CN109734910B - Polyimide, and preparation method and application thereof - Google Patents
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Abstract
The invention provides polyimide, a preparation method and application thereof. The invention introduces the polyphenylene oxide structure into the polyimide resin, so that the polyimide provided by the invention has the advantages of low water absorption, low dielectric constant, small dielectric loss and good dimensional stability, and meanwhile, the polyimide obtained by the invention has strong bonding force with the copper foil.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to polyimide, and a preparation method and application thereof.
Background
Due to high flexibility, the flexible circuit board has been widely used in high-density, light and portable communication fields and various electronic products. In recent years, the information technology revolution is moving to a stage of higher signal speed and higher transmission frequency. To process ever increasing data, the frequency of electronic devices is increasing. This puts higher demands on the electrical properties of the substrate to minimize the loss and delay of high frequency signals.
With the arrival of the 5G communication era, the traditional polyimide is not suitable for being applied to the high-frequency and high-speed field due to high water absorption rate and high dielectric constant and loss at high frequency; therefore, it is necessary to modify polyimide to reduce water absorption, reduce dielectric loss and constant, and improve high frequency performance. CN107286650A provides a method for producing a polyimide with a low dielectric constant and an application of a polyimide film, comprising providing a fluorine-containing polymer dispersion (a) and an aromatic diamine (B) dissolved in a first solvent (C); the fluoropolymer dispersion (A) comprises a fluoropolymer (a-1), a second solvent (a-2) and a dispersant (a-3); mixing a fluoropolymer dispersion (A) with an aromatic diamine (B) to form a first mixture; adding aromatic tetracarboxylic dianhydride (D) to the first mixture to form a polyamic acid solution; the polyamic acid solution is subjected to a solvent removal step and a heating step to prepare polyimide. Although the introduction of the fluorine-containing monomer can reduce the water absorption rate, dielectric constant and loss at the same time, the introduction of fluorine element can reduce the peel strength between polyimide and copper foil. CN108948354A discloses a modified polyimide resin, a preparation method and an application thereof, comprising the following steps: pre-polymerizing dianhydride and diamine to obtain pre-polymer polyamic acid; copolymerizing the prepolymer polyamic acid and a raw material for synthesizing bismaleimide triazine resin to obtain a modified prepolymer; and curing the modified prepolymer to obtain a modified polyimide resin; it improves the warpage properties of polyimide in copolymerized form, but does not pay much attention to its dielectric properties.
Therefore, polyimides having low water absorption, low dielectric constant and low dissipation factor remain a technical challenge.
Disclosure of Invention
The invention aims to provide polyimide, and a preparation method and application thereof. The polyimide provided by the invention has the characteristics of low water absorption rate, small dielectric constant and dielectric loss at high frequency and strong bonding force with copper foil, and is suitable for high-frequency and high-speed circuit substrates.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyimide having a structure represented by formula I:
wherein Ar is a residue of a dianhydride compound, R is a residue of an aromatic diamine or a residue of a terminal amino polyphenylene ether, and m is 2 to 10000, for example, 3, 4, 5, 10, 50, 100, 500, 800, 1000, 2000, 3000, 5000, 8000, 9000, 9500, and the like.
In the prior art, polyphenylene ethers are generally used as modifiers for epoxy resins, reacting with the epoxy groups of the epoxy resins. The invention introduces the polyphenylene oxide structure into the polyimide resin, so that the polyimide provided by the invention has the advantages of low water absorption, low dielectric constant, small dielectric loss and good dimensional stability, and meanwhile, the polyimide obtained by the invention has strong bonding force with the copper foil.
Preferably, the polyimide is prepared from raw materials including amino-terminated polyphenylene ether, aromatic diamine and dianhydride compound.
Preferably, the ratio of the sum of the molar amounts of the amino terminated polyphenylene ether and the aromatic diamine to the molar amount of the dianhydride compound is 0.98 to 1.02, e.g., 0.99, 1.00, 1.01, etc.
Preferably, the amount of the amino terminated polyphenylene ether is 5 to 60% by mole, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, etc., preferably 20 to 60%, more preferably 25 to 40%, based on 100% by mole of the total amount of the amino terminated polyphenylene ether and the aromatic diamine.
Preferably, the amino-terminated polyphenylene ether has a structure as shown in formula II:
wherein n is 1-100, such as 2, 4, 6, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, etc.
