CN108503831A - To form the constituent, polyimides and polyimide film of polyimides - Google Patents
To form the constituent, polyimides and polyimide film of polyimides Download PDFInfo
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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
- C08G73/1075—Partially aromatic polyimides
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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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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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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
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Abstract
The present invention provides a kind of to form the constituent, polyimides and polyimide film of polyimides, and the constituent to form polyimides includes tetracarboxylic dianhydride's monomer component, diamine monomer component and solvent.Diamine monomer component include the 4,4' diamino-diphenyls ether of 20 molar parts to 65 molar parts, 30 molar parts to 70 molar parts the melamine by formula (I) compound represented and 1 molar part to 10 molar parts:
Description
Technical field
The present invention relates to a kind of constituents, and it is more particularly to a kind of to form the constituent of polyimides, by described group
At polyimides made from object and by the polyimide film obtained by the polyimides.
Background technology
In general, polyimides (polyimide, PI) is by diamines (diamine) monomer and dicarboxylic anhydride
(dianhydride) monomer is through polycondensation reaction (polycondensation reaction) obtained high molecular material.Mesh
Before, polyimides is each due to properties such as chemical stability, electrical properties and thermostabilities, being widely used in
Kind of industry, for example, semi-conductor industry, opto-electronics, aeronautical material, raw doctor's material, textile industry, building field, auto industry,
It communicates in material, mechanical industry or thin film industry, and as material indispensable in life.In order to further promote polyamides
The application of imines, those skilled in the art carry out the research of novel polyimides and still continue in development.
Invention content
The present invention provide it is a kind of to form the constituent of polyimides, can be made with heat resistance and elasticity polyamides
Imines or polyimide film.
The present invention the constituent to form polyimides include tetracarboxylic dianhydride's monomer component, diamine monomer component with
And solvent.Diamine monomer component includes 4,4 '-diamino-diphenyl ether (ODA of 20 molar parts to 65 molar parts;4,4 '-
Diaminodiphenyl ether), 30 molar parts to 70 molar parts are by formula (I) compound represented and 1 molar part to 10
The melamine (melamine) of molar part:
The summation of wherein x and z is that 1 to 20, y is 4 to 50.
In one embodiment of the present invention, above-mentioned tetracarboxylic dianhydride's monomer component includes containing aromatic tetrabasic carboxylic acid
Dianhydride.
In one embodiment of the present invention, above-mentioned diamine monomer component includes 25 molar parts to the 4 of 65 molar parts,
4 '-diamino-diphenyl ethers, 30 molar parts to 70 molar parts are by formula (I) compound represented and 1 molar part to 10 molar parts
Melamine.
In one embodiment of the present invention, above-mentioned tetracarboxylic dianhydride's monomer component is 3,4,3 ', 4 '-diphenyl ether tetramethyls
Acid dianhydride (ODPA;3,4,3 ', 4 '-oxydiphthalic anhydride).
In one embodiment of the present invention, above-mentioned diamine monomer component includes 20 molar parts to the 4 of 45 molar parts,
4 '-diamino-diphenyl ethers, 50 molar parts to 70 molar parts are by formula (I) compound represented and 5 molar parts to 10 molar parts
Melamine.
In one embodiment of the present invention, above-mentioned tetracarboxylic dianhydride's monomer component is pyromellitic acid anhydride (PMDA;
pyromellitic dianhydride)。
In one embodiment of the present invention, above-mentioned diamine monomer component includes 25 molar parts to the 4 of 45 molar parts,
4 '-diamino-diphenyl ethers, 50 molar parts to 70 molar parts are by formula (I) compound represented and 5 molar parts to 10 molar parts
Melamine.
In one embodiment of the present invention, above-mentioned tetracarboxylic dianhydride's monomer component is 3,3 ', 4,4 '-biphenyltetracarboxyacid acids
Dianhydride (BPDA;3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride).
In one embodiment of the present invention, above-mentioned diamine monomer component further includes siloxane diamine.
In one embodiment of the present invention, above-mentioned siloxane diamine includes by formula (II) compound represented:
Wherein n is 8 to 11.
In one embodiment of the present invention, above-mentioned diamine monomer component includes 35 molar parts to the 4 of 45 molar parts,
4 '-diamino-diphenyl ethers, 40 molar parts to 50 molar parts by formula (I) compound represented, 5 molar parts to 10 molar parts
The siloxane diamine of melamine and 5 molar parts to 10 molar parts.
The polyimides of the present invention is formed by as previously described obtained by the constituent of polyimides.
The polyimides membrane system of the present invention is obtained by foregoing polyimides.
