CN111171567B - Polyimide composite film and preparation method and application thereof - Google Patents

Polyimide composite film and preparation method and application thereof Download PDF

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CN111171567B
CN111171567B CN202010115509.6A CN202010115509A CN111171567B CN 111171567 B CN111171567 B CN 111171567B CN 202010115509 A CN202010115509 A CN 202010115509A CN 111171567 B CN111171567 B CN 111171567B
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composite film
polyimide composite
dianhydride
aromatic
polyimide
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CN111171567A (en
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赵文华
马鹏常
泊依晴
戴春桃
彭绍鸿
庄雨琪
邱志东
梁静怡
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Zhongshan Polytechnic
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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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract

The invention relates to the technical field of communication materials and flexible microelectronic packaging, in particular to a polyimide composite film and a preparation method and application thereof. The polyimide composite film provided by the invention has the characteristics of low dielectric constant, low hygroscopicity, excellent dimensional stability and the like, and the dielectric constant temperature of the polyimide composite film is very small along with the fluctuation of temperature and humidity, and the comprehensive performance is high. The polyimide meets the requirement of the film on the base material of the high-frequency copper-clad plate, can improve the quality of the high-frequency copper-clad plate, and the copper-clad plate prepared from the polyimide composite film has excellent dielectric property, hygroscopicity and dimensional stability. According to the description of the embodiment, the polyimide composite film provided by the invention has the dielectric constant as low as 2.55(10GHz), the dielectric loss as low as 0.003(10GHz), the thermal expansion coefficient as low as 13.5 ppm/DEG C and the moisture absorption rate as low as 0.1%.

Description

Polyimide composite film and preparation method and application thereof
Technical Field
The invention relates to the technical field of communication materials and flexible microelectronic packaging, in particular to a polyimide composite film and a preparation method and application thereof.
Background
Currently, polyimide films are widely used as electronic packaging materials, and are mainly used as passivation layers, insulating materials, flexible printed circuit substrates, high-speed integrated circuit interconnection insulating layers and the like due to excellent thermal stability, excellent mechanical properties and dimensional stability, low dielectric constant and wide temperature range electrical insulating properties. Although the above excellent properties of polyimide satisfy the requirements of general electronic packages, it does not have the low dielectric constant and low moisture absorption of polyphenylene ether and polytetrafluoroethylene, which cannot replace polyimide due to insufficient thermal stability, and thus cannot satisfy the requirements of advanced electronic packages.
In order to solve these problems, in the past, U.S. Pat. No. 5206091 provided a method for preparing a polyimide having a low dielectric constant and a low moisture absorption. However, this method is expensive and difficult to be applied to practical production, and the polyimide film has a high thermal expansion coefficient due to the molecular structure analysis provided by this method, and thus cannot meet the demand for high-frequency and high-speed communication materials. The Chinese patent CN201910530616.2 provides a preparation method of a polyimide film meeting the requirement of advanced electronic material packaging, and the polyimide film prepared by the method has the advantages of high dielectric property, low hygroscopicity and stable thermal property, but the toughness of the film is not enough. And has high cost, complex heat treatment process and high energy consumption.
In the field of 5G high-frequency communication or advanced microelectronic packaging, reasonable selection of transmission line dielectric materials, parameter design and structure have decisive influence on the loss of transmission lines, the integrity and accuracy of signal transmission require that the transmission line dielectric materials have the characteristics of low dielectric constant and low loss, and simultaneously, a substrate is required to have the characteristics of low moisture absorption and low thermal expansion. Although the flexible dielectric material polyimide reported in the above patent documents has outstanding heat resistance, excellent dielectric properties, and excellent dimensional stability, the overall performance of the product is not high and the cost is high. That is, the polyimide film in the prior art still cannot meet the requirements of high-frequency and high-speed communication dielectric materials on comprehensive properties such as low dielectric constant (Dk), low dielectric loss (Df), low hygroscopicity, and low Coefficient of Thermal Expansion (CTE) matched with copper foil.
