CN100532429C - Method for preparing polyimide with ultra-low dielectric constant - Google Patents

Method for preparing polyimide with ultra-low dielectric constant Download PDF

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CN100532429C
CN100532429C CNB2007100323084A CN200710032308A CN100532429C CN 100532429 C CN100532429 C CN 100532429C CN B2007100323084 A CNB2007100323084 A CN B2007100323084A CN 200710032308 A CN200710032308 A CN 200710032308A CN 100532429 C CN100532429 C CN 100532429C
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polyoxometallate
dielectric constant
ultra
polyimide
low dielectric
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CN101186698A (en
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赵建青
谭麟
曾钫
刘述梅
叶华
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South China University of Technology SCUT
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Abstract

The invention discloses a process for preparing medlin with ultra-low dielectric constant, which comprises following procedures: charging gamma-propyl triethoxysilicane coupling agent in the multimetallic chlorocate solution in order to prepare multimetallic chlorocate or siliconiting hybridization material, charging the multimetallic chlorocate or siliconiting hybridization material in polyamic acid solution, mixing for 20-24h, coating film, keeping 80DEG C for 2h in -0.1 MPa vacuum condition, keeping 100DEG C for 1h, keeping 200DEG C for 1h and keeping 300DEG C for an hour in order to imide, cooling, getting medlin with ultra-low dielectric constant. The dielectric constant of the prepared medlin can be reduced to less than 2, while the thermal property and the mechanical property are improved, the dielectric constant of the medlin with PMDA and ODA as the monomer is reduced to 1.42 when the multimetallic chlorocate or siliconiting hybridization material is 20%, and Tq is improved by 80DEG C, Young's modulus is improved by 110%.

Description

The preparation method of polyimide with ultra-low dielectric constant
Technical field
The present invention relates to the preparation method of polyimide (PI), specifically relate to the preparation method of a series of polyimide with ultra-low dielectric constant.
Background technology
Polyimide replaces silicon-dioxide and obtains extensive studies as electronic apparatus with the potential material of dielectric materials owing to its outstanding high temperature resistance, chemical resistance, favorable mechanical performance and excellent chemical property become.The specific inductivity of pure polyimide is between 3.0-3.4, be lower than the specific inductivity of silicon-dioxide, but,, the too high specific inductivity of semi-conductor offset the raising of the large-scale integrated circuit performance that preparation technology's progress causes greatly because causing speed that resistance-capacitance delays (RC delay) is brought and power loss along with the large-scale integrated circuit technology of preparing enters below the 100nm.Therefore optimization design by circuit structure can not address this problem well, develops specific inductivity and is lower than the focus that 2.0 type material becomes people's research.
The specific inductivity that reduces polyimide mainly contains two kinds of methods: (1) selects the monomer synthesis of polyimides of nonpolar symmetrical configuration for use; (2) in polyimide, introduce the nanometer cavity.Preparation nanoporous polyimide mainly is but that the component of introducing thermal destruction produces the nanometer cavity and inserts the hybrid material that contains nanometer micropore both at home and abroad, but up to the present still do not solve easily problem such as reunions of mechanical properties decrease that thermal destruction causes and nano-hybrid material, the while specific inductivity is not reduced to the degree of desirable.
(Polyoxometalates is to connect a class multi-metal oxygen cluster compound that forms by oxygen by the early transition metal ion POM) to polyoxometallate.The scope of polyoxometallate, dominant species are V (V), Mo (VI), W (VI) polyanionic; Also have Nb (V), Ta (V), Ti oxometallates such as (IV) in addition.Keggin structure polyoxometallate, its general formula can be expressed as [XY 12O 40] N-(X=P, Si, Ge, As ..., Y=Mo, W).Wells-Dawson structure is derived by the condensation of two Keggin polyanionics, and its general formula is [XY 18O 60] N-Saturated polyoxometallate can degraded disappearance YO under acidic conditions 2Metal cluster lacks a YO 2The time be called single vacant polyoxometallate, lack two YO 2The time be called two vacant polyoxometallates.Have only when polyoxometallate is in enough nucleophilicities are just arranged under the vacant state, can pass through the covalent bonds organic molecule.
