CN106750426A - High fire-retardance soluble type Kapton and preparation method thereof - Google Patents
High fire-retardance soluble type Kapton and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a kind of high fire-retardance soluble type Kapton and preparation method thereof, the preparation method comprises the following steps：1) by double (4 aminophenyls) 9, the phosphoryl ethane of 10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene 10 and 2 (3 aminophenyl) 5 aminobenzimidazoles are dissolved in polar solvent, are stirred to being completely dissolved, and obtain mixed solution；2) to aromatic dianhydride is added in mixed solution, maintenance reaction system temperature obtains polyamic acid glue after reacting completely；3) polyamic acid glue is uniformly coated on flat plate mold, through temperature programming hot imidization, treats that heating schedule is finished, be cooled to room temperature rear demoulding, obtain final product high fire-retardance soluble type Kapton.In high fire-retardance soluble type Kapton of the invention the organic-dissolvable of polymer is improved by introducing the phosphorus-containing groups containing large volume, also by introducing rigid benzimidazole group, interaction of hydrogen bond is formd between strand, so as to keep the good hot property of polyimides.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of high fire-retardance soluble type Kapton and its
Preparation method.
Background technology
Polyimides (PI) is the high-molecular organic material containing imide ring in molecule structure.Rigid acid imide
Ring imparts the excellent combination property of this kind of material, such as fabulous heat endurance, and excellent mechanical performance, prominent is chemical and anti-
Radiativity, excellent dielectric properties etc..Due to its unique performance, polyimides is paid attention to by height, and is used extensively
Make insulating materials, waveguide material, high modulus fiber, selectivity through film and high-temperature composite material etc., be related to Aero-Space, chemistry
The multiple fields such as chemical industry, electrical equipment, microelectronics.In recent years, polyimides has been studied personnel and has been considered following most promising one
In 21 century most promising engineering plastics are all being listed the research of polyimides, exploitation and utilization by kind polymeric material, each state
One of.
However, phenyl ring and imide ring structure are typically contained on polyimide molecule main chain, due to electronic polarization and crystallization
Property cause polyimides exist stronger molecule inter-chain action, cause polyimide molecule chain tightly packed, so as to cause polyamides
Imines is primarily present following shortcoming：(1) most of traditional polyimides are difficult to because of indissoluble or not dissolving in usual vehicle, because
This polyimides is generally synthesized using two-step method：The first step is that dianhydride and diamines are formed in aprotic, polar transfer reaction solvent
Polyamic acid (PAA)；Second step is hot PAA imidizates to polyimides.(2) traditional polyimides is due to rigid chain spy
Levy, with melt temperature higher, be difficult to shape, this causes extreme difficulties to production application；(3) traditional polyamides is sub-
General hard, the crisp, insufficient strength of film that amine is made, being remained for microelectronics industry is reducing linear expansion coefficient with mechanical strength hardly possible
With the defect taken into account；(4) because the formation of intramolecular and intermolecular charge transfer compound (CTC) and electronic polarization cause tradition
PI films be in often yellow or dark-brown, it is impossible to meet optical waveguide material in communication field, the alignment films of liquid crystal display,
The requirement to the PI Film Optics field transparency such as flexible and transparent conductive substrate.
At the same time, due to expensive raw material price so that the preparation cost of polyimides can be in any more always.In view of polyamides
The disadvantages mentioned above of imines, the modified next performance requirement for constantly adapting to new product of Study on Polyimide molecular structure is necessary
's.
The content of the invention
Present invention aim to provide a kind of high fire-retardance soluble type Kapton and preparation method thereof, the high resistant
The organic-dissolvable of polymer is improved by introducing the phosphorus-containing groups containing large volume in combustion soluble type Kapton, with
And the ability of metal is adhered to, such that it is able to strengthen polyimides organic-dissolvable and anti-flammability；By introducing rigid benzo
Imidazole group, forms interaction of hydrogen bond between strand, so as to keep the good hot property of polyimides.
To achieve the above object, a kind of high fire-retardance soluble type Kapton provided by the present invention, its general structure
It is as follows：
In formula, Ar isIn one kind；m:n
=1:4, wherein m are that n is the integer in 4~16 in 1~4.
