CN109096758A - A kind of low dielectric coefficient polyimide film and preparation method thereof - Google Patents
A kind of low dielectric coefficient polyimide film and preparation method thereof Download PDFInfo
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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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
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- 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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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to low dielectric coefficient polyimide films and preparation method thereof, fluorine silicon dispersion liquid by the way that 15-25% is added into polyamic acid solution prepares low dielectric coefficient polyimide film, the fluorine silicon dispersion liquid: (1) deionized water, NaLS, ammonium persulfate, abutting ladder poly-siloxane into closed reactor is added, it is 2.5MPaG that tetrafluoroethene and propylene mixed gas to reacting kettle inner pressure are passed through at 70~80 DEG C, and 300rpm stirring carries out polymerization reaction；(2) mixed gas for being passed through tetrafluoroethene and propylene makes 2.49~2.51MPaG of pressure in kettle；(3) 10 DEG C of stopping polymerizations being cooled to, fluorine-containing abutting ladder poly-siloxane water-based emulsion is obtained；(4) at 60~70 DEG C, dimethyl acetamide, decompression dehydration are added dropwise into the water-based emulsion.Kapton of the present invention is keeping excellent cementability and mechanical property simultaneously, has low-k.
Description
Technical field
The present invention relates to polyimides field of functional materials, and in particular to a kind of low dielectric coefficient polyimide film and its
Preparation method.
Background technique
In recent years, polyimides is the aromatic heterocycle polymer compound in repetitive unit containing imide group, rigid acyl
Imine structure imparts the excellent mechanical property of polyimides, high and low temperature resistance and insulation performance etc., polyimides therefore and
It is widely used in the fields such as electronic apparatus, aerospace.On the other hand, with the development of microelectronic industry, electronic product is got over
Come be more intended to it is lightening, miniaturization, the requirement to electronic component etc. is also increasingly stringenter therewith.Such as require chip size
It is smaller and smaller, however when the size reduction of chip is to a certain size, the inductor-capacitor effect between wiring gradually increases, conducting wire
Influencing each other for electric current makes signal delay phenomenon become very eye-catching.Electronic signal delay caused in transmitting, is electronics
The material of low-k can be used as exhausted in order to reduce the delay of signal transmitting in the main reason for element speeds are limited
Edge layer, to reduce the capacitance between conducting wire, lift elements running speed and reduction noise jamming.Insulating layer blocks electric current and passes through,
And has and can avoid compared with the insulating materials of low-k in forming unnecessary stray capacitance on route.As a result, as excellent
The polyimides field of different insulating materials, developing has the Kapton of low-k particularly important.
Fluorine atom is introduced in Kapton skeleton to reduce molar polarization or on film currently, mostly using greatly
Cellular structure is constructed to reduce the dielectric constant of Kapton.Fluorine original is introduced in polyimide backbone however, only leaning against
Son, Kapton dielectric constant reduce limitation, if increasing the fluorine content in Kapton, although polyamides
The dielectric constant of imines film can decline therewith, but can sacrifice its certain intrinsic excellent performance, such as Kapton
Cementability and mechanical properties decrease, thus the application of the Kapton receives limitation.On the other hand, building porous structure is poly-
The problems such as imide membrane is related to the later period mostly and removes removing template, fabrication schedule is complicated, and because the presence of a large amount of microcellular structures causes
The mechanical properties decrease of Kapton and limit application.
Summary of the invention
It is an object of the present invention to overcome the above deficiencies, provides and a kind of is keeping intrinsic excellent of Kapton
Cementability and while mechanical property, the Kapton with low-k.
According to technical solution provided by the invention, it can provide and a kind of keep the intrinsic mechanical property of Kapton
Meanwhile there is low-k amount Kapton.
Specifically, the present invention provides a kind of Kapton of low-k, is added into polyamic acid solution
Enter to account for the fluorine silicon dispersion liquid that its weight percent is 15~25% to be modified, further prepares low-k polyamides through salivation
Imines film, the fluorine silicon dispersion liquid are made by following methods:
(1) deionized water, NaLS, ammonium persulfate, abutting ladder poly-siloxane are added into closed reactor,
Mixed gas to the reacting kettle inner pressure that tetrafluoroethene and propylene are passed through at 70~80 DEG C is 2.5MPaG, and stirring is polymerize
Reaction, wherein the weight ratio of the deionized water, NaLS, ammonium persulfate, abutting ladder poly-siloxane be 1700~
1800:13~15:4~5:145~155；
(2) as reaction carries out, pressure decline in reaction kettle continues to be passed through tetrafluoroethene and the mixed gas of propylene is kept
Reacting kettle inner pressure is 2.49~2.51MPaG；
(3) after reaction, 10 DEG C of stopping polymerizations being cooled to, fluorine-containing abutting ladder poly-siloxane water-based emulsion is obtained；
(4) at 60~70 DEG C, solvent, decompression dehydration is added dropwise into the fluorine-containing abutting ladder poly-siloxane water-based emulsion
Rise to temperature, obtains fluorine silicon dispersion liquid；
Wherein, abutting ladder poly-siloxane structural formula are as follows:
Wherein, the integer that x is 1~5, the integer that y is 1~200.