Based on above-mentioned, it is of the invention to formed the constituent of polyimides by include tetracarboxylic dianhydride's monomer component,
Diamine monomer component and solvent, wherein diamine monomer component include 4 of content respectively in particular range, 4 '-diamino two
Phenyl ether can have good film forming by formula (I) compound represented and melamine.Thus, through the invention
The constituent to form polyimides the excellent polyimide film of material character can be made.In addition, use through the invention
Constituent to form polyimides includes tetracarboxylic dianhydride's monomer component, diamine monomer component and solvent, wherein diamines list
Body component includes 4 of content respectively in particular range, 4 '-diamino-diphenyl ethers, by formula (I) compound represented and trimerization
Polyimides or polyimide film with heat resistance and elasticity can be made in cyanamide whereby.In addition to this, of the invention to shape
It can also be by including the siloxane diamine in particular range, with good film forming, in turn at the constituent of polyimides
It is able to be made the polyimide film with heat resistance and elasticity.
To make the foregoing features and advantages of the present invention clearer and more comprehensible, embodiment cited below particularly elaborate as
Under.
Specific implementation mode
Herein, the range indicated by " numerical value to another numerical value ", is that one kind avoids enumerating in the description
The summary representation of all numerical value in the range.Therefore, the record of a certain special value range, covers the numberical range
Interior any number and the relatively fractional value range defined by any number in the numberical range, as bright in the description
Text writes out any number and is somebody's turn to do as compared with fractional value range.
One embodiment of the present invention proposes a kind of forming the constituent of polyimides comprising tetracarboxylic dianhydride is single
Body component, diamine monomer component and solvent.In the present embodiment, the total moles percentage and tetrabasic carboxylic acid of diamine monomer component
The ratio of the total moles percentage of dianhydride monomer component is 1: 0.95 to 1: 1.05.
In the present embodiment, diamine monomer component includes 4,4 '-diamino-diphenyl ether (ODA;4,4 '-
Diaminodiphenyl ether), by formula (I) compound represented and melamine (melamine):
The summation of wherein x and z is that 1 to 20, y is 4 to 50.That is, in the present embodiment, diamine monomer group subpackage
Include three kinds of diamine monomers.In addition, by amine hydrogen equivalent (the amine hydrogen equivalent of formula (I) compound represented
Weight) between 250 to 270, number average molecular weight is about 1000.
In addition, in the present embodiment, diamine monomer component includes 4,4 '-diamino two of 20 molar parts to 65 molar parts
The melamine by formula (I) compound represented and 1 molar part to 10 molar parts of phenyl ether, 30 molar parts to 70 molar parts.
If 4,4 '-diamino-diphenyl ethers are not fallen within by the molar part of at least one of formula (I) compound represented and melamine
In aforementioned range, then the constituent to form polyimides does not have film forming.
In the present embodiment, tetracarboxylic dianhydride's monomer component includes containing aromatic tetracarboxylic dianhydride.Specifically,
Example containing aromatic tetracarboxylic dianhydride includes but not limited to:3,4,3 ', 4 '-diphenyl ether tetraformic dianhydride (ODPA;3,4,
3 ', 4 '-oxydiphthalic anhydride), pyromellitic acid anhydride (PMDA;pyromellitic dianhydride)、
3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride (BPDA;3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride),
2,2 ', 3,3 '-biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic acids
Bis- (2, the 3- dicarboxyphenyi) hexafluoropropane dianhydrides of acid dianhydride, 2,2-, bis- (3, the 4- dicarboxyphenyi) hexafluoropropane dianhydrides of 2,2-
(6FDA), bis- (2,3- dicarboxyphenyi) methane dianhydrides, bis- (3,4- dicarboxyphenyi) methane dianhydrides, 3,3 ', 4,4 '-diphenyl
Sulfone tetracarboxylic dianhydride (DSDA;3,3 ', 4,4 '-diphenylsulfone tetracarboxylic dianhydride), 2,2-
Bis- [4- (3,4- di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA;2,2-bis [4- (3,4-dicarboxyphenoxy)
Phenyl] propane), bis- (2,3- dicarboxyphenyi) sulfone dianhydrides, bis- (3,4- dicarboxyphenyi) sulfone dianhydrides or ethylene glycol it is double partially
Benzenetricarboxylic acid dianhydride (TMEG;Ethylene glycol bis (4-trimellitate anhydride)), and preferably 3,3 ',
4,4 '-biphenyltetracarboxylic dianhydrides, 3,4,3 ', 4 '-diphenyl ether tetraformic dianhydrides, pyromellitic acid dianhydride or 2, bis- (3, the 4- dicarboxyls of 2-
Base phenyl) hexafluoropropane dianhydride (6FDA).
