CN107141796A - A kind of nano modification polyimides and its preparation system and preparation method - Google Patents
A kind of nano modification polyimides and its preparation system and preparation method Download PDFInfo
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- 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
- C08L79/085—Unsaturated polyimide precursors
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- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
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- 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
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- 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
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- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2241—Titanium dioxide
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention proposes a kind of nano modification polyimides and its preparation system and method, including solution preparation system and film preparing system, the solution preparation system includes reactor, include being respectively communicated with dianhydride solvent tank and diamines solvent tank on two inlets, the inlet on the reactor；The film preparing system includes imidization stove, winder, filming-drawing mechanism, and the froth breaking tank is connected with the filming-drawing mechanism by salivating mouth, and wherein preparation method comprises the following steps：Prepared by polyimide solution and prepared by Kapton, the present invention is by several times added to solid dianhydride in the polar solvent of diamines, substantial amounts of two amine molecule is set to attack the surface of suspension dianhydride, it is rapid to occur polymerisation, so avoid dianhydride and proportioning with diamines is destroyed because of the consumption with solvent complex, generate high concentration and stable PAA solution；The Kapton parameter prepared using the system is qualified, and final product quality is superior.
Description
Technical field
The present invention relates to field of new materials, more particularly to nano modification polyimides and its preparation system and preparation method.
Background technology
Polyimide film has high-fire resistance, high electrical insulating properties, even if being film layer, can also meet required when using
Rigidity, heat resistance or electrical insulating property.Therefore, polyimide film is widely used in electrical insulating film, barrier film heat, flexible circuit board
The industrial circles such as basilar memebrane.In addition, polyimide film is also used for solar cell substrate etc. successively in recent years.
In the prior art, in the preparation process of polyimides, because dianhydride and polar solvent have strong complexing, shadow
The reactivity of dianhydride, and the presence of the minor amount of water in solvent are rung, is allowed to form micro Pyromellitic Acid, inhibition is played and makees
With, and make molecular weight very little, and the assurance of some machined parameters is bad, causes obtained Kapton parameter unqualified.
The content of the invention
In order to solve the above technical problems, the present invention proposes a kind of nano modification polyimides, including following components：Polyamides
10-15 parts of imines, 5-10 parts of tetracarboxylic anhydride, 6-11 parts of diamines, 3-5 parts of end-capping reagent, 5-10 parts of titanium dioxide and barium monoxide 6- partially
25 parts.
It is preferred that, the tetracarboxylic anhydride includes benzophenone tetracarboxylic anhydride or benzophenone tetrabasic carboxylic acid dimethyl ester or benzophenone tetrabasic carboxylic acid diethyl
Ester.
It is preferred that, the diamines includes p-phenylenediamine, 4,4 '-oxydianiline.
A kind of polyimides preparation system, including solution preparation system and film preparing system, the solution preparation system
Include being respectively communicated with dianhydride solvent tank and diamines on two inlets, the inlet including reactor, on the reactor
Solvent tank, is connected to high-order measuring tank between the dianhydride solvent tank and diamines solvent tank and the inlet, described anti-
Answer kettle output end to be connected with froth breaking tank, filter is connected between the froth breaking tank and the reactor；The film preparation system
System includes imidization stove, winder, filming-drawing mechanism, and the froth breaking tank is connected with the filming-drawing mechanism by salivating mouth.
It is preferred that, the filming-drawing mechanism includes casing, is provided with front roller and rear transfer roller in the casing, the front roller and
Afterwards between transfer roller provided with being cased with steel band, the corresponding casing of the steel band is provided with air inlet and air outlet.
A kind of polyimides preparation method of said system, comprises the following steps：Polyimide solution is prepared and polyamides
Imines film preparation；
S1：In polar solvent, PMDA is taken gradually to be added in batches in dimethyl acetamide, in normal temperature and pressure
Lower reaction, at least three times additions of the PMDA point, generates high-molecular-weight poly phthalein amino acid solution, and add titanium dioxide
With inclined barium monoxide；
S2：The solid-state PAA films for removing solvent are dried, slow continuous in vacuum or inert media or ladder step is warming up to height
It is heat-treated in 300 DEG C；
Reaction equation is：
It is preferred that, the ratio of PMDA and the biphenyl ether diamine is 1.020~1.030 ﹕ 1.