Preferably, the amino terminated polyphenylene ether has an average functionality of 1.8 or greater, e.g., 1.9, 2, 2.2, etc.
Preferably, the glass transition temperature of the amino terminated polyphenylene ether is 150 ℃ or more, such as 160 ℃, 170 ℃, 180 ℃, 200 ℃ or the like.
Preferably, the 1% thermal decomposition temperature of the amino terminated polyphenylene ether is 300 ℃ or more, for example, 310 ℃, 320 ℃, 340 ℃, etc.
Preferably, the preparation method of the amino-terminated polyphenylene ether comprises the following steps: and reacting the hydroxyl-terminated polyphenyl ether with a bromine source to obtain bromine-terminated polyphenyl ether, and then reacting with an amine source to obtain the amino-terminated polyphenyl ether.
Wherein the structural formula of the hydroxyl-terminated polyphenyl ether is as follows:
preferably, the bromine source is 2-bromo-acetyl bromide.
Preferably, the amine source is triethylamine.
Preferably, the aromatic diamine is selected from any one of diaminodiphenyl ether (ODA), 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis (4-aminophenoxy) Benzene (BAPP), 1, 4-bis (4-aminophenoxy) benzene (TPE-R), 4' -diamino-2, 2' -dimethylbiphenyl (m-TB), p-Phenylenediamine (PDA), 4' -diamino-2, 2' -bistrifluoromethylbiphenyl (TFDB), or 4,4' -bis (4-aminophenoxy) biphenyl (BAPB), or a combination of at least two thereof.
Preferably, the aromatic diamine is a combination of any one or at least two of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -diamino-2, 2' -dimethylbiphenyl, p-phenylenediamine, or 4,4' -bis (4-aminophenoxy) biphenyl, for example, a combination of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and diaminodiphenyl ether, a combination of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and 1, 3-bis (4-aminophenoxy) benzene, a mixture of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and diaminodiphenyl ether, a mixture of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and 1,4, 4' -diamino-2, 2' -bistrifluoromethylbiphenyl in combination with p-phenylenediamine and 4,4' -bis (4-aminophenoxy) biphenyl, and the like.
In the present invention, the preferred aromatic diamine includes 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, and the low water absorption polyimide having excellent high frequency performance can be obtained by introducing the fluorine-containing monomer.
Preferably, the dianhydride compound is selected from any one of pyromellitic dianhydride (PMDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 4,4'- (hexafluoroisopropylene) diphthalic anhydride (6-FDA), bis (trimellitic anhydride) phenyl ester (TAHQ), 4,4' -diphenyl ether dianhydride (ODPA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), or 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA), or a combination of at least two thereof.
Preferably, the dianhydride compound is a composition obtained by any one or at least two of 4,4'- (hexafluoroisopropylidene) diphthalic anhydride and/or bis (trimellitic anhydride) phenyl ester and pyromellitic dianhydride, 3',4,4 '-biphenyltetracarboxylic dianhydride, 4,4' -diphenyl ether dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, or 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride), such as a combination of 4,4'- (hexafluoroisopropylidene) diphthalic anhydride and pyromellitic dianhydride, a combination of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 4,4 '-diphenyl ether dianhydride and 3,3',4,4 '-benzophenonetetracarboxylic dianhydride, a combination of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and bis (trimellitic anhydride) phenyl ester and 4, a combination of 4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride), and the like.
The dianhydride compound provided by the invention preferably comprises 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and/or bis (trimellitic anhydride) phenyl ester, fluorine-containing monomers and/or ester-containing monomers are selected, and fluorine and/or ester anhydride is introduced into polyimide, so that the low-water-absorption polyimide with excellent high-frequency performance can be obtained.
In a second aspect, the present invention provides a method for producing a polyimide according to the first aspect, comprising the steps of:
and mixing the amino-terminated polyphenyl ether, the aromatic diamine and the dianhydride compound to obtain polyamic acid, and then carrying out thermal imidization reaction to obtain the polyimide.
Preferably, the mixing is performed in a solvent to obtain a polyamic acid solution.
Preferably, the solvent comprises any one of or a combination of at least two of dimethylformamide, dimethylacetamide or N-vinylpyrrolidone.
Preferably, the polyamic acid solution has a solid content of 10 to 20 wt%, such as 12 wt%, 14 wt%, 16 wt%, 18 wt%, etc.