On the other hand, in the present embodiment, tetracarboxylic dianhydride's monomer component includes a kind of tetracarboxylic dianhydride's monomer.Citing
For, in one embodiment, tetracarboxylic dianhydride's monomer component is 3,4,3 ', 4 '-diphenyl ether tetraformic dianhydrides (ODPA), and this
When, diamine monomer component includes 4,4 '-diamino-diphenyl ethers of 25 molar parts to 65 molar parts, 30 molar parts to 70 molar parts
The melamine by formula (I) compound represented and 1 molar part to 10 molar parts, and to form the composition of polyimides
Object has good film forming.For by way of further example, in one embodiment, tetracarboxylic dianhydride's monomer component is Pyromellitic Acid
Dianhydride (PMDA), and at this point, diamine monomer component includes 4,4 '-diamino-diphenyl ethers of 20 molar parts to 45 molar parts, 50
Molar part to 70 molar parts the melamine by formula (I) compound represented and 5 molar parts to 10 molar parts, and to shape
There is good film forming at the constituent of polyimides.For lifting another example, in one embodiment, tetracarboxylic dianhydride's monomer
Group is divided into 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA), and at this point, diamine monomer component includes 25 molar parts to 45 moles
Part 4,4 '-diamino-diphenyl ethers, 50 molar parts to 70 molar parts are by formula (I) compound represented and 5 molar parts to 10
The melamine of molar part, and there is good film forming to the constituent for forming polyimides.
In addition, for the viewpoint of elasticity for promoting polyimides, diamine monomer component can further include siloxane diamine.Tool
For body, the example of siloxane diamine includes but is not limited to:By following formula (II) compound represented,
Wherein n is 8 to 11.In one embodiment, diamine monomer component includes 4, the 4 '-of 35 molar parts to 45 molar parts
Diamino-diphenyl ether, 40 molar parts to 50 molar parts by formula (I) compound represented, 5 molar parts to the three of 10 molar parts
The siloxane diamine of poly cyanamid and 5 molar parts to 10 molar parts.
In the present embodiment, there is no particular restriction for solvent, as long as tetracarboxylic dianhydride's monomer component and diamines can be dissolved
Monomer component.Specifically, the example of solvent includes but not limited to:N,N-dimethylacetamide (N, N-
dimethylacetamide;DMAc), n,N-Dimethylformamide (N, N-dimethylformamide;DMF), N, N '-diethyl
Yl acetamide, N- methyl -2- Pyrrolizidine ketone (N-methyl-2-pyrrolidone;NMP), gamma-butyrolacton, hexamethyl tricresyl phosphate
The acid amides series solvents such as amide;Tetramethylurea, N, the ureas series solvent such as N- dimethyl ethyl ureas;Dimethyl sulfoxide (DMSO), diphenyl sulfone, tetramethyl
The sulfoxides such as base sulfone or sulfone series solvent;The halogenated alkyls series solvent such as chloroform, dichloromethane;The aromatic hydrocarbon series solvents such as benzene, toluene;Benzene
The phenol systems solvent such as phenol, cresols;Or the ether series solvents such as tetrahydrofuran, 1,3- dioxolanes, dimethyl ether, diethyl ether, methyl para-cresol.
Above-mentioned solvent may be used alone or in combination a variety of use.To improve the molten of tetracarboxylic dianhydride's monomer component and diamine monomer component
Solution property and reactivity, the acid amides series solvents such as preferred solvents DMAc, DMF, NMP.
It is worth noting that as described above, in the present embodiment, by including tetracarboxylic dianhydride's monomer component, diamines
Monomer component and solvent, wherein diamine monomer component include 4 of content respectively in particular range, 4 '-diamino-diphenyls
Ether, by formula (I) compound represented and melamine, whereby to formed polyimides constituent can have it is good at
Film property.
Another embodiment of the present invention provides a kind of polyimides, by being formed in any aforementioned embodiments
Obtained by the constituent of polyimides.The diamine monomer component in constituent, tetracarboxylic dianhydride to form polyimides is single
Body component and the associated description of solvent are at large illustrated in aforementioned embodiments, therefore are repeated no more in this.
Specifically, in the present embodiment, polyimides is by diamine monomer component and tetracarboxylic dianhydride's monomer component
Condensation polymerization reaction is carried out in solvent to prepare.In one embodiment, three kinds of diamine monomers and one can be used in polyimides
Tetracarboxylic dianhydride's monomer is planted to prepare.In another embodiment, four kinds of diamine monomers and one kind can be used in polyimides
It is prepared by tetracarboxylic dianhydride monomer.It should be noted that gathering since diamine monomer and tetracarboxylic dianhydride's monomer generate reaction
Acid imide, therefore the ratio of the total mole number of the amino in diamine monomer and the total mole number of the anhydride group in tetracarboxylic dianhydride's monomer
Example about 1: 1.In more detail, the ratio can be between 1: 0.95 to 1: 1.05.
In addition, in the present embodiment, polyimides is, for example, to be prepared by thermal cyclization method or chemical imidization method.Hot ring
Change method and chemical imidization method can be carried out respectively using any step well known to those of ordinary skill in the art.