Disclosure of Invention
The invention aims to provide a polyimide composite film, a preparation method and application thereof, wherein the polyimide composite film has the advantages of high dielectric property, low hygroscopicity, excellent dimensional stability, stable dielectric constant, small fluctuation along with temperature and humidity, high comprehensive performance, capability of meeting the preparation requirement of a high-frequency copper-clad plate on a base material and improvement on the quality of the copper-clad plate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyimide composite film, which comprises polyimide and polyphenyl ether, wherein the polyimide has a structure shown in a formula I:
Figure BDA0002391368870000021
wherein R is H or F; r is 1 Is H or trifluoromethyl; the value range of m is 10-6000, and the value range of n is 0-6000;
R 3 is composed of
Figure BDA0002391368870000022
Figure BDA0002391368870000023
One or more of the above;
R 4 is composed of
Figure BDA0002391368870000024
Figure BDA0002391368870000025
One or more of R 5 Is H or CH 3 ；
The mass ratio of the polyimide to the polyphenyl ether is (75-100): (0-25), and the mass of the polyphenylene ether is not 0.
The invention also provides a preparation method of the polyimide composite film, which comprises the following steps:
mixing aromatic diamine, aromatic dianhydride, polyphenyl ether, a homogeneous promoter and an organic solvent, copolymerizing and blending, and adding a capping agent for capping to obtain polyamic acid-polyphenyl ether homogeneous slurry;
mixing the polyimide-polyphenyl ether homogeneous phase slurry with an imidization reagent, and carrying out chemical imidization to obtain a partially imidized polyamic acid-polyphenyl ether homogeneous phase solution; the imidization rate of the partially imidized polyamic acid-polyphenyl ether homogeneous solution is 20 to 50 percent;
carrying out tape casting coating on the partially imidized polyamic acid-polyphenyl ether homogeneous solution, and drying to obtain a partially imidized polyimide composite film; the imidization rate of the partially imidized polyimide composite film is 50 to 90 percent;
carrying out thermal imidization reaction on the partially imidized polyimide composite film to obtain a polyimide composite film;
the aromatic diamine comprises a first aromatic diamine and a second aromatic diamine; the first aromatic diamine is p-phenylenediamine or 4, 4' -benzidine; the second aromatic diamine is one or more of 3,3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 2, 5-bis (trifluoromethyl) -p-phenylenediamine and 4,4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl;
the aromatic dianhydrides comprise a first aromatic dianhydride and a second aromatic dianhydride; the first aromatic dianhydride is biphenyl tetracarboxylic dianhydride and/or 2,2 '-difluoro-4, 4' -biphenyl dianhydride; the second aromatic dianhydride is one or more of pyromellitic dianhydride, 3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride and 4,4 ' -thioether dianhydride.
Preferably, the molar ratio of the aromatic diamine to the aromatic dianhydride is 1: (1-1.1).
Preferably, the molar ratio of the first aromatic diamine to the second aromatic diamine is (1-10): (10-1);
the molar ratio of the first aromatic dianhydride to the second aromatic dianhydride is (10-0): (0 to 10);
the dosage of the first aromatic dianhydride and the second aromatic dianhydride is not 0 at the same time.
Preferably, the mass ratio of the total mass of the aromatic dianhydride and the aromatic diamine to the polyphenylene ether is (80-100): (0 to 20);
and the polyphenylene ether is not 0 by mass.
Preferably, the mass ratio of the aromatic diamine to the imidizing agent is (11-20): (39-95);
the mass ratio of the aromatic diamine to the end-capping reagent is (16-23): (0.04-0.18);
the homogeneous phase promoter is a silane coupling agent;
the mass ratio (20-80) of the total mass of the polyphenyl ether, the aromatic diamine and the aromatic dianhydride to the homogeneous phase accelerator is as follows: (1-5).
Preferably, the temperature of the chemical imidization is-10 to 30 ℃, and the time of the chemical imidization is 10 to 80 min.
Preferably, the temperature of the thermal imidization reaction is 120-280 ℃, and the time of the thermal imidization reaction is 10-60 min.
The invention also provides the application of the polyimide composite film in the technical scheme or the application of the polyimide composite film prepared by the preparation method in the technical scheme in the fields of communication materials and flexible microelectronic packaging.