In addition, in step (1), the deionized water, NaLS, ammonium persulfate, abutting ladder poly-siloxane
Weight ratio 1792:14:4.4:150.
In addition, in step (1), mixing speed 300rpm.
In addition, the molar ratio of tetrafluoroethene and propylene is 85~90:10~12 in mixed gas, in step in step (1)
Suddenly in (2), the molar ratio of tetrafluoroethene and propylene is 54~58:42~46 in mixed gas.
Further, in step (1), the molar ratio of tetrafluoroethene and propylene is 88:12 in mixed gas, in step (2)
In, the molar ratio of tetrafluoroethene and propylene is 56:44 in mixed gas.
In addition, setting the weight ratio of abutting ladder poly-siloxane and mixed gas as 145~155:600 in step (3)
Shi Fanying terminates.
In addition, the weight ratio of fluorine-containing abutting ladder poly-siloxane water-based emulsion and solvent is 1000 in step (4):
1300~1500.
It is made in addition, the polyamic acid reacts for dibasic anhydride with diamine in a solvent；
Further, the dibasic anhydride is pyromellitic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,3 ', 3,4 '-
Bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3 ', 6,7 '-naphthalenetetracarbacidic acidic dianhydrides, pyridine -2,3,
One or more of 5,6- tetracarboxylic acid dianhydride；
Further, the diamine be p-phenylenediamine, m-phenylene diamine (MPD), benzidine, p dimethylamine, 4,4 '-two
Aminodiphenyl base ether, 3,4 '-diamino-diphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfones, 3,
3 '-dimethyl -4,4 '-diaminodiphenyl-methane, 1,5 '-diaminonaphthalenes, 3,3 '-dimethoxy benzidines, 1,4 '-bis- (3-
- 5 aminophenyl of methyl) one or more of benzene and the amide formative derivative of above-mentioned diamine；
Further, the solvent is pyrrolidones series solvent, phenol system solvent or hexamethyl phosphoramide, the non-matter of r- butyrolactone
One or more of sub- property polar solvent.
Further, as the concrete example of solvent, solvent can be n,N-dimethylacetamide, N, N- dimethyl formyl
One or more of amine, N-Methyl pyrrolidone, dimethyl acetamide, dimethyl sulfoxide.
Further, the molar ratio of the dibasic anhydride and diamine is 1.1~1.0:1.
The present invention also provides low dielectric coefficient polyimide films made from a kind of preparation method as described above.
In the present invention, the fluorine silicon dispersion liquid as made from specific reaction as described above, using big tomb electronics ELS-2000
It is tested using dynamic light scattering method, solid content was surveyed after cooling in a using 105 degree of heated air circulation type baking oven * 3 hours
Examination, average grain diameter are 75nm or so, and the solid content of the water-based emulsion is 30% or so.
In the present invention, when preparing polyamic acid solution, each constituent concentration is not particularly limited, preferably dibasic anhydride and binary
The mass fraction of amine is respectively 5~10%, thus can sufficiently keep the good dispersibility of each ingredient, not easy to reunite, forms molecule
The polyamic acid solution of narrowly distributing is measured, the polyamic acid solution with good fluidity is further obtained, is conducive to subsequent addition
Fluorine silicon dispersion liquid is modified reaction.Furthermore it is preferred that the molar ratio of dibasic anhydride and diamine is 1.1~1.0:1, it is micro- in dibasic anhydride
In excessive situation, the polyimides of acid anhydride sealing end can be formed, is better than the polyimides of amine sealing end in mechanical property, therefore excellent
Selecting the molar ratio of dibasic anhydride and diamine is 1.1~1.0:1.