For example, included the following steps to prepare polyimides by thermal cyclization method:Using with formed the constituent of polyimides into
After row polymerisation is to form polyamic acid solution, heating polyamic acid solution is to carry out imidization reaction (i.e. cyclodehydration
Reaction) form polyimides.Specifically, to formed polyimides constituent preparation method be, for example, at 5 DEG C extremely
Within the temperature range of 40 DEG C, diamine monomer component and tetracarboxylic dianhydride's monomer component are uniformly mixed in solvent.Mixed side
There is no particular restriction for method, as long as diamine monomer component and tetracarboxylic dianhydride's monomer component can be made to be uniformly mixed in solvent.
In one embodiment, in the step of forming polyamic acid solution, reaction temperature is, for example, between 5 DEG C to 40 DEG C;Instead
It is, for example, between 3 hours to 12 hours between seasonable.In one embodiment, the condition for carrying out imidization reaction is, for example,
It is reacted respectively 1 to 2 hour under 100 DEG C, 150 DEG C and 220 DEG C of temperature environment.
For by way of further example, included the following steps to prepare polyimides by chemical imidization method:Using to form polyamides
After the constituent of imines carries out polymerisation to form polyamic acid solution, polyamic acid is added in dehydrating agent and acid imide agent
In solution polyimides is formed to carry out imidization reaction (i.e. cyclodehydration reacts).Specifically, forming polyamides
The preparation method of the constituent of imines is, for example, within the temperature range of 5 DEG C to 40 DEG C, by diamine monomer component and tetrabasic carboxylic acid two
Anhydride monomer component is uniformly mixed in solvent.There is no particular restriction for mixed method, as long as can make diamine monomer component and tetracarboxylic acid
Acid dianhydride monomer component is uniformly mixed in solvent.In one embodiment, in the step of forming polyamic acid solution,
Reaction temperature is, for example, between 5 DEG C to 40 DEG C;Reaction time is, for example, between 3 hours to 12 hours.Implement one
In mode, the condition for carrying out imidization reaction is, for example, to react 2 hours to 5 hours under 120 DEG C of temperature environment, preferably
3 hours.In one embodiment, the example of dehydrating agent includes but not limited to:Acetic anhydride, propionic andydride, n butanoic anhydride, benzoyl oxide
Or trifluoroacetic anhydride;The example of acid imide agent includes but not limited to:Pyridine, picoline, quinoline or isoquinolin.Implement one
In mode, relative to the amide groups of polyamic acid, the additive amount of dehydrating agent is, for example, 0.5 to 10.0 times of molar equivalent, and acyl is sub-
The additive amount of aminating agent is, for example, for 0.5 to 5.0 times of molar equivalent.
It is worth noting that as described above, in the present embodiment, due to passing through to the constituent that forms polyimides
Including tetracarboxylic dianhydride's monomer component including content respectively 4, the 4 '-diamino-diphenyl ethers in particular range, by formula (I)
Compound represented and the diamine monomer component and solvent of melamine and can have good film forming, therefore by shape
Polyimides obtained by constituent at polyimides can form the film with elite clone property.
On the other hand, by including tetracarboxylic dianhydride's monomer component including content to the constituent that forms polyimides
4 in particular range respectively, 4 '-diamino-diphenyl ethers, by the diamine monomer of formula (I) compound represented and melamine
Component and solvent, polyimides not only has excellent film forming whereby, and is formed by film and has more heat resistance and bullet
Property.Thus, which the polyimides of the present invention is substantially improved in various industrial applicabilities and commercial value.
In addition, do not undermine the present invention polyimides essential effect in the range of, polyimides can on demand and with
Additive blends, to further increase the application and commercial value of polyimides.The additive for example including conductive material,
Fire retardant, colorant, filler or combinations thereof object.For example, in order to assign polyimides electric conductivity to meet needle in industry
Demand to electric conductivity, polyimides can be blended with conductive material, wherein conductive material for example including graphene, carbon nanotubes,
Nano silver, nano-silver thread or conducting polymer;The method of blending for example including directly make polyimides mixed with conductive material or
Person further includes conductive material using with the constituent for forming polyimides.
Although in addition, as it was noted above, can make with good film forming to the constituent for forming polyimides
Film can be formed by its polyimides obtained, but the polyimides of the present invention can also the form of powder or solution etc. exist.
Another embodiment of the present invention provides a kind of polyimide film, sub- by the polyamides in any aforementioned embodiments
Obtained by amine.The associated description of polyimides is at large illustrated in aforementioned embodiments, therefore is repeated no more in this.
In present embodiment, the thickness of polyimide film is different according to application purpose, and in general, thickness is about at 15 μm to 200 μ
Between m, preferably then be 15 μm to 100 μm between.
In addition, in the present embodiment, polyimide film can pass through those of ordinary skill in the art institute week
It is prepared by any method for knowing.It for example, in one embodiment, can be by making polyimides carry out solution casting method come shape
At polyimide film.For by way of further example, in one embodiment, with reference to the preparation method previously for polyimides, polyamides
The preparation method of imines film may include after forming polyamic acid solution, is applied to polyamic acid solution by coating process
On one base material, and it is then made to carry out imidization reaction.Specifically, coating process can utilize and have in technical field
Any rubbing method well known to usual skill carries out, for example, scraper for coating method, method of spin coating, Pneumatic scraper rubbing method,
Slit coating method, squash type rubbing method or roller rubbing method;According to actual application, base material can be any suitable base
The base materials such as material, such as fabric, copper foil, glass, Teflon or plastic cement.