Further, the glass transition temperature of the high fire-retardance soluble type Kapton is 354.22~375.27
℃。
Further, the limited oxygen index of the high fire-retardance soluble type transparent polyimide film is 47.5~50.1.
Further, the tensile strength of the high fire-retardance soluble type transparent polyimide film is 99.21~130.07MPa,
Stretch modulus is 2.08~3.19GPa.
The preparation method of high fire-retardance soluble type Kapton of the present invention, comprises the following steps：
1) will double miscellaneous -10- phospho hetero phenanthrenes -10- phosphoryls ethane of (4- aminophenyls) -9,10- dihydro-9-oxies and 2- (3- ammonia
Base phenyl) -5- aminobenzimidazoles are dissolved in polar solvent, are stirred to being completely dissolved, and obtain mixed solution；
2) to aromatic dianhydride is added in mixed solution, maintenance reaction system temperature obtains polyamic acid after reacting completely
Glue；
3) polyamic acid glue is uniformly coated on flat plate mold, through temperature programming hot imidization, treats that heating schedule is complete
Finish, be cooled to room temperature rear demoulding, obtain final product high fire-retardance soluble type Kapton.
Further, in the step 1) in, double miscellaneous -10- phospho hetero phenanthrenes -10- of (4- aminophenyls) -9,10- dihydro-9-oxies
The ratio between molal quantity of phosphoryl ethane and 2- (3- aminophenyls) -5- aminobenzimidazoles is 1:4.
Further, in the step 1) in, polar solvent is N, N-dimethyl pyrrolidone or N, N- dimethylacetamide
Amine.
Further, in the step 1) in, the temperature of mixed solution is maintained 20~25 using heating water bath mode
Between DEG C.
Further, in the step 2) in, the aromatic dianhydride be 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 3,3',
4,4'- biphenyl tetracarboxylic dianhydrides, 3,3', the one kind in 4,4'- benzophenone tetracarboxylic dianhydrides.
Further, in the step 2) in, double (4- aminophenyls) -9,10- dihydro-9-oxies in the mixed solution
The total moles and aromatic dianhydride of miscellaneous -10- phospho hetero phenanthrenes -10- phosphoryls ethane and 2- (3- aminophenyls) -5- aminobenzimidazoles
The ratio between molal quantity be 1:1.
Yet further, in the step 2) in, between 20~25 DEG C, the reaction time is 10 to maintenance reaction system temperature
~15h.
Further, in the step 3) in, temperature programming is：Successively at 80 DEG C, 120 DEG C, 180 DEG C, 240 DEG C and
1~1.5h is maintained under 300 DEG C of temperature conditionss.
Compared with prior art, the invention has the advantages that：
First, the present invention is selecting fluoric dianhydride monomers 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids (6FDA), due to trifluoro
Methyl has larger volume and stronger electronegativity, can increase distance between polyimide molecule, and hinders the movement of electronics, favorably
In the formation for suppressing CTC, so as to improve thin-film transparent；From the 3,3' with the big biphenyl structural of rigidity, 4,4'- biphenyl four
Carboxylic acid dianhydride (BPDA), can strengthen the heat resistance of polyimides；From dianhydride 3,3', the 4,4'- benzophenone containing carbonyl
Tetracarboxylic acid dianhydride (BTDA), increased the compliance of polymer chain, have certain improvement to the mechanical property of film.
Second, miscellaneous -10- phosphines phenanthrene -10- phosphorus the ethane of double (4- aminophenyls) -9,10- dihydro-9-oxies in the present invention
(ADOPPE) it is a kind of phosphorous diamine monomer of new aromatic, introducing the phosphorus-containing groups containing large volume can improve polymer
Organic-dissolvable and anti-flammability；The cooperative flame retardant effect of phosphorus and nitrogen can well overcome lacking for phosphorus flame retardant presence
Fall into, increase its stability and heat resistance, further improve the fire resistance of polyimides.