Further, the present invention is modified polyamic acid solution by the silicon-fluorine polymer object of specific structure and obtains low dielectric
The Kapton of constant.According to Clausius-Mosottid equation, the dielectric constant of material and mole polarizability and mole
Volume is closely related, if molecular symmetry is good, is not easy to be polarized in extra electric field, and material has lower dielectric normal
Number.Therefore, in the present invention, preferentially select molecular symmetry good as the dibasic anhydride of synthesizing polyamides acid solution and diamine
Dibasic anhydride and diamine.In addition, for the flucride siloxane polymer architecture of modified polyimide as it appears from the above, tool in the present invention
There is very excellent molecular symmetry.Also, the flucride siloxane polymer has biggish molecular volume, is formed in the molecule
Stronger steric hindrance can inhibit the morphotropism of Kapton, cause the more difficult polarization of polyimide molecule, so as to drop
Its low dielectric constant, and the cavity structure that abutting ladder poly-siloxane has also increases the microscopic void of Kapton
Rate makes modified Kapton that lower dielectric constant be presented to reduce its molar density.On the other hand, usually
In the case of, fluorine atom is directly bonded to a degree of adhesive property for destroying Kapton of the meeting on polyimide backbone,
However, the present invention for modified fluorine atom not Direct Bonding in polyimide backbone, but with the poly- silicon oxygen of abutting ladder poly
Alkane bonds together to form silicon-fluorine polymer object, to maintain the excellent adhesive property of Kapton.In addition, being bonded with fluorine atom
There is certain molecular separating force, so that it is thin to improve polyimides between abutting ladder poly-siloxane and polyimide molecule skeleton
The mechanical property of film itself.
Beneficial effects of the present invention: the present invention is first by carrying out it to the bonded fluorine element of abutting ladder poly-siloxane
It is modified to obtain silicon-fluorine polymer object, it is further modified to polyamic acid solution by the silicon-fluorine polymer object, further obtained by film forming
Fluorinated silicone modified Kapton, the Kapton have lower dielectric constant, and maintain polyamides Asia
The excellent adhesive property of amine film and mechanical property.
Specific embodiment
It enumerates embodiment more specifically to illustrate the present invention, but the present invention is not by any limit of these embodiments
System, in the technical concept of the present invention, those skilled in the art can carry out various deformation.
In various embodiments of the present invention, the structural formula of abutting ladder poly-siloxane is as follows, only repeats in each embodiment
Element number x and y are different.
Embodiment 1
It is de-gassed inside the stainless steel pressure-resistant reaction vessel for the internal volume 3000ml for having stirring anchor formula blade
Later, deionized water, 14g NaLS, the Ammonium Persulfate 98.5 of 4.4g and the 150g bridge of 1792g are added in the reactor
Base ladder polysiloxane (x=5, y=100).Then, at 75 DEG C, indentation tetrafluoroethene (TFE)/propylene (being denoted as P below)=
The monomer mixed gas of 88/12 (molar ratio) is so that reactor internal pressure becomes 2.5MPaG.Revolve anchor formula blade with 300rpm
Turn, initiated polymerization.
With the progress of polymerization, pressure reduction in reactor, therefore dropped in the internal pressure of reactor
The time point of 2.49MPaG makes inside reactor in the monomer mixed gas from pressure indentation TFE/P=56/44 (molar ratio)
Until pressure rises to 2.51MMPaG.Repeat the operation, keep reactor internal pressure be 2.49~2.51MPaG, continue into
Row polymerization reaction.The time point for being 600g in the total amount of the monomer entrained gas intrusion of TFE/P, by the internal temperature of reactor
10 DEG C are cooled to, stops polymerization reaction, obtains fluorine-containing abutting ladder poly-siloxane water-based emulsion.Polymerization speed is 73g/L.h, should
Water-based emulsion solid content is 30%, partial size 75nm.
The above-mentioned fluorine-containing abutting ladder poly-siloxane water-based emulsion of 1000g is taken to put into the 2L glass glass bottle with stirring,
It is warming up to 70 DEG C in the case of stirring, and is slowly added into the DMAC of 1400g by dropping funel, the shape stirred later at 70 DEG C
Decompression dehydration is carried out under state, controls the pressure of decompression, prevents from foaming.Being dehydrated the point that extremely evaporation balances always, (temperature is bright in system
It is aobvious to rise), adjusting final solid content by DMAC is 20%, and solid content is tested for * 1 hour using 150 DEG C in the process.Most
The fluorine silicon dispersion liquid that solid content is 20% in DMAC is obtained eventually.