It is worth noting that as it was noted above, in the present embodiment, by forming the constituent packet of polyimides
Include 4 of tetracarboxylic dianhydride's monomer component including content respectively in particular range, 4 '-diamino-diphenyl ethers, by formula (I) institute
The diamine monomer component and solvent of the compound and melamine shown, whereby polyimide film can have excellent heat resistance and
Elasticity.Thus, which the polyimide film of the present invention is substantially improved in various industrial applicabilities and commercial value.
In addition, as it was noted above, in the range of not undermining the essential effect of polyimides of the present invention, led to meet
Electrical demand, polyimides of the invention can be blended with conductive material, and then being formed by polyimide film can be with conduction
Property.In one embodiment, the polyimide film for having electric conductivity can be for example followed by by being mixed with conductive material in polyimides
Carry out solution casting method to be formed.In another embodiment, the polyimide film for having electric conductivity for example can be by following step
It is rapid to be formed:Conductive material is set to be added in polyamic acid solution and after evenly mixing, be coated with mixed solution by coating process
To a base material, and it is then made to carry out imidization reaction.It is noted that the polyimide film of tool electric conductivity is due to same
When have excellent film quality, heat resistance and elasticity, can be applied to e.g. wisdom fabric (such as heartbeat band, body-sensing wisdom gloves),
The intelligent wearing element such as drawing display device, body surface electronics patch system or electronic skin.
Below in reference to embodiment 1-25, the feature of the present invention is more specifically described.Although describing following example 1-
25, but in the case of insurmountability scope, can suitably change material therefor, its amount and ratio, processing details with
And process flow etc..Therefore, restricting property of the present invention should not be explained by embodiments described just below.Especially, by
Reaction is generated into polyimides, and the total mole number of the amino in diamine monomer component in diamine monomer and tetracarboxylic dianhydride's monomer
Ratio with the total mole number of the anhydride group in tetracarboxylic dianhydride's monomer component is about 1: 1, therefore it can be seen that tetracarboxylic dianhydride is single
The molar part of body should be total moles part of the amino in diamine monomer component after EQUILIBRIUM CALCULATION FOR PROCESS as a result, and the ratio can be between
Between 0.95: 1 to 1.05: 1.
The information for the main material that the polyimide film of preparation embodiment 1-25 uses is as follows.
Diamine monomer component:
4,4 '-diamino-diphenyl ethers (hereinafter referred to as ODA):Purchased from Ao Ruiqi companies of Sigma (Sigma-Aldrich);
By formula (I) compound represented:The entitled RT-1000 of product is purchased from Hensel Mann (Huntsman Ltd.);Melamine:Purchase
From Ao Ruiqi companies of Sigma;Siloxane diamine:Purchased from science macromolecule product company (Scientific Polymer
Products, Inc.).
Tetracarboxylic dianhydride's monomer component:
3,4,3 ', 4 '-diphenyl ether tetraformic dianhydrides (hereinafter referred to as ODPA):Purchased from Ao Ruiqi companies of Sigma;Equal benzene four
Formic acid dianhydride (hereinafter referred to as PMDA):Purchased from Ao Ruiqi companies of Sigma;3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides are (hereinafter referred to as
BPDA):Purchased from Ao Ruiqi companies of Sigma.
Dehydrating agent:
Acetic anhydride:Purchased from Ao Ruiqi companies of Sigma.
Acid imide agent:
Pyridine:Purchased from Ao Ruiqi companies of Sigma.
Conductive material:
Graphene:Research institute (TTRI) is closed from juridical person's textile industry to obtain.
Embodiment 1
First, high-purity nitrogen is passed through in the three-necked bottle of 150mL, to remain dry in bottle.Then, at room temperature, will
DMAc (as solvent) additions of the ODA of 49 molar parts, the RT-1000 of 50 molar parts, the melamine of 1 molar part and 25mL
In three-necked bottle, and it is uniformly mixed.Later, at room temperature, the ODPA of 100.5 molar parts is added in aforementioned mixed solution, and held
Continue and reacted 12 hours under nitrogen, to form the polyamic acid solution that solid content is 35%.Then, by the acetic anhydride of 20mL with
The pyridine of 10mL is added in polyamic acid solution, and progress imidization reaction 3 hours at 120 DEG C.It waits for after reaction, it will
Gained mixed solution is cooled to room temperature.Then, after gained mixed solution being poured slowly into a large amount of methanol in stirring, pass through
Filtering is to obtain solid portion.Later, obtained solid is rinsed with methanol, and 2 hours dry at 120 DEG C, to obtain
The polyimides of embodiment 1.Then, the polyimides of embodiment 1 is dissolved in suitable DMAc, it is molten to form polyimides
Liquid.Later, on a glass by polyimide solution casting, it and is toasted 3 hours at 80 DEG C, the polyamides of embodiment 1 is made
Imines film.