The invention provides a polyimide composite film which has the characteristics of low dielectric constant, low hygroscopicity, excellent dimensional stability and the like, and the polyimide composite film has stable dielectric constant, small fluctuation along with temperature and humidity and high comprehensive performance. The polyimide composite film can completely meet the requirement of a high-frequency copper-clad plate on a base material, the quality of the high-frequency copper-clad plate can be improved, and the copper-clad plate prepared from the polyimide composite film has excellent dielectric property, hygroscopicity and dimensional stability. According to the description of the embodiment, the polyimide composite film provided by the invention has the dielectric constant as low as 2.55(10GHz), the dielectric loss as low as 0.003(10GHz), the thermal expansion coefficient as low as 13.5 ppm/DEG C and the moisture absorption rate as low as 0.1%; meanwhile, the polyimide composite film provided by the invention has high heat resistance and low moisture absorption expansion performance, and specifically, the initial thermal decomposition temperature of the polyimide composite film can reach 504 ℃ at most, and the moisture absorption amplification of the dielectric constant of 40% R.H. can reach 0.1% at least.
The invention also provides a preparation method of the polyimide composite film, which is simple, energy-saving and environment-friendly.
Detailed Description
The invention provides a polyimide composite film, which comprises polyimide and polyphenyl ether, wherein the polyimide has a structure shown in a formula I:
Figure BDA0002391368870000041
wherein R is H or F; r 1 Is H or trifluoromethyl; the value range of m is 10-6000, and the value range of n is 0-6000;
R 3 is composed of
Figure BDA0002391368870000051
Figure BDA0002391368870000052
One or more of the above;
R 4 is composed of
Figure BDA0002391368870000053
Figure BDA0002391368870000054
One or more of R 5 Is H or CH 3 ；
The mass ratio of the polyimide to the polyphenylene oxide is (75-100): (0-25), and the mass of the polyphenylene ether is not 0.
In the present invention, when n is 0, R is preferably H, R 1 Preferably H;
when n ≠ 0, R is preferably H or F, R 1 Preferably H, R 3 Preferably a
Figure BDA0002391368870000055
Figure BDA0002391368870000056
One or more of the above;
R 4 preferably, it is
Figure BDA0002391368870000057
Figure BDA0002391368870000058
One or more of R 5 Is H or CH 3 。
When said R is 3 Preferably, it is
Figure BDA0002391368870000061
Figure BDA0002391368870000062
(iv) a plurality of (a); or R 4 Preferably a
Figure BDA0002391368870000063
Figure BDA0002391368870000064
Figure BDA0002391368870000065
Can be understood as that in the structure of the polyimide, R is 3 In the circulation unit thereof
Figure BDA0002391368870000066
The circulation structures can be the same or different; r 4 In the circulation unit thereof
Figure BDA0002391368870000067
The circulation structures may be the same or different.
In the invention, the mass ratio of the polyimide to the polyphenylene ether is (75-100): (0-25), preferably (80-95): (5-20).
In the invention, the thickness of the polyimide composite film is preferably 10-30 μm, more preferably 15-25 μm, and most preferably 18-22 μm.