421.65g (450ml) solvent n,N-dimethylacetamide (DMAC) is added in dry there-necked flask, leads to nitrogen and protects
Shield, add 4,4 '-diaminodiphenyl ether (ODA) of 38g (200mmol), stir, it is to be dissolved sufficiently after, be added 45.78g
After fully reacting is abundant the above-mentioned fluorine silicon dispersion liquid of 101.08g is added, to anti-in the pyromellitic acid dianhydride (PMDA) of (210mmol)
After the completion of answering；Solution coating is toasted to film forming (Kapton) on the glass substrate.The technique of baking are as follows: 80 degree 1 small
When, 150 degree 20 minutes, 250 degree 20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate, test dielectric is normal
The performances such as number, peel strength, tensile strength, initial modulus, surface tension, the results are shown in Table 1.
Embodiment 2
It is de-gassed inside the stainless steel pressure-resistant reaction vessel for the internal volume 3000ml for having stirring anchor formula blade
Later, deionized water, 13g NaLS, the Ammonium Persulfate 98.5 of 4.0g and the 150g bridge of 1700g are added in the reactor
Base ladder polysiloxane (x=3, y=200).Then, at 75 DEG C, indentation tetrafluoroethene (TFE)/propylene (being denoted as P below)=
The monomer mixed gas of 85/10 (molar ratio) is so that reactor internal pressure becomes 2.5MPaG.Revolve anchor formula blade with 300rpm
Turn, initiated polymerization.
With the progress of polymerization, pressure reduction in reactor, therefore dropped in the internal pressure of reactor
The time point of 2.49MPaG makes inside reactor in the monomer mixed gas from pressure indentation TFE/P=58/46 (molar ratio)
Until pressure rises to 2.51MMPaG.Repeat the operation, keep reactor internal pressure be 2.49~2.51MPaG, continue into
Row polymerization reaction.The time point for being 600g in the total amount of the monomer entrained gas intrusion of TFE/P, by the internal temperature of reactor
10 DEG C are cooled to, stops polymerization reaction, obtains fluorine-containing abutting ladder poly-siloxane water-based emulsion.Polymerization speed is 71g/L.h, should
Water-based emulsion solid content is 31%, partial size 75nm.
The above-mentioned fluorine-containing abutting ladder poly-siloxane water-based emulsion of 1000g is taken to put into the 2L glass glass bottle with stirring,
It is warming up to 70 DEG C in the case of stirring, and is slowly added into the DMAC of 1300g by dropping funel, the shape stirred later at 70 DEG C
Decompression dehydration is carried out under state, controls the pressure of decompression, prevents from foaming.Being dehydrated the point that extremely evaporation balances always, (temperature is bright in system
It is aobvious to rise), adjusting final solid content by DMAC is 20%, and solid content is tested for * 1 hour using 150 DEG C in the process.Most
The fluorine silicon dispersion liquid that solid content is 20% in DMAC is obtained eventually.
421.65g (450ml) solvent n,N-dimethylacetamide (DMAC) is added in dry there-necked flask, leads to nitrogen and protects
Shield, add 4,4 '-diaminodiphenyl ether (ODA) of 38g (200mmol), stir, it is to be dissolved sufficiently after, be added 45.78g
After fully reacting is abundant the above-mentioned fluorine silicon dispersion liquid of 75.81g is added, to anti-in the pyromellitic acid dianhydride (PMDA) of (210mmol)
After the completion of answering；Solution coating is toasted to film forming (Kapton) on the glass substrate.The technique of baking are as follows: 80 degree 1 small
When, 150 degree 20 minutes, 250 degree 20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate, test dielectric is normal
The performances such as number, peel strength, tensile strength, initial modulus, surface tension, the results are shown in Table 1.
Embodiment 3
It is de-gassed inside the stainless steel pressure-resistant reaction vessel for the internal volume 3000ml for having stirring anchor formula blade
Later, deionized water, 15g NaLS, the Ammonium Persulfate 98.5 of 5.0g and the 155g bridge of 1800g are added in the reactor
Base ladder polysiloxane (x=5, y=150).Then, at 75 DEG C, indentation tetrafluoroethene (TFE)/propylene (being denoted as P below)=
The monomer mixed gas of 90/12 (molar ratio) is so that reactor internal pressure becomes 2.5MPaG.Revolve anchor formula blade with 300rpm
Turn, initiated polymerization.