Third, miscellaneous -10- phosphines phenanthrene -10- phosphorus the ethane of double (4- aminophenyls) -9,10- dihydro-9-oxies in the present invention
(ADOPPE) contain phosphine oxygen ring grease phenyl macoradical, prevent the accumulation of polymer chain, reduce intermolecular interaction, and
Increased fractional free volume so that PI dissolubilities are improved.
Fourth, the present invention can increase the dissolubility of polyimides using copolymerization process, and compared with homopolymerization PI, copolymerization PI tools
There is relatively low molecule regular, intermolecular force can be reduced, the dissolubility of copolymerization PI is so as to be strengthened.
Fifth, the present invention forms hydrogen bond phase interaction by introducing more multiple stiffness benzimidazolyl group between strand
With so as to keep the good hot property of polyimides.
Brief description of the drawings
Fig. 1 is the synthetic route chart of high fire-retardance soluble type Kapton of the present invention；
Fig. 2 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA, BPDA, BTDA
Synthesize thermogravimetric analysis (TGA) curve map of PI for dianhydride monomer；
Fig. 3 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA, BPDA, BTDA
Synthesize thermo-mechanical analysis (TMA) curve map of PI for dianhydride monomer；
Fig. 4 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA, BPDA, BTDA
Synthesize the ultraviolet-visible spectrogram of PI for dianhydride monomer.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
1) glass apparatus that will be used in experiment all cleans up rear drying for standby, equipped with mechanical agitation bar, nitrogen
Double (4- the aminophenyls) -9,10- dihydros -9- of 0.5117g (1.2mmol) are first added in the 100mL there-necked flasks of gas shielded device
Oxa- -10- phospho hetero phenanthrenes -10- phosphoryls ethane (ADOPPE) and 1.0764g (4.8mmol) 2- (3- aminophenyls) -5- aminobenzenes
And imidazoles (i-DAPBI), be subsequently adding 17.0140g N, N- dimethyl pyrrolidones (NMP), stirred under room temperature condition to
ADOPPE and i-DAPBI all dissolves；
2) it is to be dissolved to finish, to rapidly joining 2.6654g (6mmol) 4,4'- (hexafluoro isopropyl alkene) two phthaleins in there-necked flask
Acid anhydrides (6FDA), total solid content be 20% (total solid content for ADOPPE, i-DAPBI and 6FDA weight sum, compared to
The weight sum of ADOPPE, i-DAPBI, 6FDA and NMP)；After charging is finished, temperature of reaction system is maintained 20 using water-bath
Between~25 DEG C and 12h is reacted, obtain brown color polyamic acid glue；
3) brown color polyamic acid glue is uniformly coated on clean glass plate by film instrument, then glass plate is put
In baking oven, through temperature programming hot imidization, treat that heating schedule is finished, naturally cool to room temperature, it is de- with hot-water soak glass plate
Film obtains high fire-retardance soluble type Kapton (obtaining PI-1 films), and the temperature and time of temperature programming is：80℃、
120 DEG C, 180 DEG C, 240 DEG C and 300 DEG C each maintenance 1h.
Embodiment 2
1) glass apparatus that will be used in experiment all cleans up rear drying for standby, equipped with mechanical agitation bar, nitrogen
Double (4- the aminophenyls) -9,10- dihydros -9- of 0.5117g (1.2mmol) are first added in the 100mL there-necked flasks of gas shielded device
Oxa- -10- phospho hetero phenanthrenes -10- phosphoryls ethane (ADOPPE) and 1.0764g (4.8mmol) 2- (3- aminophenyls) -5- aminobenzenes
And imidazoles (i-DAPBI), be subsequently adding 13.4136g DMAs (DMAc) solvent, stirred under room temperature condition to
ADOPPE and i-DAPBI all dissolves；
2) it is to be dissolved to finish, to rapidly joining the biphenyltetracarboxyacid acids two of 1.7653g (6mmol) 3,3', 4,4'- in there-necked flask
Acid anhydride (BPDA), total solid content be 20% (total solid content for ADOPPE, i-DAPBI and BPDA weight sum, compared to
The weight sum of ADOPPE, i-DAPBI, BPDA and DMAc)；After charging is finished, temperature of reaction system is maintained using water-bath
Between 20~25 DEG C and 12h is reacted, obtain yellow polyamic acid glue；
3) yellow polyamic acid glue is uniformly coated on clean glass plate by film instrument, then glass plate is placed in
In baking oven, through temperature programming hot imidization, treat that heating schedule is finished, naturally cool to room temperature, with hot-water soak glass plate demoulding
High fire-retardance soluble type Kapton (obtaining PI-2 films) is obtained, the temperature and time of temperature programming is：80℃、120
DEG C, 180 DEG C, 240 DEG C and 300 DEG C are each maintains 1.5h.