The invention also provides a preparation method of the polyimide composite film, which comprises the following steps:
mixing aromatic diamine, aromatic dianhydride, polyphenyl ether, a homogeneous promoter and an organic solvent, copolymerizing and blending, and adding a capping agent for capping to obtain polyimide-polyphenyl ether homogeneous slurry;
mixing the polyimide-polyphenyl ether homogeneous phase slurry with an imidizing reagent, and carrying out chemical imidization to obtain a partially imidized polyamic acid-polyphenyl ether homogeneous phase solution; the imidization rate of the partially imidized polyamic acid-polyphenyl ether homogeneous solution is 20 to 50 percent;
carrying out tape casting coating on the partially imidized polyamic acid-polyphenyl ether homogeneous solution, and drying to obtain a partially imidized polyimide composite film; the imidization rate of the partially imidized polyimide composite film is 50-90 percent;
carrying out thermal imidization reaction on the partially imidized polyimide composite film to obtain a polyimide composite film;
the aromatic diamine comprises a first aromatic diamine and a second aromatic diamine; the first aromatic diamine is p-phenylenediamine or 4, 4' -benzidine; the second aromatic diamine is one or more of 3,3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 2, 5-bis (trifluoromethyl) -p-phenylenediamine and 4,4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl;
the aromatic dianhydrides comprise a first aromatic dianhydride and a second aromatic dianhydride; the first aromatic dianhydride is biphenyl tetracarboxylic dianhydride and/or 2,2 '-difluoro-4, 4' -biphenyl dianhydride; the second aromatic dianhydride is one or more of pyromellitic dianhydride, 3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride and 4,4 ' -thioether dianhydride.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, aromatic diamine, aromatic dianhydride, polyphenyl ether, homogeneous phase promoter and organic solvent are mixed, and then are copolymerized and blended, and then are added with a capping reagent for capping, so as to obtain the polyimide-polyphenyl ether homogeneous phase slurry.
In the present invention, the aromatic diamine includes a first aromatic diamine and a second aromatic diamine; the first aromatic diamine is p-phenylenediamine (PPD) or 4, 4' -benzidine (DABP); the second aromatic diamine is one or more of 3,3 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (TFMB), 2, 5-bis (trifluoromethyl) -p-phenylenediamine (2TFMPD), 4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl (FAPB) and 2, 2', 6,6 '-tetramethyl-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (TMFAPB); when the second aromatic diamine is two or more of the above specific choices, the present invention does not have any particular limitation on the ratio of the specific substances, and the specific substances may be mixed in any ratio. In the present invention, the molar ratio of the first aromatic diamine to the second aromatic diamine is preferably (1 to 10): (10-1), more preferably (2-8): (8-2), most preferably (4-6): (6-4). In the present invention, the aromatic dianhydrides include a first aromatic dianhydride and a second aromatic dianhydride; the first aromatic dianhydride is biphenyl tetracarboxylic dianhydride (BPDA) and/or 2,2 '-difluoro-4, 4' -biphenyl dianhydride (2 FBPDA); the second aromatic dianhydride is one or more of pyromellitic dianhydride (PMDA), 3 ', 4,4 ' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4 ' -thioether dianhydride (SPDA); when the second aromatic dianhydride is more than two of the above specific choices, the specific material proportion is not limited in any way, and the second aromatic dianhydride can be mixed according to any proportion. In the present invention, the molar ratio of the first aromatic dianhydride to the second aromatic dianhydride is preferably (10 to 0): (0 to 10), and the amounts of the first aromatic dianhydride and the second aromatic dianhydride are not 0 at the same time, more preferably (8 to 2): (2-8), most preferably (6-4): (4-6). In the present invention, the molar ratio of the aromatic diamine to the aromatic dianhydride is preferably 1: (1 to 1.1), more preferably 1: (1.02-1.08), most preferably 1: (1.04-1.06).
In the invention, the structure of the p-phenylenediamine (PPD) is shown as the formula II:
Figure BDA0002391368870000081
the structure of the 2, 5-bis (trifluoromethyl) -p-phenylenediamine (2TFMPD) is shown as a formula III:
Figure BDA0002391368870000082
the structure of the 4, 4' -benzidine (DABP) is shown as a formula IV:
Figure BDA0002391368870000083
the structure of the 3,3 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl (TFMB) is shown as the formula V:
Figure BDA0002391368870000084
the structure of the 4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl is shown as a formula VI:
Figure BDA0002391368870000085
wherein when R is 5 When H, specifically 4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, designated FAPB; when R is 5 ＝CH 3 Specifically, 2 ', 6,6 ' -tetramethyl-4, 4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl is used and is denoted as TMFAPB.