With the progress of polymerization, pressure reduction in reactor, therefore dropped in the internal pressure of reactor
The time point of 2.49MPaG makes inside reactor in the monomer mixed gas from pressure indentation TFE/P=54/42 (molar ratio)
Until pressure rises to 2.51MMPaG.Repeat the operation, keep reactor internal pressure be 2.49~2.51MPaG, continue into
Row polymerization reaction.The time point for being 600g in the total amount of the monomer entrained gas intrusion of TFE/P, by the internal temperature of reactor
10 DEG C are cooled to, stops polymerization reaction, obtains fluorine-containing abutting ladder poly-siloxane water-based emulsion.Polymerization speed is 75g/L.h, should
Water-based emulsion solid content is 32%, partial size 75nm.
The above-mentioned fluorine-containing abutting ladder poly-siloxane water-based emulsion of 1000g is taken to put into the 2L glass glass bottle with stirring,
It is warming up to 70 DEG C in the case of stirring, and is slowly added into the DMAC of 1500g by dropping funel, the shape stirred later at 70 DEG C
Decompression dehydration is carried out under state, controls the pressure of decompression, prevents from foaming.Being dehydrated the point that extremely evaporation balances always, (temperature is bright in system
It is aobvious to rise), adjusting final solid content by DMAC is 20%, and solid content is tested for * 1 hour using 150 DEG C in the process.Most
The fluorine silicon dispersion liquid that solid content is 20% in DMAC is obtained eventually.
421.65g (450ml) solvent n,N-dimethylacetamide (DMAC) is added in dry there-necked flask, leads to nitrogen and protects
Shield, add 4,4 '-diaminodiphenyl ether (ODA) of 38g (200mmol), stir, it is to be dissolved sufficiently after, be added 45.78g
After fully reacting is abundant the above-mentioned fluorine silicon dispersion liquid of 126.35g is added, to anti-in the pyromellitic acid dianhydride (PMDA) of (210mmol)
After the completion of answering；Solution coating is toasted to film forming (Kapton) on the glass substrate.The technique of baking are as follows: 80 degree 1 small
When, 150 degree 20 minutes, 250 degree 20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate, test dielectric is normal
The performances such as number, peel strength, tensile strength, initial modulus, surface tension, the results are shown in Table 1.
Embodiment 4
It is de-gassed inside the stainless steel pressure-resistant reaction vessel for the internal volume 3000ml for having stirring anchor formula blade
Later, deionized water, 14g NaLS, the Ammonium Persulfate 98.5 of 4.4g and the 150g bridge of 1792g are added in the reactor
Base ladder polysiloxane (x=5, y=100).Then, at 75 DEG C, indentation tetrafluoroethene (TFE)/propylene (being denoted as P below)=
The monomer mixed gas of 88/12 (molar ratio) is so that reactor internal pressure becomes 2.5MPaG.Revolve anchor formula blade with 300rpm
Turn, initiated polymerization.
With the progress of polymerization, pressure reduction in reactor, therefore dropped in the internal pressure of reactor
The time point of 2.49MPaG makes inside reactor in the monomer mixed gas from pressure indentation TFE/P=56/44 (molar ratio)
Until pressure rises to 2.51MMPaG.Repeat the operation, keep reactor internal pressure be 2.49~2.51MPaG, continue into
Row polymerization reaction.The time point for being 600g in the total amount of the monomer entrained gas intrusion of TFE/P, by the internal temperature of reactor
10 DEG C are cooled to, stops polymerization reaction, obtains fluorine-containing abutting ladder poly-siloxane water-based emulsion.Polymerization speed is 73g/L.h, should
Water-based emulsion solid content is 30%, partial size 75nm.
The above-mentioned fluorine-containing abutting ladder poly-siloxane water-based emulsion of 1000g is taken to put into the 2L glass glass bottle with stirring,
It is warming up to 70 DEG C in the case of stirring, and is slowly added into the DMAC of 1400g by dropping funel, the shape stirred later at 70 DEG C
Decompression dehydration is carried out under state, controls the pressure of decompression, prevents from foaming.Being dehydrated the point that extremely evaporation balances always, (temperature is bright in system
It is aobvious to rise), adjusting final solid content by DMAC is 20%, and solid content is tested for * 1 hour using 150 DEG C in the process.Most
The fluorine silicon dispersion liquid that solid content is 20% in DMAC is obtained eventually.