It is preferred that, the polar solvent includes dimethyl methyl phthalein amine or dimethyl acetamide or N- methyl adjoins pyrrolidone or adjoined
Smack one's lips or dimethyl sulfoxide (DMSO).
It is preferred that, in S2, polyamic acid (PAA) solution after froth breaking, before stainless steel solution reservoir is pressed into by the road
In salivation mouth storage tank on head；Steel band travels at the uniform speed, and the solution in storage tank is taken away through salivating mouth front scrapping plate, and forms thickness
Dry in uniform liquid film, the rear drying road that enters；The air of clean dried is preheating to after certain temperature by air blower feeding heater
Into upper and lower drying road；
Hot wind flow direction with steel band traffic direction on the contrary, so as to make liquid film dry when temperature gradually rise, solvent by
Gradually volatilize, increase drying effect.
Polyamic Acid Film is operated therewith one week on steel band, and solvent evaporation turns into solid film, under being peeled off from steel band
Film guide imidization stove into through guide roller.
It is preferred that, imidization stove is multiple roll cartridge form, and Polyamic Acid Film is guided with the guide roller of slobbering machine synchronizing speed
Into imidization stove, after high temperature imidization, Kapton is wound by winder.
Polyimides preparation system proposed by the present invention and preparation method thereof has following beneficial effect：1st, solid dianhydride point
It is secondary to be added in the polar solvent of diamines, substantial amounts of two amine molecule is attacked the surface of suspension dianhydride, polymerisation occurs rapidly, this
Sample avoids dianhydride and proportioning with diamines is destroyed because of the consumption with solvent complex, generates high concentration and stable PAA solution；
2nd, the polyimide material prepared using the system adds titanium dioxide and inclined barium monoxide, considerably increases polyimide material
Proof voltage, wearability and high temperature resistant degree；3rd, in this process preparation process, PAA viscosity is greatly reduced, and
Preparation method is convenient.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described.
Fig. 1 is structural representation of the invention；
Wherein, 1- solution preparation system, 2- film preparing systems, 3- reactors, 4- dianhydride solvent tanks, the amine solvents of 5- bis-
Tank, 6- high position measuring tanks, 7- froth breaking tanks, 8- filters, 9- imidization stoves, 10- winders, 11- filming-drawing mechanisms, 12- front rollers,
Transfer roller after 13-, 14- steel bands, 15- air inlets, 16- air outlets, 17- salivation mouths.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described.
As shown in figure 1, the present invention proposes a kind of polyimides preparation system, including solution preparation system 1 and film system
Standby system 2, the solution preparation system 1 includes including on two inlets, the inlet on reactor 3, the reactor 3
Be respectively communicated with dianhydride solvent tank 4 and diamines solvent tank 5, the dianhydride solvent tank 4 and diamines solvent tank 5 and the inlet it
Between be connected to high-order measuring tank 6, the output end of reactor 3 is connected with froth breaking tank 7, the froth breaking tank 7 and the reaction
Filter 8 is connected between kettle 3；
Influence of the preparation technology parameter to PAA molecular weight
1st, temperature：At 15~20 DEG C, temperature HMW is low；
2nd, match：The ﹕ 1 of Er Gan ﹕ diamines=1.020~1.030；
3rd, feed order：Acid anhydride is added in the solution of amine；
4th, water content：Dianhydride, diamines and solvent must purify to exclude water in advance；
5th, solvent species：Influence PAA viscositys, dimethyl sulfoxide (DMSO) ＞ DMAC ＞ DMF.