In the invention, the structure of the biphenyl tetracarboxylic dianhydride (BPDA) is shown as the formula VII:
Figure BDA0002391368870000091
the structure of the 2,2 '-difluoro-4, 4' -biphenyl dianhydride (2FBPDA) is shown as a formula VIII:
Figure BDA0002391368870000092
the structure of pyromellitic dianhydride (PMDA) is shown as the formula IX:
Figure BDA0002391368870000093
the structure of the 3,3 ', 4, 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) is shown as the formula X:
Figure BDA0002391368870000094
the structure of the 4, 4' -thioether dianhydride (SPDA) is shown as a formula XI:
Figure BDA0002391368870000095
in the present invention, the mass ratio of the total mass of the aromatic dianhydride and the aromatic diamine to the polyphenylene ether is preferably (80 to 100): (0-20), more preferably (85-95): (5-15), most preferably (88-92): (8-12); and the mass of the polyphenylene ether is not 0.
In the invention, the structural formula of the polyphenyl ether is shown in a formula XII:
Figure BDA0002391368870000101
the value range of n in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the homogeneous accelerator is preferably a silane coupling agent. In the present invention, the silane coupling agent is preferably 3-Aminopropyltriethoxysilane (APTES), 3-Aminopropyltrimethoxysilane (APTMS) or Octyltrimethoxysilane (OTMS), and more preferably 3-Aminopropyltrimethoxysilane (APTMS). In the present invention, the mass ratio of the total mass of the polyphenylene ether, the aromatic diamine and the aromatic dianhydride to the homogeneous phase accelerator is preferably (20 to 80): (1-5), more preferably (25-75): (1.5-4.5), most preferably (30-65): (2-4).
In the invention, the homogeneous phase promoter can fully and uniformly mix the polyamic acid obtained by copolymerizing the polyphenyl ether, and effectively compound, thereby ensuring that the polyamic acid/polyphenyl ether solution after blending and compounding is not subjected to phase separation in the subsequent imidization process and is not subjected to layering in the subsequent tape-casting coating process, and further obtaining the high-quality composite film.
In the present invention, the organic solvent is preferably N, N ' -dimethylacetamide, N ' -dimethylformamide, N-methylpyrrolidone, or dioxane, and more preferably N, N ' -dimethylacetamide. In the present invention, the mass ratio of the total mass of the aromatic diamine, the aromatic dianhydride and the polyphenylene ether to the organic solvent is preferably (5 to 25): (75-95), more preferably (7-20): (80-93), most preferably (8-17): (83-92).
In the present invention, the mixing preferably comprises the steps of:
mixing polyphenyl ether, a homogeneous phase promoter and a part of organic solvent until the polyphenyl ether, the homogeneous phase promoter and the part of organic solvent are completely dissolved to obtain a first mixture;
mixing the first mixture, aromatic diamine, aromatic dianhydride, and remaining organic solvent.
The invention has no special limit on the proportion of the partial organic solvent and the residual organic solvent, and ensures that the mixing process in each step is completely dissolved.
In the invention, the mixing process is used for smoothly carrying out polymerization reaction, so that the polyamic acid and the polyphenyl ether obtained by copolymerization are fully and uniformly mixed and effectively compounded, and therefore, the polyamic acid/polyphenyl ether solution after blending and compounding is ensured not to be subjected to phase separation in the subsequent chemical imidization process and not to be subjected to layering in the subsequent casting coating process, and a high-quality composite film is obtained.
The present invention is not limited to any particular manner of mixing, and may be carried out in a manner known to those skilled in the art.
In the invention, the copolymerization and blending processes are preferably carried out simultaneously, namely the aromatic diamine and the aromatic dianhydride with rigid symmetrical structures undergo copolymerization reaction to form polyamic acid solution, and are blended and compounded with the polyphenyl ether during polymerization to obtain the polyamic acid/polyphenyl ether homogeneous slurry. In the present invention, the copolymerization and blending are preferably carried out in a protective atmosphere; the protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere, and more preferably a nitrogen atmosphere. In the present invention, the temperature of the copolymerization and blending is preferably room temperature; the time for copolymerization and blending is preferably 8-36 h, more preferably 10-28 h, and most preferably 12-24 h.