421.65g (450ml) solvent n,N-dimethylacetamide (DMAC) is added in dry there-necked flask, leads to nitrogen and protects
Shield, add 3,4 '-diamino-diphenyl ether of 26.31g (130mmol), stir, it is to be dissolved sufficiently after, be added 42.165g
The above-mentioned fluorine silicon dispersion liquid of 98.02g is added after fully reacting is abundant in (143mmol) 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride,
To after the reaction was completed；Solution coating is toasted to film forming (Kapton) on the glass substrate.The technique of baking are as follows: 80 degree 1
A hour, 150 degree 20 minutes, 250 degree 20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate, tests dielectric
The performances such as constant, peel strength, tensile strength, initial modulus, surface tension, the results are shown in Table 1.
Embodiment 5
It is de-gassed inside the stainless steel pressure-resistant reaction vessel for the internal volume 3000ml for having stirring anchor formula blade
Later, deionized water, 14g NaLS, the Ammonium Persulfate 98.5 of 4.4g and the 150g bridge of 1792g are added in the reactor
Base ladder polysiloxane (x=5, y=100).Then, at 75 DEG C, indentation tetrafluoroethene (TFE)/propylene (being denoted as P below)=
The monomer mixed gas of 88/12 (molar ratio) is so that reactor internal pressure becomes 2.5MPaG.Revolve anchor formula blade with 300rpm
Turn, initiated polymerization.
With the progress of polymerization, pressure reduction in reactor, therefore dropped in the internal pressure of reactor
The time point of 2.49MPaG makes inside reactor in the monomer mixed gas from pressure indentation TFE/P=56/44 (molar ratio)
Until pressure rises to 2.51MMPaG.Repeat the operation, keep reactor internal pressure be 2.49~2.51MPaG, continue into
Row polymerization reaction.The time point for being 600g in the total amount of the monomer entrained gas intrusion of TFE/P, by the internal temperature of reactor
10 DEG C are cooled to, stops polymerization reaction, obtains fluorine-containing abutting ladder poly-siloxane water-based emulsion.Polymerization speed is 73g/L.h, should
Water-based emulsion solid content is 30%, partial size 75nm.
The above-mentioned fluorine-containing abutting ladder poly-siloxane water-based emulsion of 1000g is taken to put into the 2L glass glass bottle with stirring,
It is warming up to 70 DEG C in the case of stirring, and is slowly added into the DMAC of 1400g by dropping funel, the shape stirred later at 70 DEG C
Decompression dehydration is carried out under state, controls the pressure of decompression, prevents from foaming.Being dehydrated the point that extremely evaporation balances always, (temperature is bright in system
It is aobvious to rise), adjusting final solid content by DMAC is 20%, and solid content is tested for * 1 hour using 150 DEG C in the process.Most
The fluorine silicon dispersion liquid that solid content is 20% in DMAC is obtained eventually.
426.6g (450ml) solvent n,N-Dimethylformamide is added in dry there-necked flask, logical nitrogen protection adds
4,4 '-diaminodiphenyl ether (ODA) of 31.334g (158mmol), stirring, it is to be dissolved sufficiently after, be added 51.192g (158mmol)
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, after fully reacting is abundant, be added the above-mentioned fluorine silicon dispersion liquid of 101.83g, to
After the reaction was completed；Solution coating is toasted to film forming (Kapton) on the glass substrate.The technique of baking are as follows: 80 degree 1
Hour, 150 degree 20 minutes, 250 degree 20 minutes, 400 degree 10 minutes.After cooling, film is removed from substrate, test dielectric is normal
The performances such as number, peel strength, tensile strength, initial modulus, surface tension, the results are shown in Table 1.
Embodiment 6
It is de-gassed inside the stainless steel pressure-resistant reaction vessel for the internal volume 3000ml for having stirring anchor formula blade
Later, deionized water, 14g NaLS, the Ammonium Persulfate 98.5 of 4.4g and the 150g bridge of 1792g are added in the reactor
Base ladder polysiloxane (x=5, y=100).Then, at 75 DEG C, indentation tetrafluoroethene (TFE)/propylene (being denoted as P below)=
The monomer mixed gas of 88/12 (molar ratio) is so that reactor internal pressure becomes 2.5MPaG.Revolve anchor formula blade with 300rpm
Turn, initiated polymerization.