Embodiment 2-14
According to preparation procedure similar to Example 1, and according to shown by table 1 ingredient and its molar part prepare reality
Apply the polyimide film of a 2-14.
Embodiment 15
According to preparation procedure similar to Example 1, and according to shown by table 1 ingredient and its adding proportion prepare
The polyimide film of embodiment 15, its right difference essentially consist in following steps:After the polyimides that embodiment 15 is made, make
It just pours and is cast from glass plate after being dissolved in the NMP of 15mL together with the polyimides of embodiment 15 and the graphene of 5wt%.
Embodiment 16-19
According to preparation procedure similar with embodiment 15, and according to shown by table 1 ingredient and its adding proportion make
The polyimide film of standby embodiment 16-19.
Embodiment 20
According to preparation procedure similar to Example 1, and according to shown by table 1 ingredient and its adding proportion prepare
The polyimide film of embodiment 20, its right difference essentially consist in following steps:In embodiment 20, by ODA, RT-1000, trimerization
Cyanamide and siloxane diamine are added in DMAc together;And in embodiment 1, and siloxane diamine is not used.
Embodiment 21-22
According to preparation procedure similar with embodiment 20, and according to shown by table 1 ingredient and its adding proportion make
The polyimide film of standby embodiment 21-22.
Embodiment 23
According to preparation procedure similar with embodiment 20, and according to shown by table 1 ingredient and its adding proportion make
The polyimide film of standby embodiment 23, its right difference essentially consist in following steps:After the polyimides that embodiment 23 is made,
Make just to pour after being dissolved in the NMP of 15mL together with the polyimides and the graphene of 16.7wt% of embodiment 23 and casts from glass plate
On.In addition, the thickness of the polyimide film of embodiment 23 is 100 μm.
Embodiment 24-25
According to preparation procedure similar with embodiment 23, and according to shown by table 1 ingredient and its adding proportion make
The polyimide film of standby embodiment 24-25, the wherein thickness of the polyimide film of embodiment 24 are 25 μm, the polyamides of embodiment 25
The thickness of imines film is 100 μm.
Later, the evaluation for carrying out film forming to the polyimide film of embodiment 1-25 respectively, respectively to embodiment 1-6,9-
14,20,22 polyimide film carries out 5% thermogravimetric weight loss temperature (TD5%), 10% thermogravimetric weight loss temperature (TD10%) measurement, point
The other polyimide film to embodiment 1-6,9-14 carries out 800 DEG C of residual weight ratio (Rw800) measurement, respectively to implement
Polyimide film progress glass transition temperature (the glass transition temperature of example 3,10,12,20-22;Tg)
Measurement, respectively to embodiment 3,10,12, the polyimide film of 20-21 carry out tensile strength (tensile strength), with
And the measurement of elongation at break (elongation), storage modulus is carried out to the polyimide film of embodiment 10,20 respectively
The measurement of (storage modulus), and surface resistivity is carried out to the polyimide film of embodiment 15-19,23-25 respectively
Measurement.Aforementioned items measurement project is described as follows, and evaluation or measurement are shown in table 2.
<The evaluation of film forming>
The polyimide film of embodiment 1-25 is visually observed respectively and optical microphotograph sem observation, and according to practical feelings
Shape is divided into complete, damaged and can not be molded three aspects.
<TD5%、TD10%And Rw800Measurement>
Measure the T of the polyimides of embodiment 1-6,9-14,20,22 respectively using thermogravimetry (TGA)D5%、
TD10%, and using thermogravimetry (TGA) respectively measure embodiment 1-6,9-14 polyimides Rw800.Thermogravimetric amount point
Analysis condition is in a nitrogen atmosphere (airflow rate 60cm3/min), with constant speed heating (rate of heat addition is 10 DEG C/min) sample
And the weight change of recording materials, and measuring instrument is thermogravimetric analyzer (model Q50, by TA Instruments corporations
It makes).
TD5%Refer to temperature of the weight loss up to 5 weight %, wherein TD5%The heat resistance of higher representative sample is better.TD10%
Refer to temperature of the weight loss up to 10 weight %, wherein TD10%The heat resistance of higher representative sample is better.Rw800It refer to heating temperature
Material residues weight rate when spending up to 800 DEG C.
<TgMeasurement>
Measured respectively using differential scanning calorimetry method (DSC) embodiment 3,10,12,20-22 polyimide film Tg,
Its analysis condition is the heat content variation with constant speed heating (rate of heat addition is 10 DEG C/min) sample and recording materials, wherein measurement instrument
Device is differential scanning calorimetry instrument (model:Q10 is manufactured by TA Instruments companies).