The film preparing system 2 include imidization stove 9, winder 10, filming-drawing mechanism 11, the froth breaking tank 7 with it is described
Filming-drawing mechanism 11 is connected by salivating mouth 17, and the filming-drawing mechanism 11 is included in casing, the casing provided with front roller 12 with after
Transfer roller 13, provided with being cased with steel band 14 between the front roller 12 and rear transfer roller 13, the corresponding casing of the steel band 14 be provided with into
Polyamic acid (PAA) solution after air port 15 and air outlet 16, froth breaking, is pressed on preceding head by the road by stainless steel solution reservoir
The storage tank of salivation mouth 17 in.Steel band 14 is traveled at the uniform speed with scheming shown direction, by the solution in storage tank through salivating the front scrapping plate band of mouth 17
Walk, and form liquid film in uniform thickness, dried subsequently into drying road.It is pre- that the air of clean dried sends into heater by air blower
Heat is to entering upper and lower drying road after certain temperature.
Hot wind flow direction with the traffic direction of steel band 14 on the contrary, so as to make liquid film dry when temperature gradually rise, solvent
Gradually volatilize, increase drying effect.
Polyamic Acid Film is operated therewith one week on steel band 14, and solvent evaporation turns into solid film, is shelled from steel band 14
Film under guides imidization stove 9 into through guide roller.
Imidization stove 9 is generally multiple roll cartridge form, enters with the guide roller guiding Polyamic Acid Film of slobbering machine synchronizing speed
Enter imidization stove 9, after high temperature imidization, Kapton is wound by winder 10.
Technological parameter
1st, film thickness is regularly determined apart from solids content one between the salivation front scrapping plate of mouth 17 and steel band 14.
2nd, PAA solids contents about 20wt%
3rd, to coordinate between temperature, speed, air quantity
Temperature is low to easily cause the phenomenon of steel bonding band 14, peels off difficulty, temperature is high to take off band again.Speed is beneficial to improve production effect soon
Rate.Speed is by drying road length and the film road length limitation of imidization stove 9.Air quantity determines solvent steam concentration.Early stage dries temperature
When spending low, air quantity is preferably small,
When later stage drying temperature is high, air quantity is preferably big.
A kind of polyimides preparation method of said system, comprises the following steps：Polyimide solution is prepared and polyamides
Imines film preparation；
S1：In polar solvent, PMDA is taken gradually to be added in batches in dimethyl acetamide, in normal temperature and pressure
Lower reaction, at least three times additions of the PMDA point, generates high-molecular-weight poly phthalein amino acid solution, and add titanium dioxide
With inclined barium monoxide；
S2：The solid-state PAA films for removing solvent are dried, slow continuous in vacuum or inert media or ladder step is warming up to height
It is heat-treated in 300 DEG C；
Reaction equation is：
It is preferred that, the ratio of PMDA and the biphenyl ether diamine is 1.020~1.030 ﹕ 1.
It is preferred that, the polar solvent includes dimethyl methyl phthalein amine or dimethyl acetamide or N- methyl adjoins pyrrolidone or adjoined
Smack one's lips or dimethyl sulfoxide (DMSO).
It is preferred that, in S2, polyamic acid (PAA) solution after froth breaking, before stainless steel solution reservoir is pressed into by the road
In the storage tank of salivation mouth 17 on head；Steel band 14 travels at the uniform speed, and the solution in storage tank is taken away through salivating the front scrapping plate of mouth 17, and shape
Into liquid film in uniform thickness, the rear drying road that enters is dried；The air of clean dried is preheating to necessarily by air blower feeding heater
Enter upper and lower drying road after temperature；
Hot wind flow direction with the traffic direction of steel band 14 on the contrary, so as to make liquid film dry when temperature gradually rise, solvent
Gradually volatilize, increase drying effect.
Polyamic Acid Film is operated therewith one week on steel band 14, and solvent evaporation turns into solid film, is shelled from steel band 14
Film under guides imidization stove 9 into through guide roller.
It is preferred that, imidization stove 9 is multiple roll cartridge form, and Polyamic Acid Film is guided with the guide roller of slobbering machine synchronizing speed
Into imidization stove 9, after high temperature imidization, Kapton is wound by winder 10.