With the progress of polymerization, pressure reduction in reactor, therefore dropped in the internal pressure of reactor
The time point of 2.49MPaG makes inside reactor in the monomer mixed gas from pressure indentation TFE/P=56/44 (molar ratio)
Until pressure rises to 2.51MMPaG.Repeat the operation, keep reactor internal pressure be 2.49~2.51MPaG, continue into
Row polymerization reaction.The time point for being 600g in the total amount of the monomer entrained gas intrusion of TFE/P, by the internal temperature of reactor
10 DEG C are cooled to, stops polymerization reaction, obtains fluorine-containing abutting ladder poly-siloxane water-based emulsion.Polymerization speed is 73g/L.h, should
Water-based emulsion solid content is 30%, partial size 75nm.
The above-mentioned fluorine-containing abutting ladder poly-siloxane water-based emulsion of 1000g is taken to put into the 2L glass glass bottle with stirring,
It is warming up to 70 DEG C in the case of stirring, and is slowly added into the DMAC of 1400g by dropping funel, the shape stirred later at 70 DEG C
Decompression dehydration is carried out under state, controls the pressure of decompression, prevents from foaming.Being dehydrated the point that extremely evaporation balances always, (temperature is bright in system
It is aobvious to rise), adjusting final solid content by DMAC is 20%, and solid content is tested for * 1 hour using 150 DEG C in the process.Most
The fluorine silicon dispersion liquid that solid content is 20% in DMAC is obtained eventually.
462.6g (450ml) solvent N-methyl pyrilidone is added in dry there-necked flask, logical nitrogen protection adds
22.93g (212mmol) m-phenylene diamine (MPD), stirring, it is to be dissolved sufficiently after, be added 46.26g (212mmol) pyromellitic acid dianhydride
(PMDA), after fully reacting is abundant, the above-mentioned fluorine silicon dispersion liquid of 106.36g is added, to after the reaction was completed；By solution coating in glass
Baking film forming (Kapton) on glass substrate.The technique of baking are as follows: 80 degree of 1 hours, 150 degree 20 minutes, 250 degree 20 points
Clock, 400 degree 10 minutes.After cooling, film is removed from substrate, tests dielectric constant, peel strength, tensile strength, surface
The performances such as tension, the results are shown in Table 1.
Comparative example 1
Other than adding fluorine silicon dispersion liquid not into polyamic acid solution when preparing Kapton, with embodiment 1
It is identical.
Comparative example 2
Other than adding fluorine silicon dispersion liquid not into polyamic acid solution when preparing Kapton, with embodiment 4
It is identical.
Comparative example 3
When preparing Kapton, added outside 202.17g fluorine silicon dispersion liquid into polyamic acid solution, with embodiment
1 is identical.
Test case
(1) dielectric constant (Dk) and fissipation factor (Df) test: sample to be tested is impregnated 10 minutes in deionized water, is connect
Be placed in baking oven to toast with about 110 DEG C of temperature and be dried for about 30 minutes, with precise impedance analyzer (model
Agilent4294A the Dk/Df value of the test sample) is measured.
(2) peel strength test: Kapton configuration, which is cut into width together with copper foil on copper foil, is
The test sample of 0.3175mm.Then, using universal testing machine, (Shimadzu scientific instrument limited liability company (SHIMADZU) is made
Make, the entitled AG-1S of equipment), under conditions of tensile speed is set as 50.8mm/min, those test samples are stretched to stretching
Length is 30mm, obtains peel strength (kgf/cm) at this time.
(3) surface tension: dyne pen test；
(4) thermal expansion coefficient: Mei Tele company static heat mechanical tester TMA/SDTA 2+ is used, in measuring temperature model
Enclosing is 50-200 DEG C, and heating rate measures under conditions of being 10 DEG C/min；
(5) Kapton is fabricated to the membrane material that length and width dimensions are 25.4mm × 3.2mm respectively, uses universal test
Machine (being manufactured by Shimadzu scientific instrument limited liability company (SHIMADZU), the entitled AG-1S of equipment) is strong to measure the tension of membrane material
Spend (MPa), elongation (%).
Table 1
By the embodiment 1-6 of table 1 it is found that specific the present invention is added in polyamic acid solution compared with comparative example 1-2
Silicon-fluorine polymer object forms a film after being modified, and the dielectric constant of Kapton is decreased obviously, fissipation factor reduces, while polyamides
Imines film maintains good adhesive property and does not change, and mechanical property is also improved to some extent.In addition, by implementing
Example 1-3 and embodiment 4-6 can be seen that the adding proportion increase with silicon-fluorine polymer object, and dielectric constant decreases, cementability
Can be constant, mechanical property increases therewith；On the other hand, it when silicon-fluorine polymer object adding proportion is significantly increased, such as increases to
Comparative example 3 40% when, although dielectric produce constant be greatly reduced, fissipation factor obviously increases, cementability and mechanical property
Also it is affected, it will limit its application.