Summary of the invention
The object of the present invention is to provide the preparation specific inductivity to be lower than 2.0, simultaneously mechanical property and thermal property are kept even the method for the polyimide material that improves, to solve the problem that heat, mechanical property and dielectric properties that present polyimide material exists can not be taken into account.
To achieve the above object of the invention, the present invention has taked following technical scheme:
The preparation method of polyimide with ultra-low dielectric constant comprises the steps:
(1) the γ-An Bingjisanyiyangjiguiwan coupling agent being joined the quality percentage composition is in 1%～3% the polyoxometallic acid salt brine solution, regulating the pH value is 1～2,20～40 ℃ of reaction 20～24h, remove by filter γ-An Bingjisanyiyangjiguiwan hydrolysis autopolymer, filtrate underpressure distillation under nitrogen protection removes desolvates, recrystallization in ether obtains polyoxometallate/silane hybrid material then; The silane coupling agent add-on is 10～20 times of polyoxometallate molar weight; Described polyoxometallate is the K of the Keggin structure of single omission or two omissions 8XY 11O 39Or K 8XY 10O 36, wherein X=Si, P; Y=W, Mo; Perhaps be the K of the Dawson structure of single omission or two omissions 6XY 17O 58Or K 6X 2Y 16O 56, wherein X=Si, P; Y=W, Mo.
(2) polyoxometallate/silane hybrid material of step (1) gained is joined previously prepared, be in the polyamic acid solution of solvent with the N-Methyl pyrrolidone, after stirring 16～24h under 20～40 ℃, film, vacuum tightness is-the following 80 ℃ of heating 2h of vacuum condition of 0.1MPa, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ of heating 1h hot-imides, and the cooling back is the polyimide with ultra-low dielectric constant film; Wherein polyoxometallate/silane hybrid material is pressed 5%～20% adding of polyamic acid quality.
The K of the Keggin structure of described single omission or two omissions 8XY 11O 39Or K 8XY 10O 36Polyoxometallate is prepared by following method: be dissolved in the water with Starso and sodium wolframate or with sodium phosphate and the Sodium orthomolybdate mol ratio with 1:11, with salt acid for adjusting pH value to 5～6, add KCl and obtain single vacant Keggin structure polyoxometallate; Single vacant Keggin structure polyoxometallic acid salt brine solution K 2CO 3The aqueous solution is regulated pH value to 9～11, adds KCl and obtains two vacant Keggin structure polyoxometallates.
The K of the Dawson structure of described single omission or two omissions 6XY 17O 58Or K 6X 2Y 16O 56Polyoxometallate is prepared by following method: be dissolved in the water with Starso and sodium wolframate or with sodium phosphate and the Sodium orthomolybdate mol ratio with 1:18, with phosphorus acid for adjusting pH value to 5～6, add KCl and obtain single vacant Dawson structure polyoxometallate; Single Dawson structure oxygen acid salt aqueous solution K that lacks 2CO 3The aqueous solution is regulated pH value to 9～11, adds KCl and obtains two vacant Dawson structure polyoxometallates.
The preparation method of step (2) polyamic acid solution is: add the N-Methyl pyrrolidone through underpressure distillation in the there-necked flask that has the mechanical stirring slurry; add diamines then; the powerful stirring led to nitrogen protection simultaneously; after dissolving fully, diamines adds equimolar dianhydride with three equal parts; stirring at room 1h; obtain polyamic acid solution, wherein the mass percent of polyamic acid is 10%～15%
Described dianhydride is symmetrical configuration, do not contain the aromatics dianhydride pyromellitic acid anhydride, 2 of polar functional group, 2-two (trifluoromethyl) p-phenylene dianhydride.
Described diamines is symmetrical configuration, do not contain the aromatics diamines phenyl ether diamines, 2 of polar functional group, 2-two (to aminocarbonyl phenyl) propane, 2,2-two (to aminocarbonyl phenyl)-two (trifluoromethyl) propane, 3,3,6, two pairs of aminocarbonyl phenyl methane of 6-tetramethyl-
Compared with prior art, the present invention has following advantage and beneficial effect:
The prepared polymide dielectric constant of the present invention can be reduced to below 2, thermal property and mechanical property also are improved simultaneously, when polyoxometallate/when silane hybrid material add-on is 20%, with PMDA and ODA is monomeric polyimide, specific inductivity is reduced to 1.42, Tg has improved 80 ℃ simultaneously, and Young's modulus improves 110%; With 6FBA and 6FDA is monomeric polyimide, and its specific inductivity is reduced to 1.25, and mechanics and thermal property also obtain raising in various degree.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the related scope of embodiment.