<The measurement of tensile strength and elongation at break>
Use universal testing machine (model:HT-8336-S , You Hung reaches equipment company (HUNG TA Instruments)
Manufacture) measure respectively embodiment 3,10,12,20-21 polyimide film tensile strength and elongation at break, wherein sample is
Dumbbell-shaped test piece, and rate of extension is 3mm/min.
<Store the measurement of modulus>
The storage modulus of the polyimide film of embodiment 10,20 is measured using dynamic mechanical analysis (DMA).Store modulus
Analysis condition be with constant speed heating (rate of heat addition be 5 DEG C/min, frequency:1Hz) the change of the storage modulus of sample and recording materials
Change, wherein measuring instrument is Dynamic Mechanical Analyzer (model:Q800 is manufactured by TA Instruments companies).
<The measurement of surface resistivity>
Measure the surface resistivity of the polyimide film of embodiment 15-19,23-25 respectively using four-point probe method, wherein
Measuring instrument is that (MITSUBISHI CHEMICAL companies manufacture four-point probe Low ESR rate meter, model:LORESTA-GP MCP-
T600).The standard of tool electric conductivity is assessed using the classification standard of FTTS-FA-009 institutes specification;Wherein, when surface resistivity is big
In 1 × 1012Ω/cm2, then insulating materials is represented;When surface resistivity is between 1 × 105Ω/cm2With 1 × 1012Ω/cm2Between,
Then represent electrostatic dissipation material;When surface resistivity is less than 1 × 104Ω/cm2, then conductive material is represented, surface resistivity is lower
Then electric conductivity is more excellent.
By above-mentioned table 2 it is found that the polyimide film of embodiment 1-14 all has good behaviour in the evaluation of film forming.This
It indicates, the constituent to form polyimides through the invention includes tetracarboxylic dianhydride's monomer component including content difference
4 in particular range, 4 '-diamino-diphenyl ethers, by the diamine monomer component of formula (I) compound represented and melamine
And solvent, there can be good film forming whereby to form the constituent of polyimides, and obtained material is able to by it
Different polyimide film of fine quality.
In addition, by above-mentioned table 2 it is found that the polyimide film of embodiment 20-22 all has well in the evaluation of film forming
Performance.This indicate, through make the present invention the constituent to form polyimides include tetracarboxylic dianhydride's monomer component including
Content respectively 4, the 4 '-diamino-diphenyl ethers in particular range, by the diamines of formula (I) compound represented and melamine
Monomer component and solvent, even if diamine monomer component further includes siloxane diamine, to form the constituent of polyimides still
There can be good film forming, and the excellent polyimide film of obtained material character is able to by it.
In addition, by above-mentioned table 2 it is found that the polyimide film of embodiment 15-19 not only all has in the evaluation of film forming
Good behaviour also each has electric conductivity.This expression, includes tetracarboxylic acid by making the constituent to form polyimides of the present invention
Acid dianhydride monomer component including content respectively 4, the 4 '-diamino-diphenyl ethers in particular range, change shown in formula (I)
The diamine monomer component and solvent for closing object and melamine, can not only be made the excellent polyimide film of material character, more may be used
In the case where not undermining essential effect, to have additionally to assign polyimide film by blending polyimides and additive
Characteristic, such as electric conductivity, and then increase the application and commercial value of polyimide film.
In addition, by above-mentioned table 2 it is found that the polyimide film of embodiment 23-25 not only all has in the evaluation of film forming
Good behaviour also each has electric conductivity.This indicate, through make the present invention the constituent to form polyimides include tetracarboxylic acid
Acid dianhydride monomer component including content respectively 4, the 4 '-diamino-diphenyl ethers in particular range, change shown in formula (I)
The diamine monomer component and solvent for closing object and melamine, even if diamine monomer component further includes siloxane diamine, still not
The excellent polyimide film of material character can only be made, it more can be in the case where not undermining essential effect, through polyamides is sub-
Amine is blended with additive has additional characteristic, such as electric conductivity to assign polyimide film, and then increases polyimide film
Application and commercial value.
In addition, by above-mentioned table 2 about TD5%、TD10%、Rw800、Tg, tensile strength and elongation at break etc. knot
Fruit is it is found that the constituent to form polyimides through the invention includes tetracarboxylic dianhydride's monomer component including content point
4,4 '-diamino-diphenyl ethers not in particular range, by the diamine monomer group of formula (I) compound represented and melamine
Point and solvent, whereby polyimide film can have heat resistance and elasticity.
In addition, by above-mentioned table 2 it is found that the polyimide film of embodiment 20-21 is equal in tensile strength and extension at break
With good behaviour.This indicates that the constituent to form polyimides through the present invention includes tetracarboxylic dianhydride's monomer group
Point including content respectively 4, the 4 '-diamino-diphenyl ethers in particular range, by formula (I) compound represented, melamine
And the diamine monomer component and solvent of siloxane diamine, thereby obtained polyimide film can have ductility or elasticity.