Claims (10)
1. a kind of preparation method of low dielectric coefficient polyimide film, which is characterized in that it is added into polyamic acid solution
Enter to account for the fluorine silicon dispersion liquid that its weight percent is 15~25% to be modified, further prepares low-k polyamides through salivation
Imines film, the fluorine silicon dispersion liquid are made by following methods:
(1) deionized water, NaLS, ammonium persulfate, abutting ladder poly-siloxane are added into closed reactor, 70
Mixed gas to the reacting kettle inner pressure that tetrafluoroethene and propylene are passed through at~80 DEG C is 2.5MPaG, and stirring carries out polymerization reaction,
Wherein the deionized water, NaLS, ammonium persulfate, abutting ladder poly-siloxane weight ratio be 1700~1800:
13~15:4~5:145~155；
(2) as reaction carries out, pressure decline in reaction kettle continues to be passed through tetrafluoroethene and react with the holding of the mixed gas of propylene
Pressure is 2.49~2.51MPaG in kettle；
(3) after reaction, 10 DEG C of stopping polymerizations being cooled to, fluorine-containing abutting ladder poly-siloxane water-based emulsion is obtained；
(4) at 60~70 DEG C, solvent, decompression dehydration to temperature is added dropwise into the fluorine-containing abutting ladder poly-siloxane water-based emulsion
Degree rises, and obtains fluorine silicon dispersion liquid；
Wherein, abutting ladder poly-siloxane structural formula are as follows:
Wherein, the integer that x is 1~5, the integer that y is 1~200.
2. preparation method according to claim 1, which is characterized in that in step (1), the deionized water, lauryl
Sodium sulphate, ammonium persulfate, abutting ladder poly-siloxane weight ratio 1792:14:4.4:150.
3. preparation method according to claim 1, which is characterized in that in step (1), mixing speed 300rpm.
4. preparation method according to claim 1, which is characterized in that in step (1), in mixed gas tetrafluoroethene with
The molar ratio of propylene is 85~90:10~12, and in step (2), the molar ratio of tetrafluoroethene and propylene is 54 in mixed gas
~58:42~46.
5. the preparation method according to claim 4, which is characterized in that in step (1), in mixed gas tetrafluoroethene with
The molar ratio of propylene is 88:12, and in step (2), the molar ratio of tetrafluoroethene and propylene is 56:44 in mixed gas.
6. preparation method according to claim 1, which is characterized in that in step (3), set abutting ladder poly-siloxane
Terminate with the weight ratio of mixed gas to be reacted when 145~155:600.
7. preparation method according to claim 1, which is characterized in that in step (4), fluorine-containing abutting ladder poly-siloxane
The weight ratio of water-based emulsion and solvent is 1000:1300~1500.
8. preparation method according to claim 1, which is characterized in that the polyamic acid is dibasic anhydride and diamine molten
It reacts and is made in agent；
Dibasic anhydride be pyromellitic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 2,3 ', 3,4 '-bibenzene tetracarboxylic dianhydrides, 3,
3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,3 ', 6,7 '-naphthalenetetracarbacidic acidic dianhydrides, in pyridine -2,3,5,6- tetracarboxylic acid dianhydride
It is one or more of；
The diamine be p-phenylenediamine, m-phenylene diamine (MPD), benzidine, p dimethylamine, 4,4 '-diamino-diphenyl ethers,
3,4 '-diamino-diphenyl ethers, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino diphenyl sulfones, 3,3 '-dimethyl -4,
4 '-diaminodiphenyl-methanes, 1,5 '-diaminonaphthalenes, 3,3 '-dimethoxy benzidines, Isosorbide-5-Nitrae '-bis- (- 5 aminobenzenes of 3- methyl
Base) one or more of benzene and the amide formative derivative of above-mentioned diamine；
The solvent is pyrrolidones series solvent, phenol system solvent or hexamethyl phosphoramide, r- butyrolactone aprotic polar solvent
One or more of.
9. preparation method according to claim 8, which is characterized in that the molar ratio of the dibasic anhydride and diamine is 1.1
~1.0:1.
10. low dielectric coefficient polyimide film made from a kind of preparation method as described in any one of claim 1-9.
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| CN111081470A (en) * | 2019-12-19 | 2020-04-28 | 南京中鸿润宁新材料科技有限公司 | Polyimide capacitor |
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