-1) 15.924g (0.05mol) are added to 340mlN, N '-diformazan
In yl acetamide solution, after stirring and dissolving, 10.01g (0.05mol) 4,4 '-diaminodiphenyl ether is added, is added after stirring and dissolving
3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride of 31.021g (0.1mol) obtains polyamic acid solution after reaction for 24 hours is stirred at room temperature,
Be subsequently added into (III-11) 8.543g that average molecular weight is 2000, and ultrasonic disperse is uniform, obtain solid content be 15% it is mixed
Close solution.By mixed solution curtain coating on matrix, and it is 30% in humidity, solidifies 10h at 80 DEG C of temperature, obtain polyamide
Sour film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, is risen to from room temperature with the heating rate of 3 DEG C/min
300 DEG C, 1h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 100 DEG C are risen to from 50 DEG C of heating rates with 1 DEG C/min, is protected
3h is held, then rises to 150 DEG C with the heating rate of 1 DEG C/min, 3h is kept, then rise to 260 DEG C with the heating rate of 1 DEG C/min, protects
1h is held, then rises to 310 DEG C with the heating rate of 1 DEG C/min, 1h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.31, and glass transition temperature is 320 DEG C, tensile strength 84.5MPa, elongation at break 6.23%.
Embodiment 11
(I-3) 31.645g (0.1mol) is added to 450ml N, in N '-dimethylacetamide solution, after stirring and dissolving,
Bis- (trifluoromethyl) -2 of Isosorbide-5-Nitrae-are added, 3,5,6- benzene tertacarbonic acid's dianhydride 35.6g (0.1mol) are obtained after reaction for 24 hours is stirred at room temperature
Polyamic acid solution is subsequently added into (III-12) 10.09g that average molecular weight is 1000, and ultrasonic disperse is uniform, admittedly contained
The mixed solution that amount is 15%.By mixed solution curtain coating on matrix, and it is 20% in humidity, solidifies under temperature 60 C
12h obtains Polyamic Acid Film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, from room temperature with 5 DEG C/min
Heating rate rise to 300 DEG C, keep 1h to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 100 DEG C are risen to from 50 DEG C of heating rates with 2 DEG C/min, is protected
3h is held, then rises to 150 DEG C with the heating rate of 2 DEG C/min, 3h is kept, then rise to 260 DEG C with the heating rate of 2 DEG C/min, protects
1h is held, then rises to 300 DEG C with the heating rate of 2 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.40, and glass transition temperature is 359 DEG C, tensile strength 112.3MPa, elongation at break 5.88%.
Embodiment 12
(I-5) 17.722g (0.05mol) is added to 150ml N, in N '-dimethylacetamide solution, stirring and dissolving
Afterwards, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 32.22g (0.1mol) are added, after reaction for 24 hours is stirred at room temperature, obtain polyamides
Amino acid solution is subsequently added into (III-13) 9.988g that average molecular weight is 1000, and ultrasonic disperse is uniform, obtains mixing molten
Liquid by mixed solution curtain coating on matrix, and is 12% in humidity, solidifies 10h at 80 DEG C of temperature, it is thin to obtain polyamic acid
Film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, rises to 300 from room temperature with the heating rate of 5 DEG C/min
DEG C, keep 1h to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 250 DEG C are risen to from room temperature with the heating rate of 3 DEG C/min, is protected
2h is held, then rises to 300 DEG C with the heating rate of 3 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.25, and glass transition temperature is 339 DEG C, tensile strength 89.8MPa, elongation at break 6.57%.
Embodiment 13
(I-6) 63.824g (0.1mol) is added to 700ml N, in N '-dimethylacetamide solution, after stirring and dissolving,
Bis- (trifluoromethyl) the xanthene dianhydride 45.82g (0.1mol) of 2,3,6,7- tetracarboxylics -9,9- are added, reaction is stirred at room temperature for 24 hours
Afterwards, polyamic acid solution is obtained, is subsequently added into (III-14) 21.93g that average molecular weight is 1000, and ultrasonic disperse is uniform,
Obtain mixed solution.By mixed solution curtain coating on matrix, and it is 20% in humidity, solidifies 12h under temperature 60 C, obtain
Polyamic Acid Film.Polyamic Acid Film is placed in the heating device under condition of nitrogen gas, from room temperature with the heating speed of 1 DEG C/min
Rate rises to 290 DEG C, and 1h is kept to obtain Kapton.