Preferably, the viscosity of the polyamic acid solution is 10000-50000cps, such as 20000cps, 30000cps, 40000cps, and the like.
Preferably, the solvent is removed prior to performing the thermal imidization reaction.
Preferably, the temperature for removing the solvent is 80-120 deg.C, such as 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, etc., and the time is 5-15min, such as 8min, 10min, 12min, etc., and more preferably 100-120 deg.C, 5-10 min.
Preferably, the conditions of the thermal imidization reaction are: keeping at 150-220 deg.C (such as 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, etc.) for 45-75min (such as 50min, 60min, 70min, etc.), keeping at 220-260 deg.C (such as 230 deg.C, 240 deg.C, 250 deg.C, etc.) for 15-45min (such as 20min, 25min, 30min, 35min, 40min, etc.), and keeping at 280-320 deg.C (such as 290 deg.C, 300 deg.C, 310 deg.C, etc.) for 45-75min (such as 50min, 60min, 70min, etc.).
In a third aspect, the present invention provides a polyimide film, wherein a raw material for preparing the polyimide film comprises the polyimide of the first aspect.
In a fourth aspect, the invention provides a copper-clad plate, which comprises the polyimide film in the third aspect.
In a fifth aspect, the invention provides an application of the copper-clad plate according to the fourth aspect in a flexible circuit board.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the prior art, polyphenylene ethers are generally used as modifiers for epoxy resins, reacting with the epoxy groups of the epoxy resins. The invention introduces the polyphenylene oxide structure into the polyimide resin, so that the polyimide provided by the invention has the advantages of low water absorption, low dielectric constant, small dielectric loss and good dimensional stability, and meanwhile, the polyimide obtained by the invention has strong bonding force with the copper foil.
(2) According to the invention, polyphenylene oxide is introduced into a main chain of polyimide, so that the finally obtained polyimide has low water absorption rate, low dielectric constant and dielectric loss, and high peel strength with copper foil, wherein the water absorption rate is lower than 0.8%, the dielectric constant is lower than 3.45(10GHz), the dielectric loss is lower than 0.0047(10GHz), and the peel strength with the copper foil layer is more than 1N/mm.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
The preparation example provides an amino-terminated polyphenylene ether, which has the following structure:
the preparation method comprises the following steps:
100g of hydroxyl-terminated polyphenylene ether (SA 90, molecular weight 1800) is dissolved in 250mL of dichloromethane, and a proper amount of 3mL of triethylamine is added; slowly adding 25mL of 2-bromo-acetyl bromide under stirring, reacting at room temperature for 2h, concentrating the reaction solution to 100mL, precipitating into 600mL of ethanol to obtain a brown solid, filtering, washing, and drying at 80 ℃ to obtain the terminal bromo polyphenylene oxide.
1H NMR(500MHz,CD2Cl2,298K)δ[ppm]7.14-7.65 (phenylring hydrogen), 2.13 (methylhydrogen), 2.30 (terminal bromohydrido).
Dissolving 70g of terminal bromo polyphenylene oxide in 250mL of dichloromethane, adding 3mL of triethylamine under stirring, reacting at room temperature for 5h, concentrating the reaction solution to 100mL, precipitating into 600mL of ethanol to obtain a brown solid, filtering, washing, and drying at 80 ℃ to obtain terminal amino polyphenylene oxide; wherein the molecular weight is 2200 (gel chromatography, THF is used as solvent, polystyrene is used as standard sample), the functionality is 1.9, the glass transition temperature is 158 deg.C (determined by differential scanning calorimeter, the temperature rising and falling speed is 10 deg.C/min), and the 1% thermal decomposition temperature is 375 deg.C (thermogravimetric analyzer, N2Atmosphere, 10 ℃/min).
1H NMR(500MHz,CD2Cl2,298K)δ[ppm]7.14-7.65 (phenylring hydrogen), 2.13 (methylhydrogen), 2.30 (terminal amino hydrogen).
Examples 1 to 6
Preparing a polyimide film (the unit of the amount of the raw materials is mmol) according to the components shown in the table 1, and preparing a single-sided copper-clad plate according to the following preparation method:
the aromatic diamine and the aminoterminated polyphenylene ether prepared in preparation example were dissolved in 15mL of dimethylformamide in the prescribed amounts, and the resulting solution was stirred at room temperature and then dissolved in ice water. Adding dianhydride compound under stirring, stirring in ice water for 3h, and adding trace dianhydride compound to adjust viscosity to obtain viscous yellow polyamic acid solution with viscosity of about 20000 cps.