Embodiment 1
In the 1000ml there-necked flask, add 300ml distilled water, 182g Na 2WO 4.2H 2O stirs, and treats that solution clarification back slowly drips 4mol/l hydrochloric acid 165ml, dropwises the back and adds 14.6g Na 2SiO 39H 2O/100ml H 2O is adjusted to 5.5 and kept 1 hour with the pH value with 4mol/l HCl, adds 75g KCl then, filters, and white precipitate vacuum-drying obtains the K of single vacant Keggin structure 8SiW 11O 39
The above-mentioned product that takes by weighing 1mmol is dissolved in 1000ml H 2Among the O; slowly drip the γ-An Bingjisanyiyangjiguiwan (KH-550 of 20mmol; excessive 10 times); wait to dropwise the back and the pH value is adjusted to 1.0 with 2mol/l HCl; 20 ℃ were stirred 24 hours down, removed by filter the siloxanes autopolymer, and removal of solvent under reduced pressure obtains white solid under the nitrogen protection; the ether recrystallization obtains [KH550] 2K 8SiW 11O 39, yield 42%.
Embodiment 2
In the 500ml there-necked flask, add 5mmol K 8SiW 11O 39, 200ml H 2O uses 2mol/l K under the vigorous stirring 2CO 3The pH value is adjusted to 9.1 and keep 18min, adds 40g KCl, an amount of K that drips when noting adding KCl 2CO 3The pH value is remained unchanged.Filter, white precipitate ether recrystallization final vacuum drying obtains the K of two vacant Keggin structures 8SiW 10O 36
Take by weighing the above-mentioned product of 1mmol and be dissolved in 1000ml H 2Among the O, slowly drip 30mmol KH-550 (excessive 15 times), dropwise back pH value and be adjusted to 2 with 2mol/1HCl; 40 ℃ were stirred 20 hours down, removed by filter the siloxanes autopolymer, and removal of solvent under reduced pressure obtains white solid under the nitrogen protection; the ether recrystallization obtains [KH550] 2K 8SiW 10O 36, yield 62%.
Embodiment 3
With 113g Na 2MoO 42H 2O is dissolved in the 150ml hot water, and powerful the stirring adds 125ml H down 3PO 4(85%), solution backflow 5h adds small amount of H NO in the reflux course 3Prevent reduction reaction.Reduce to room temperature after reaction finishes and add about 70g KCl, filtering solution obtains pale yellow powder, and recrystallization in the ether obtains the K of Dawson structure 6P 2Mo 18O 60Get the above-mentioned product of 5mmol and be dissolved in 200ml H 2Under the vigorous stirring pH value used 2mol/l H among the O 3PO 4Be adjusted to 5, keep 1h, add KCl and separate out precipitation, drying obtains the K of the Dawson structure of single omission 6P 2Mo 17O 58
Take by weighing the above-mentioned product of 1mmol and be dissolved in 1000ml H 2Among the O, slowly drip 40mmol KH-550 (excessive 20 times), dropwise back pH value 2mol/l H 3PO 4Be adjusted to 1.5,30 ℃ and stirred 22 hours down, remove by filter the siloxanes autopolymer, removal of solvent under reduced pressure obtains white solid under the nitrogen protection, and the ether recrystallization obtains [KH550] 2K 6P 2Mo 17O 58, yield 54%.