Following parameter detecting is carried out using film made from the above method：
Tensile strength, elongation at break, power frequency electrical strength, surface resistivity, specific insulation etc. are tested.
With the increase of draw ratio, the tensile strength and modulus of polyimides have increase, when non-stretched (draw ratio is 1)
When, the tensile strength and modulus of film are respectively 91.09MPa and 1794.6MPa；When draw ratio reaches 3 times.Tensile strength reaches
Arrive 154.5MPa, about non-stretched 1.7 times, and modulus has reached 2472.4MPa, is non-stretched 1.4 times.It can see
Go out, by drawing polyamide sorrel, the mechanical property of Kapton is significantly improved really.
The embodiment of the following modified polyimide produced using above-mentioned process and system：
Embodiment 1
A kind of nano modification polyimides, including following components：10 parts of polyimides, 5 parts of benzophenone tetracarboxylic anhydride, 4,4 '-
6 parts of oxydianiline, 3 parts of end-capping reagent, 5 parts of titanium dioxide and inclined 6 parts of barium monoxide, end-capping reagent can be norbornene acid mono ethyl ester
Or norbornene acid mono-methyl, the present embodiment is from norbornene acid mono ethyl ester.
Embodiment 2
A kind of nano modification polyimides, including following components：12 parts of polyimides, 7 parts of benzophenone tetracarboxylic anhydride, 4,4 '-
8 parts of oxydianiline, 4 parts of end-capping reagent, 8 parts of titanium dioxide and inclined 15 parts of barium monoxide, end-capping reagent can be norbornene acid list second
Ester or norbornene acid mono-methyl, the present embodiment select norbornene acid mono ethyl ester.
Embodiment 3
A kind of nano modification polyimides, including following components：15 parts of polyimides, 10 parts of benzophenone tetracarboxylic anhydride, 4,4 '-
11 parts of oxydianiline, 5 parts of end-capping reagent, 10 parts of titanium dioxide and inclined 25 parts of barium monoxide, end-capping reagent can be norbornene acid list
Ethyl ester or norbornene acid mono-methyl, the present embodiment select borneol olefin(e) acid mono-methyl.
Comparative example
A kind of nano modification polyimides, including following components：15 parts of polyimides, 10 parts of benzophenone tetracarboxylic anhydride, 4,4 '-
11 parts of oxydianiline, 5 parts of end-capping reagent, end-capping reagent can be norbornene acid mono ethyl ester or norbornene acid mono-methyl, this reality
Example is applied from borneol olefin(e) acid mono-methyl.
0.005g polypyromelliticimide, biphenyl polyimide, bis ether acid anhydride type polyimides are added to respectively
In 20mlDMF, DMAc, NMP, methanesulfonic acid, the concentrated sulfuric acid, dissolubility is determined.
TG, DTA analysis, air atmosphere, heating are carried out to the polyimides of synthesis using differential thermal thermogravimetric synthesis thermal analyzer
10 DEG C/min of speed, determines its Td, fusion and decomposition temperature.
Dsc analysis is carried out to the polyimides of synthesis using differential scanning calorimeter, air atmosphere, 10 DEG C of heating rate/
Min, determines its Tg.
A variety of modifications to embodiment will be apparent for those skilled in the art, determine herein
The General Principle of justice can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and features of novelty
Consistent most wide scope.
Claims (10)
1. a kind of nano modification polyimides, it is characterised in that including following components：10-15 parts of polyimides, tetracarboxylic anhydride 5-
10 parts, 6-11 parts of diamines, 3-5 parts of end-capping reagent, 5-10 parts of titanium dioxide and inclined 6-25 parts of barium monoxide.
2. nano modification polyimides preparation system according to claim 1, it is characterised in that the tetracarboxylic anhydride includes
Benzophenone tetracarboxylic anhydride or benzophenone tetrabasic carboxylic acid dimethyl ester or benzophenone tetrabasic carboxylic acid diethylester.
3. polyimides preparation system according to claim 1, it is characterised in that the diamines includes p-phenylenediamine or 4,
4 '-oxydianiline or two aminodiphenylmethane.