By above-mentioned Kapton under air atmosphere, 100 DEG C are risen to from 50 DEG C of heating rates with 1 DEG C/min, is protected
3h is held, then rises to 150 DEG C with the heating rate of 1 DEG C/min, 3h is kept, then rise to 260 DEG C with the heating rate of 1 DEG C/min, protects
1h is held, then rises to 300 DEG C with the heating rate of 1 DEG C/min, 2h is kept, obtains polyimide nano foam.After tested, dielectric
Constant is 2.15, and glass transition temperature is 312 DEG C, tensile strength 105.3MPa, elongation at break 7.93%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of polyimide nano foam, which is characterized in that include the following steps：
A) diamine compound of the group containing adamantane, the diamine compound without adamantane group and two compound anhydrides are existed
Polymerization reaction is carried out in solvent, obtains polyamic acid solution；
B successively by evenly dispersed, curtain coating, solidification and heat after) heat-labile compound is mixed with the polyamic acid solution
Imidization obtains Kapton；
C the Kapton) is obtained into polyimide nano foam by thermally decomposing；
The heat-labile compound is selected from one of compound below with formula (III-10)~formula (III-14) structure
Or it is a variety of：
Wherein, the number-average molecular weight of the heat-labile compound is 500~5000.
2. a kind of preparation method of polyimide nano foam, which is characterized in that include the following steps：
A) by the diamine compound of the group containing adamantane, the diamine compound without adamantane group, two compound anhydrides and
Heat-labile compound carries out polymerization reaction in a solvent, obtains polyamic acid solution；
B) polyamic acid solution is obtained into Kapton successively by curtain coating, solidification and hot imidization；
C) Kapton obtains polyimide nano foam by thermal decomposition；
The heat-labile compound be selected from one of compound with formula (III-1)~formula (III-9) structure below or
It is a variety of：
Wherein, the number-average molecular weight of the heat-labile compound is 500~5000.
3. preparation method according to claim 1 or 2, which is characterized in that the diamine compound of the group containing adamantane
Selected from one of compound below with formula (I-1)~formula (I-7) structure or a variety of：
4. preparation method according to claim 1 or 2, which is characterized in that two amine compounds without adamantane group
Object is selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-diamino hexichol first
Alkane, 4,4 '-diaminobenzophenones, 4,4 '--3,3 '-dimethyl diphenyls of diamino, 4,4' diaminodiphenyl sulfone, 2- (4- ammonia
Base phenyl) -5- aminopyrimidine, 2,2 '-two (trifluoromethyl) -4,4 '-benzidines, 2,5- bis- (4- aminophenyl) pyrimidine,
2,5- bis- (4- aminophenyl) pyridine, 2- (4- aminophenyl) one of -5- aminopyridine and 2,6- diamino-pyridine or more
Kind.
5. preparation method according to claim 1 or 2, which is characterized in that two compound anhydride is selected to be had below
One of formula (II-1)~formula (II-5) structure compound is a variety of：
Wherein, A be selected from S, O,
6. preparation method according to claim 1 or 2, which is characterized in that the additional amount of the heat-labile compound accounts for
Diamine compound, the diamine compound without adamantane group and the two compound anhydride gross masses of the group containing adamantane
3wt%~30wt%, the solid content of the polyamic acid solution is 9wt%~40wt%.
7. preparation method according to claim 1 or 2, which is characterized in that the cured humidity is described solid less than 30%
The temperature of change be 50~150 DEG C, the cured time be 10~for 24 hours；The hot imidization carries out under atmosphere of inert gases,
The temperature of the hot imidization is 280~350 DEG C, and the time of the hot imidization is 20min~60min；
The thermal decomposition process is：Under air atmosphere, with the heating rate of 1~10 DEG C/min from 20~50 DEG C of ladder-elevating temperatures to
250~350 DEG C, and keep 1~10h.
8. a kind of polyimide nano foam that the preparation method as described in claim 1~7 any one is prepared.
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| CN107189436B (en) * | 2017-07-20 | 2019-12-27 | 中国科学院长春应用化学研究所 | Polyimide nano foam and preparation method thereof |
| WO2020150886A1 (en) * | 2019-01-22 | 2020-07-30 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite separator, and lithium-ion battery |
| CN110078920B (en) * | 2019-04-30 | 2022-03-15 | 京东方科技集团股份有限公司 | Modified polyimide, preparation method of alignment film and display device |
| CN113429601B (en) * | 2021-06-21 | 2023-03-31 | 浙江中科玖源新材料有限公司 | Preparation method of high-barrier polyimide film |
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