Embodiment 3
1) glass apparatus that will be used in experiment all cleans up rear drying for standby, equipped with mechanical agitation bar, nitrogen
Double (4- the aminophenyls) -9,10- dihydros -9- of 0.5117g (1.2mmol) are first added in the 100mL there-necked flasks of gas shielded device
Oxa- -10- phospho hetero phenanthrenes -10- phosphoryls ethane (ADOPPE) and 1.0764g (4.8mmol) 2- (3- aminophenyls) -5- aminobenzenes
And imidazoles (i-DAPBI), be subsequently adding 14.0856g DMAs (DMAc) solvent, stirred under room temperature condition to
ADOPPE and i-DAPBI all dissolves；
2) it is to be dissolved to finish, to rapidly joining the benzophenone tetramethyls of 1.9333g (6mmol) 3,3', 4,4'- in there-necked flask
Acid dianhydride (BTDA), total solid content be 20% (total solid content for ADOPPE, i-DAPBI and BTDA weight sum, compared to
The weight sum of ADOPPE, i-DAPBI, BTDA and DMAc)；After charging is finished, temperature of reaction system is maintained using water-bath
Between 20~25 DEG C and 12h is reacted, obtain light yellow polyamic acid glue；
3) light yellow polyamic acid glue is uniformly coated on clean glass plate by film instrument, then glass plate is put
In baking oven, through temperature programming hot imidization, treat that heating schedule is finished, naturally cool to room temperature, it is de- with hot-water soak glass plate
Film obtains high fire-retardance soluble type Kapton (obtaining PI-3 films), and the temperature and time of temperature programming is：80℃、
120 DEG C, 180 DEG C, 240 DEG C and 300 DEG C each maintenance 1h.
Effect example：
Performance measurement is carried out to PI films prepared by 1~embodiment of embodiment 3.
Effect example 1：Deliquescent measure
Taken in sample prepared by 1~embodiment of embodiment 3 in a certain amount of PI samples addition correspondence solvent, stand 24h,
Observe its dissolving situation.Table 1 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA,
BPDA, BTDA are the dissolubility result that dianhydride monomer synthesizes PI films.
The dissolubility of the PI films of table 1
++：Room temperature is solvable；+：Heating is solvable；+：Heating part is molten；-：Heating is insoluble
NMP：N, N-dimethyl pyrrolidone；DMF：N,N-dimethylformamide；DMAc：DMAC N,N' dimethyl acetamide；
CHCl3：Chloroform；Acetone:Acetone
As shown in table 1, the series polyimide is respectively provided with good dissolubility, and phosphine oxygen ring is contained mainly due to ADOPPE
Alphyl macoradical, prevents the accumulation of polymer chain, reduces intermolecular interaction, and increased free body integration
Number so that PI dissolubilities are improved.In addition, the dissolubility of polyimides can be increased using copolymerization process, with homopolymerization PI phases
Than copolymerization PI has relatively low molecule regular, can reduce intermolecular force, and the dissolubility of copolymerization PI is so as to be increased
By force.
Effect example 2：The measure of hot property
The heat endurance of PI samples is tested using TG thermogravimetric analyzers, in a nitrogen atmosphere, heating rate is 20 DEG C/min
Under conditions of test；Using TMA thermomechanical analyzers in a nitrogen atmosphere, heating rate be 10 DEG C/min under conditions of determine PI
Glass transition temperature.