Although the present invention is disclosed as above with embodiment, however, it is not to limit the invention, any affiliated technology neck
Technical staff in domain, without departing from the spirit and scope of the present invention, when can make a little change with retouching, but these change with
Retouching should all be fallen within the scope of protection of the present invention.
Claims (13)
1. a kind of forming the constituent of polyimides, which is characterized in that including:
Tetracarboxylic dianhydride's monomer component;
Diamine monomer component, including 4, the 4'- diamino-diphenyls ether of 20 molar parts to 65 molar parts, 30 molar parts are to 70 moles
The melamine by formula (I) compound represented and 1 molar part to 10 molar parts of part:
The summation of wherein x and z is that 1 to 20, y is 4 to 50;And
Solvent.
2. according to claim 1 forming the constituent of polyimides, which is characterized in that the tetracarboxylic dianhydride is single
Body component includes containing aromatic tetracarboxylic dianhydride.
3. according to claim 1 forming the constituent of polyimides, which is characterized in that the diamine monomer component
4,4'- diamino-diphenyls ether, 30 molar parts to 70 molar parts including 25 molar parts to 65 molar parts are shown in formula (I)
The melamine of compound and 1 molar part to 10 molar parts.
4. according to claim 3 forming the constituent of polyimides, which is characterized in that the tetracarboxylic dianhydride is single
Body group is divided into 3,4,3', 4'- diphenyl ether tetraformic dianhydrides.
5. according to claim 1 forming the constituent of polyimides, which is characterized in that the diamine monomer component
4,4'- diamino-diphenyls ether, 50 molar parts to 70 molar parts including 20 molar parts to 45 molar parts are shown in formula (I)
The melamine of compound and 5 molar parts to 10 molar parts.
6. according to claim 5 forming the constituent of polyimides, which is characterized in that the tetracarboxylic dianhydride is single
Body group is divided into pyromellitic acid anhydride.
7. according to claim 1 forming the constituent of polyimides, which is characterized in that the diamine monomer component
4,4'- diamino-diphenyls ether, 50 molar parts to 70 molar parts including 25 molar parts to 45 molar parts are shown in formula (I)
The melamine of compound and 5 molar parts to 10 molar parts.
8. according to claim 7 forming the constituent of polyimides, which is characterized in that the tetracarboxylic dianhydride is single
Body group is divided into 3,3', 4,4'- biphenyltetracarboxylic dianhydrides.
9. according to claim 1 forming the constituent of polyimides, which is characterized in that the diamine monomer component
It further include siloxane diamine.
10. according to claim 9 forming the constituent of polyimides, which is characterized in that the siloxane diamine
Including by formula (II) compound represented:
Wherein n is 8 to 11.
11. according to claim 9 forming the constituent of polyimides, which is characterized in that the diamine monomer group
Point include the 4,4'- diamino-diphenyls ether of 35 molar parts to 45 molar parts, 40 molar parts to 50 molar parts by shown in formula (I)
Compound, the melamine of 5 molar parts to 10 molar parts and the siloxane diamine of 5 molar parts to 10 molar parts.
12. a kind of polyimides, which is characterized in that it is by forming polyamides Asia described in any one of claim 1-11
Obtained by the constituent of amine.
13. a kind of polyimide film, which is characterized in that it is obtained by the polyimides described in claim 12.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101472975A (en) * | 2006-06-16 | 2009-07-01 | 宇部兴产株式会社 | Polyether polyamide elastomer |
WO2012048888A1 (en) * | 2010-10-14 | 2012-04-19 | Tata Steel Nederland Technology B.V. | Preparation of a polyetherimide intermediate and its application on metal substrates |
KR20150037572A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Thermoplastic Resin comprising Polyamide |
CN105745265A (en) * | 2013-09-23 | 2016-07-06 | 沙特基础全球技术有限公司 | Nitrogen containing polymer compositions having reduced combustion toxicity |
-
2017
- 2017-02-24 CN CN201710105902.5A patent/CN108503831B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101472975A (en) * | 2006-06-16 | 2009-07-01 | 宇部兴产株式会社 | Polyether polyamide elastomer |
WO2012048888A1 (en) * | 2010-10-14 | 2012-04-19 | Tata Steel Nederland Technology B.V. | Preparation of a polyetherimide intermediate and its application on metal substrates |
CN105745265A (en) * | 2013-09-23 | 2016-07-06 | 沙特基础全球技术有限公司 | Nitrogen containing polymer compositions having reduced combustion toxicity |
KR20150037572A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Thermoplastic Resin comprising Polyamide |
Non-Patent Citations (1)
Title |
---|
冯新德等: "《高分子词典》", 30 June 1998, 中国石化出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111347746A (en) * | 2018-12-21 | 2020-06-30 | 利诺士尖端材料有限公司 | Flexible copper foil laminated film |
CN111347746B (en) * | 2018-12-21 | 2021-11-09 | 利诺士尖端材料有限公司 | Flexible copper foil laminated film |
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