Uniformly coating a polyamic acid solution on a low-profile copper foil in a wet film thickness of 250 mu m, drying at 120 ℃ for 10min to remove a solvent, and putting the copper foil in a nitrogen protection oven; maintaining at 150 deg.C for 20min, 200 deg.C for 20min, 250 deg.C for 20min, 300 deg.C for 20min, and 35 deg.C for 20 min. And cooling to obtain the single-sided copper-clad plate.
Comparative examples 1 to 3
Polyimide films (the unit of the used amount of the raw materials is mmol) are prepared according to the components shown in the table 2, and the single-sided copper-clad plate is manufactured according to the manufacturing method provided by the embodiment.
TABLE 1
Performance testing
The performance test of the single-sided copper-clad plates provided in examples 1 to 6 and comparative examples 1 to 3 is carried out by the following method:
(1) water absorption: drying the polyimide film at 105 ℃ for 2h, cooling and weighing, putting into water, taking out after 24h, wiping surface moisture with absorbent paper, and weighing again. Dividing the secondary mass difference by the initial weight to obtain the water absorption rate;
(2) dielectric constant and dielectric loss: drying the polyimide film at 105 ℃ for 2h, balancing the polyimide film at 23 ℃ for 48h under the condition of 50 RH%, and testing the polyimide film by using a medium separation resonant cavity produced by Agilent, wherein the testing frequency is 10 GHz;
(3) peel strength: and testing the single-sided copper-clad plate by referring to the IPC-TM-6502.4.9 method.
The test results are shown in Table 2.
TABLE 2
As can be seen from the examples and performance tests, the polyphenylene oxide is introduced into the main chain of the polyimide, so that the finally obtained polyimide has low water absorption rate, low dielectric constant and dielectric loss and high peel strength with a copper foil, wherein the water absorption rate is lower than 0.8%, the dielectric constant is lower than 3.45(10GHz), the dielectric loss is lower than 0.0047(10GHz), and the peel strength with the copper foil layer is more than 1N/mm. From examples 2 to 4, it is understood that a low water-absorbing polyimide having excellent high-frequency characteristics can be obtained by introducing a fluorine-containing monomer or an ester anhydride-containing monomer. As is clear from comparison of examples 1 to 6, in the present invention, it is preferable that the molar amount of the amino terminated polyphenylene ether is 20 to 60%, and the polyimide obtained in this case has a relatively excellent balance of properties. As can be seen from comparison of examples 1,3 to 4 and comparative examples 1 to 3, without addition of the amino terminated polyphenylene ether, a polyimide having both low water absorption, low dielectric constant and low dielectric loss and high peel strength could not be obtained.
The applicant states that the present invention is illustrated by the above examples to the polyimide of the present invention and the preparation method and application thereof, but the present invention is not limited to the above detailed method, i.e. it does not mean that the present invention must be implemented by the above detailed method. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (21)
1. A polyimide having a structure according to formula I:
wherein Ar is the residue of dianhydride compound, R is the residue of aromatic diamine or the residue of amino-terminated polyphenyl ether, and m is 2-10000;
the preparation raw materials of the polyimide comprise amino-terminated polyphenyl ether, aromatic diamine and dianhydride compound;
the amino-terminated polyphenyl ether has a structure shown in a formula II:
wherein n is 1-100;
the mol weight of the amino-terminated polyphenyl ether is 5-60% based on the total mol weight of the amino-terminated polyphenyl ether and the aromatic diamine as 100%;
the aromatic diamine is selected from one or a combination of at least two of diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -diamino-2, 2' -dimethylbiphenyl, p-phenylenediamine, 4' -diamino-2, 2' -bistrifluoromethylbiphenyl or 4,4' -bis (4-aminophenoxy) biphenyl.
2. The polyimide according to claim 1, wherein the ratio of the sum of the molar amounts of the amino terminated polyphenylene ether and the aromatic diamine to the molar amount of the dianhydride compound is 0.98 to 1.02.
3. The polyimide according to claim 1, wherein the molar amount of the amino terminated polyphenylene ether is 20 to 60% based on 100% of the total molar amount of the amino terminated polyphenylene ether and the aromatic diamine.