4. a kind of nano modification polyimides preparation system, it is characterised in that including solution preparation system and film preparing system,
The solution preparation system includes including being respectively communicated with two inlets, the inlet on reactor, the reactor
Dianhydride solvent tank and diamines solvent tank, height is connected between the dianhydride solvent tank and diamines solvent tank and the inlet
Position measuring tank, the reactor output end is connected with froth breaking tank, filter is connected between the froth breaking tank and the reactor；
The film preparing system includes imidization stove, winder, filming-drawing mechanism, and the froth breaking tank passes through salivation with the filming-drawing mechanism
Mouth is connected.
5. nano modification polyimides preparation system according to claim 4, it is characterised in that the filming-drawing mechanism includes
Front roller and rear transfer roller are provided with casing, the casing, is provided between the front roller and rear transfer roller and is cased with steel band, the steel band
Corresponding casing is provided with air inlet and air outlet.
6. a kind of nano modification polyimides preparation method as claimed in claim 1, it is characterised in that comprise the following steps：
Prepared by polyimide solution and prepared by Kapton；
S1：In polar solvent, PMDA is taken gradually to be added in batches in dimethyl acetamide, at normal temperatures and pressures instead
Answer, at least three times additions of the PMDA point generate high-molecular-weight poly phthalein amino acid solution, and add titanium dioxide and inclined
Barium monoxide；
S2：The solid-state PAA films for removing solvent are dried, slow continuous in vacuum or inert media or ladder step is warming up to and is higher than
300 DEG C are heat-treated；
Reaction equation is：
7. nano modification polyimides preparation method according to claim 6, it is characterised in that the PMDA
Ratio with biphenyl ether diamine is 1.020~1.030 ﹕ 1.
8. nano modification polyimides preparation method according to claim 6, it is characterised in that the polar solvent includes
Dimethyl methyl phthalein amine or dimethyl acetamide or N- methyl adjoin pyrrolidone or adjoin smack one's lips or dimethyl sulfoxide (DMSO).
9. nano modification polyimides preparation method according to claim 6, it is characterised in that in S2, after froth breaking
Polyamic acid solution, is pressed into the salivation mouth storage tank on preceding head by the road by stainless steel solution reservoir；Steel band travels at the uniform speed, will
Solution in storage tank is taken away through salivating mouth front scrapping plate, and forms liquid film in uniform thickness, and the rear drying road that enters is dried；Clean dried
Air by air blower feeding heater be preheating to after certain temperature enter upper and lower drying road；
Hot wind flow direction is opposite with steel band traffic direction；
Polyamic Acid Film is operated therewith one week on steel band, and solvent evaporation turns into solid film, thin under being peeled off from steel band
Film guides imidization stove into through guide roller.
10. nano modification polyimides preparation method according to claim 9, it is characterised in that imidization stove is multiple roll
Cartridge form, enters imidization stove, after high temperature imidization, by receiving with the guide roller guiding Polyamic Acid Film of slobbering machine synchronizing speed
Volume machine winds Kapton.
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| CN113715236A (en) * | 2021-09-02 | 2021-11-30 | 江苏传艺科技股份有限公司 | Low-retardation polyimide film processing technology and production equipment thereof |
| CN113913123A (en) * | 2021-11-12 | 2022-01-11 | 深圳宏瑞新材料股份有限公司 | Pressure-sensitive matte black PI (polyimide) adhesive tape and manufacturing method thereof |
| CN114102944A (en) * | 2020-09-01 | 2022-03-01 | 山东巨野盛鑫电器材料有限公司 | Paint production equipment and production method thereof |
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| CN113715236A (en) * | 2021-09-02 | 2021-11-30 | 江苏传艺科技股份有限公司 | Low-retardation polyimide film processing technology and production equipment thereof |
| CN113913123A (en) * | 2021-11-12 | 2022-01-11 | 深圳宏瑞新材料股份有限公司 | Pressure-sensitive matte black PI (polyimide) adhesive tape and manufacturing method thereof |
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