Embodiment 4
In the 50ml there-necked flask, add 0.01mol phenyl ether diamines (ODA); the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection; treat that diamines dissolves the back fully and adds equimolar pyromellitic acid anhydride (PMDA) with three equal parts under the mechanical stirring, add [KH550] of polyamic acid quality 10% behind the reaction 1h 2K 8SiW 11O 39, 30 ℃ are stirred 20h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 5
In the 50ml there-necked flask, add 0.01mol phenyl ether diamines; the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection, treating that diamines dissolves under the mechanical stirring of back fully adds equimolar pyromellitic acid anhydride with three equal parts, adds [KH550] of polyamic acid quality 20% behind the reaction 1h 2K 6P 2Mo 17O 58, 20 ℃ are stirred 24h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 6
In the 50ml there-necked flask, add 0.01mol 2; 2-two (to aminocarbonyl phenyl)-two (trifluoromethyl) propane (6FBA); the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection; treat that diamines dissolves the back fully and adds equimolar 2 with three equal parts under the mechanical stirring; 2-two (trifluoromethyl) p-phenylene's dianhydride (6FDA) adds [KH550] of polyamic acid quality 5% behind the reaction 1h 2K 8SiW 10O 36, 20 ℃ are stirred 24h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 7
In the 50ml there-necked flask, add 0.01mol 2; 2-two (to aminocarbonyl phenyl)-two (trifluoromethyl) propane; the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection; treat that diamines dissolves the back fully and adds equimolar 2 with three equal parts under the mechanical stirring; 2-two (trifluoromethyl) p-phenylene dianhydride adds [KH550] of polyamic acid quality 15% behind the reaction 1h 2K 6P 2Mo 17O 58, 30 ℃ are stirred 21h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 8
In the 50ml there-necked flask, add 0.01mol 2; 2-two (to aminocarbonyl phenyl)-two (trifluoromethyl) propane; the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection; treat that diamines dissolves the back fully and adds equimolar 2 with three equal parts under the mechanical stirring; 2-two (trifluoromethyl) p-phenylene dianhydride adds [KH550] of polyamic acid quality 17% behind the reaction 1h 2K 8SiW 11O 39, 25 ℃ are stirred 22h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 9
In the 50ml there-necked flask, add 0.01mol 2; 2-two (to aminocarbonyl phenyl)-two (trifluoromethyl) propane; the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection; treat that diamines dissolves the back fully and adds equimolar 2 with three equal parts under the mechanical stirring; 2-two (trifluoromethyl) p-phenylene dianhydride adds [KH550] of polyamic acid quality 20% behind the reaction 1h 2K 8SiW 10O 36, 25 ℃ are stirred 23h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 10
In the 50ml there-necked flask, add 0.01mol 3; 3; 6; two pairs of aminocarbonyl phenyl methane of 6-tetramethyl-; the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection, treating that diamines dissolves under the mechanical stirring of back fully adds equimolar pyromellitic acid anhydride with three equal parts, adds [KH550] of polyamic acid quality 5% behind the reaction 1h 2K 8SiW 10O 36, 25 ℃ are stirred 23h down.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 11
In the 50ml there-necked flask, add 0.01mol 3; 3; 6; two pairs of aminocarbonyl phenyl methane of 6-tetramethyl-; the 20ml N-Methyl pyrrolidone; logical simultaneously nitrogen protection, treating that diamines dissolves under the mechanical stirring of back fully adds equimolar pyromellitic acid anhydride with three equal parts, adds [KH550] of polyamic acid quality 10% behind the reaction 1h 2K 6P 2Mo 17O 58, 25 ℃ are stirred 23h down, and reaction is filmed after finishing.Film after reaction finishes, vacuum tightness be-vacuum condition of 0.1MPa under, 80 ℃ of heating 2h, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ heat the 1h hot-imides, slowly cool to room temperature then, obtain Kapton.
Embodiment 4～11 Kapton performances
Kapton among the embodiment is carried out the mensuration of second-order transition temperature (Tg), specific inductivity (dielectricconstant) and Young's modulus (E '), and the result is as shown in table 1.From the table data as can be seen, the specific inductivity of polyimide can be reduced to about 2 behind interpolation polyoxometallate/silane hybrid material, thermal property and mechanical property also are improved simultaneously, with PMDA/ODA is example, when polyoxometallate/when silane hybrid material add-on is 20%, Tg has improved 80 ℃, Young's modulus has improved 110%, specific inductivity is reduced to 1.42 simultaneously, the of the same type of report is monomeric polyimide matrix with PMDA/ODA, the Nano film of multiporous polyimide of thermooxidative degradation thermally labile component preparation.When specific inductivity is reduced to 1.5 when following, its Tg then reduces about 110 ℃, and mechanical property descends more than 50% especially, is difficult to satisfy the requirement of electronic industry to dielectric materials.Therefore this class polyoxometallate/polyimide material will become replacement electronic apparatus SiO 2Ideal material.