4. The polyimide according to claim 1, wherein the preparation method of the amino terminated polyphenylene ether comprises the following steps: reacting hydroxyl-terminated polyphenyl ether with a bromine source to obtain bromine-terminated polyphenyl ether, and then reacting with an amine source to obtain amino-terminated polyphenyl ether;
wherein the structural formula of the hydroxyl-terminated polyphenyl ether is as follows:
5. the polyimide of claim 4, wherein the bromine source is 2-bromo-acetyl bromide.
6. The polyimide of claim 4, wherein the amine source is triethylamine.
7. The polyimide according to claim 1, wherein the aromatic diamine is a combination of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and one or at least two selected from diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -diamino-2, 2' -dimethylbiphenyl, p-phenylenediamine and 4,4' -bis (4-aminophenoxy) biphenyl.
8. The polyimide according to claim 1, wherein the dianhydride compound is selected from any one of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4,4'- (hexafluoroisopropylidene) diphthalic anhydride, bis (trimellitic anhydride) phenyl ester, 4,4' -diphenyl ether dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, or 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride), or a combination of at least two thereof.
9. The polyimide according to claim 1, wherein the dianhydride compound is a composition obtained by mixing 4,4'- (hexafluoroisopropylidene) diphthalic anhydride and/or phenyl bis (trimellitic anhydride) ester with any one or at least two of pyromellitic dianhydride, 3',4,4 '-biphenyltetracarboxylic dianhydride, 4,4' -diphenyl ether dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, or 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride).
10. The method for producing a polyimide according to any one of claims 1 to 9, comprising the steps of:
and mixing the amino-terminated polyphenyl ether, the aromatic diamine and the dianhydride compound to obtain polyamic acid, and then carrying out thermal imidization reaction to obtain the polyimide.
11. The production method according to claim 10, wherein the mixing is performed in a solvent to obtain a polyamic acid solution.
12. The method of claim 11, wherein the solvent comprises any one of dimethylformamide, dimethylacetamide, or N-vinylpyrrolidone, or a combination of at least two thereof.
13. The method according to claim 10, wherein the polyamic acid solution has a solid content of 10 to 20 wt%.
14. The method as claimed in claim 10, wherein the polyamic acid solution has a viscosity of 10000-50000 cps.
15. The method according to claim 10, wherein the solvent is removed before the thermal imidization is performed.
16. The method of claim 15, wherein the solvent removal is carried out at a temperature of 80-120 ℃ for a period of 5-15 min.
17. The method as claimed in claim 15, wherein the temperature for removing the solvent is 100-120 ℃ and the time is 5-10 min.
18. The method according to claim 10, wherein the thermal imidization is performed under the following conditions: keeping the temperature at 150-220 ℃ for 45-75min, keeping the temperature at 220-260 ℃ for 15-45min, and finally keeping the temperature at 280-320 ℃ for 45-75 min.
19. A polyimide film, wherein a raw material for producing the polyimide film comprises the polyimide according to any one of claims 1 to 9.
20. A copper-clad plate characterized in that it comprises the polyimide film of claim 19.
21. The use of the copper-clad plate of claim 20 in a flexible circuit board.
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| CN112048240B (en) * | 2019-06-06 | 2022-03-01 | 达迈科技股份有限公司 | Primer composition, metal laminate and method for producing the same |
| CN111341983B (en) * | 2020-04-13 | 2023-01-31 | 上海极紫科技有限公司 | High-temperature-resistant lithium battery diaphragm, composition and preparation method thereof |
| CN113637324A (en) * | 2020-05-11 | 2021-11-12 | 北京八亿时空液晶科技股份有限公司 | Low-dielectric polyimide resin composition, polyimide film and application thereof |
| CN113861929A (en) * | 2021-09-22 | 2021-12-31 | 广东东溢新材料科技有限公司 | Adhesive, preparation method thereof, low dielectric loss pure adhesive film applying adhesive and manufacturing process thereof |
| CN113913149A (en) * | 2021-11-18 | 2022-01-11 | 广州联茂电子科技有限公司 | Improved polyimide adhesive, flexible metal foil substrate and preparation method |
| TWI801103B (en) * | 2022-01-22 | 2023-05-01 | 南亞塑膠工業股份有限公司 | Copper-clad laminate, polyimide resin and manufacturing method thereof |
| CN114854012A (en) * | 2022-06-20 | 2022-08-05 | 杭州福斯特电子材料有限公司 | Polyimide resin, polyimide film, preparation method of polyimide film and copper clad plate |
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