Fig. 2 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA, BPDA, BTDA
Synthesize thermal weight loss (TGA) curve of PI for dianhydride monomer, Fig. 3 is the thermo-mechanical analysis that 1~embodiment of embodiment 3 synthesizes PI
(TMA) curve, table 2 is the thermal weight loss data of synthesis PI.
The hot property of the PI films of table 2
Data are found out from Fig. 2 and table 2, and 3 groups of synthesized polyimides are respectively provided with excellent heat resistance, wherein PI-1
The heat resistance of (embodiment 1) is best, because the trifluoromethyl that 6FDA has large volume will not destroy polyimide molecule chain
Rigidity；The heat resistance of PI-3 (embodiment 3) is relatively low, because BTDA contains carbonyl flexible group, increased the submissive of strand
Property.Under nitrogen atmosphere, 5% thermal weight loss temperature of the series polyimide film between 406.9 to 480.2 DEG C, lose by 10% heat
Between 433.8 to 508.7 DEG C, this is, because ADOPPE contains a phosphine oxygen ring grease phenyl macoradical structure, to reduce to degree of reviewing
The regularity and crystallizing power of PI strands so that the heat decomposition temperature of polymer is relatively low.Residual mass at 700 DEG C still exists
Between 50.49% to 59.27%, illustrating the PI films of synthesis has fabulous oxidation resistance.
Can be obtained by TMA tests, in ADOPPE molecular structures, methyl and biphenyl phosphine are perfectly asymmetric so that polymerization
Thing chain is difficult rotation, so 3 groups of synthesized glass transition temperature Tgs of polyimides are very high.Wherein because PI-1 is (real
Applying example 1) the middle 6FDA for introducing contains large volume trifluoromethyl and the BPDA of PI-2 (embodiment 2) introducings contains the big biphenyl of rigidity
Structure, so its glass transition temperature is higher, and BTDA increased the submissive of polymer chain because of the presence of carbonyl flexible group
Property, reduce the glass transition temperature of PI-3 (embodiment 3).
Effect example 3：The measure of ultraviolet-visible spectrum
The transmitance of PI films is measured using ultraviolet-visible photometer, sweep limits is 200~800nm.
Fig. 4 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA, BPDA, BTDA
Synthesize the ultraviolet-visible spectrogram of PI for dianhydride monomer.
Figure 4, it is seen that the ultraviolet cut-on wavelength of Series P I films is in 400nm or so, maximum transmission rate is equal
More than 85%, showing the PI films of synthesis has preferable optical transparence.Wherein, the ultraviolet cut-on wavelength of PI-1 (embodiment 1)
Minimum, the trifluoromethyl being primarily due in the dianhydride monomer 6FDA for using has larger volume and stronger electronegativity, can increase
Addition polymerization acid imide intermolecular distance, and the movement of electronics is hindered, be conducive to suppressing the formation of CTC, so as to improve thin-film transparent.
In addition, in BTDA flexible carbonyl presence, also have certain improvement result to the transparency of film.
Effect example 4：The measure of limited oxygen index
PI films are made the sample strip of 120mm × 100mm, operating limit oxygen index measurer presses testing standard GB/
The limited oxygen index of T2406.2-2009 determination samples, adjusts gas flowmeter, and oxygen concentration when record sample extinguishes is the limit
Oxygen index (OI).
Table 3 be 1~embodiment of embodiment 3 with ADOPPE, i-DAPBI as diamine monomer, respectively with 6FDA, BPDA, BTDA
Synthesize the limited oxygen index of PI films for dianhydride monomer.
The limited oxygen index (LOI) of the PI films of table 3
From result in table 3, synthesized PI films have LOI values very high, between 47.5 to 50.1, illustrate that this is
Row PI films are respectively provided with high flame retardant, introduce ADOPPE monomers, and the phosphorus-containing groups of large volume are conducive to improving the fire-retardant of polymer
Performance.In addition, the cooperative flame retardant effect of phosphorus and nitrogen can well overcome the defect that phosphorus flame retardant is present, it is increased
Stability and heat resistance, further improve the fire resistance of polyimides.
Effect example 4：The measure of mechanical property
PI films are made the sample strip of 80mm × 20mm, are marked by test using CMT6503 electronic universal material testing machines
The mechanical property of quasi- GB13022-91 determination samples, rate of extension is 50mm/min, and sample gauge length is 50mm.