Table 1 embodiment Kapton performance table
P Pure PI Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11
Tg(℃) 317 383 390 331 387 325 336 357 386
Specific inductivity 3.49 1.63 1.42 2.01 1.49 1.32 1.25 2.12 1.58
E’(GPa) 1.6 3.4 3.6 2.8 4.0 2.8 3.2 2.7 3.3
PI-Polyimide (polyimide)
Tg-second-order transition temperature
Temperature rise rate is 10 ℃/min during the Tg test, and specific inductivity records under 1M Hz frequency, and the E value records under 25 ℃ of environment.

Claims (4)

1, the preparation method of polyimide with ultra-low dielectric constant is characterized in that comprising the steps:
(1) the γ-An Bingjisanyiyangjiguiwan coupling agent being joined the quality percentage composition is in 1%～3% the polyoxometallic acid salt brine solution, regulating the pH value is 1～2,20～40 ℃ of reaction 20～24h, remove by filter γ-An Bingjisanyiyangjiguiwan hydrolysis autopolymer, filtrate underpressure distillation under nitrogen protection removes desolvates, recrystallization in ether obtains polyoxometallate/silane hybrid material then; The silane coupling agent add-on is 10～20 times of polyoxometallate molar weight; Described polyoxometallate is the K of the Keggin structure of single omission or two omissions 8XY 11O 39Or K 8XY 10O 36, wherein X=Si, P; Y=W, Mo; Perhaps be the K of the Dawson structure of single omission or two omissions 6XY 17O 58Or K 6X 2Y 16O 56, wherein X=Si, P, Y=W, Mo;
(2) polyoxometallate/silane hybrid material of step (1) gained is joined previously prepared, be in the polyamic acid solution of solvent with the N-Methyl pyrrolidone, after stirring 16～24h under 20～40 ℃, film, vacuum tightness is-the following 80 ℃ of heating 2h of vacuum condition of 0.1MPa, 100 ℃ of heating 1h, 200 ℃ of heating 1h, 300 ℃ of heating 1h hot-imides, and the cooling back is the polyimide with ultra-low dielectric constant film; Wherein polyoxometallate/silane hybrid material is pressed 5%～20% adding of polyamic acid quality.
2, the preparation method of polyimide with ultra-low dielectric constant according to claim 1 is characterized in that the K of the Keggin structure of described single omission or two omissions 8XY 11O 39Or K 8XY 10O 36Polyoxometallate is prepared by following method: be dissolved in the water with Starso and sodium wolframate or with sodium phosphate and the Sodium orthomolybdate mol ratio with 1:11, with salt acid for adjusting pH value to 5～6, add KCl and obtain single vacant Keggin structure polyoxometallate; Single vacant Keggin structure polyoxometallic acid salt brine solution K 2CO 3The aqueous solution is regulated pH value to 9～11, adds KCl and obtains two vacant Keggin structure polyoxometallates.
3, the preparation method of polyimide with ultra-low dielectric constant according to claim 1 is characterized in that the K of the Dawson structure of described single omission or two omissions 6XY 17O 58Or K 6X 2Y 16O 56Polyoxometallate is prepared by following method: be dissolved in the water with Starso and sodium wolframate or with sodium phosphate and the Sodium orthomolybdate mol ratio with 1:18, with phosphorus acid for adjusting pH value to 5～6, add KCl and obtain single vacant Dawson structure polyoxometallate; Single Dawson structure oxygen acid salt aqueous solution K that lacks 2CO 3The aqueous solution is regulated pH value to 9～11, adds KCl and obtains two vacant Dawson structure polyoxometallates.
4, the preparation method of polyimide with ultra-low dielectric constant according to claim 1; the preparation method who it is characterized in that step (2) polyamic acid solution is: add the N-Methyl pyrrolidone through underpressure distillation in the there-necked flask that has the mechanical stirring slurry; add diamines then; the powerful stirring led to nitrogen protection simultaneously; after dissolving fully, diamines adds equimolar dianhydride with three equal parts; stirring at room 1h; obtain polyamic acid solution, wherein the mass percent of polyamic acid is 10%～15%.
CNB2007100323084A 2007-12-10 2007-12-10 Method for preparing polyimide with ultra-low dielectric constant Expired - Fee Related CN100532429C (en)

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