The mechanical property of the PI films of table 4
PI films to the synthesis of embodiment 1,2,3 carry out Mechanics Performance Testing, as shown in table 4, the tensile strength of PI films
Respectively 130.07,99.21,119.41MPa, stretch modulus is respectively 3.19,2.08,2.56GPa, generally, synthesis it is thin
Film is presented excellent mechanical property.The flexible carbonyl in trifluoromethyl, BTDA molecular structures in 6FDA molecular structures is one
Determine to be enhanced in degree the mechanical property of PI films.
In sum, polyimides (PI) film of present invention production is significantly improved in performance, especially fire-retardant
Property, dissolubility, heat resistance aspect.
The above, specific embodiment only of the invention, it is noted that any those of ordinary skill in the art exist
Disclosed herein technical scope in, the change or replacement that can be readily occurred in, should all cover protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of high fire-retardance soluble type Kapton, it is characterised in that its general structure is as follows：
In formula, Ar isIn one kind；m:N=1:
4, wherein m are the integer in 1~4, and n is the integer in 4~16.
2. high fire-retardance soluble type Kapton according to claim 1, it is characterised in that the high fire-retardance soluble type
The limited oxygen index of transparent polyimide film is 47.5~50.1.
3. a kind of preparation method of the high fire-retardance soluble type Kapton described in claim 1 or 2, it is characterised in that bag
Include following steps：
1) will double miscellaneous -10- phospho hetero phenanthrenes -10- phosphoryls ethane of (4- aminophenyls) -9,10- dihydro-9-oxies and 2- (3- aminobenzenes
Base) -5- aminobenzimidazoles are dissolved in polar solvent, are stirred to being completely dissolved, and obtain mixed solution；
2) to aromatic dianhydride is added in mixed solution, maintenance reaction system temperature obtains polyamic acid glue after reacting completely；
3) polyamic acid glue is uniformly coated on flat plate mold, through temperature programming hot imidization, treats that heating schedule is finished, it is cold
But to room temperature rear demoulding, high fire-retardance soluble type Kapton is obtained final product.
4. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that described
Step 1) in, double miscellaneous -10- phospho hetero phenanthrenes -10- phosphoryls ethane of (4- aminophenyls) -9,10- dihydro-9-oxies and 2- (3- aminobenzenes
Base) the ratio between the molal quantity of -5- aminobenzimidazoles is 1:4.
5. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that described
Step 1) in, polar solvent is N, N-dimethyl pyrrolidone or DMA.
6. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that described
Step 1) in, the temperature of mixed solution is maintained between 20~25 DEG C using heating water bath mode.
7. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that described
Step 2) in, the aromatic dianhydride be 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides, 3,
One kind in 3', 4,4'- benzophenone tetracarboxylic dianhydride.
8. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that described
Step 2) in, the miscellaneous -10- phospho hetero phenanthrenes -10- phosphoryl second of double (4- aminophenyls) -9,10- dihydro-9-oxies in the mixed solution
The ratio between the total moles of alkane and 2- (3- aminophenyls) -5- aminobenzimidazoles and the molal quantity of aromatic dianhydride are 1:1.
9. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that described
Step 2) in, between 20~25 DEG C, the reaction time is 10~15h to maintenance reaction system temperature.
10. the preparation method of high fire-retardance soluble type Kapton according to claim 3, it is characterised in that in institute
State step 3) in, temperature programming is：Successively under 80 DEG C, 120 DEG C, 180 DEG C, 240 DEG C and 300 DEG C of temperature conditionss maintain 1~
1.5h。
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| CN110655472A (en) * | 2019-10-10 | 2020-01-07 | 中国科学院深圳先进技术研究院 | Diamine monomer with bulky side group and preparation method and application thereof |
| CN111319332A (en) * | 2020-04-13 | 2020-06-23 | 安徽松泰包装材料有限公司 | Multilayer composite film |
| CN112708132A (en) * | 2020-11-30 | 2021-04-27 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film containing benzimidazole structure and preparation method thereof |
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