In the present invention, the blocking agent is preferably Maleic Anhydride (MAH) or Phthalic Anhydride (PA), more preferably Maleic Anhydride (MAH). In the present invention, the mass ratio of the aromatic diamine to the end-capping agent is preferably (16 to 23): (0.04-0.18), more preferably (17-22): (0.05-0.16), preferably (18-21): (0.06-0.15). In the invention, the end-capping reagent is used for effectively controlling the degree of polymerization reaction, thereby ensuring that the polyamic acid solution has better film-forming property in the subsequent imidization and curtain coating processes.
The addition mode of the blocking agent is not limited in any way, and can be any addition mode known to those skilled in the art. In the present invention, the conditions for the end-capping are preferably the same as those for the copolymerization and blending.
After the polyimide-polyphenyl ether homogeneous phase slurry is obtained, the polyimide-polyphenyl ether homogeneous phase slurry and an imidization reagent are mixed for chemical imidization to obtain a partially imidized polyamic acid-polyphenyl ether homogeneous phase solution; the imidization rate of the partially imidized polyamic acid-polyphenyl ether homogeneous solution is 20 to 50 percent.
In the present invention, the imidizing agent preferably includes a dehydrating agent and a catalyst; the dehydrating agent is preferably acetic anhydride or trifluoroacetic anhydride; the catalyst is preferably pyridine substances or triethanolamine; the pyridine substance is preferably one or more of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and 2, 4-dimethylpyridine; when the pyridine substances are more than two of the above specific choices, the specific proportion of the pyridine substances is not limited in any way, and the pyridine substances can be mixed according to any proportion. In the invention, the molar ratio of the dehydrating agent to the catalyst is preferably (4-8): (2-10), more preferably (5-7): (3-9), most preferably (5-6): (3-7). In the present invention, the mass ratio of the aromatic diamine to the imidizing agent is preferably (11 to 20): (39-95), more preferably (12-18): (42-90), most preferably (13-17): (43 to 85)
The present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art.
In the invention, the temperature of the chemical imidization is preferably-10-30 ℃, more preferably-5-25 ℃, and most preferably 0-20 ℃; the chemical imidization time is preferably 10-80 min, more preferably 15-60 mi, and most preferably 20-50 min. In the present invention, the imidization rate of the partially imidized polyamic acid-polyphenylene ether homogeneous solution is preferably 25% to 46%. In the invention, the chemical imidization process is to partially imidize the polyamic acid-polyphenylene ether homogeneous slurry, so that the temperature of subsequent thermal imidization is reduced, the imidization time is shortened, the energy is saved, the environment is protected, the overall quality of the polyimide film is improved, and the roughness and the thermal expansion coefficient of the film are reduced.
After the homogeneous phase solution of the partially imidized polyamic acid-polyphenyl ether is obtained, the partially imidized polyamic acid-polyphenyl ether homogeneous phase solution is subjected to tape casting coating and then is dried to obtain a partially imidized polyimide composite film; the imidization rate of the partially imidized polyimide composite film is 50-90%.
In the present invention, the temperature of the casting coating is preferably room temperature. The base for casting coating is preferably silicate glass, and the thickness of the silicate glass is preferably 2-4 mm, and more preferably 3 mm. The manner of the casting coating is not particularly limited in the present invention, and may be performed in a manner known to those skilled in the art.
In the invention, the drying temperature is preferably 25-110 ℃, more preferably 30-100 ℃, and most preferably 35-90 ℃; the drying time is not limited in any way, and the solid content of the obtained partially imidized polyimide composite film can be ensured to be within the range of 40-95%, and the imidization rate of the partially imidized polyimide composite film is within the range of 50-90%. In the present invention, the solid content of the partially imidized polyimide composite film is more preferably 50 to 90%, and most preferably 60 to 90%. In the present invention, the imidization ratio of the partially imidized polyimide composite film is preferably 56 to 87%, more preferably 60 to 85%. In the present invention, the drying may further promote imidization of the film in addition to the reduction of the solid content of the partially imidized polyimide composite film.
After the partially imidized polyimide composite film is obtained, the partially imidized polyimide composite film is subjected to thermal imidization reaction to obtain the polyimide composite film.
In the invention, the temperature of the thermal imidization reaction is preferably 120-280 ℃, more preferably 130-260 ℃, and most preferably 130-250 ℃; the time of the thermal imidization reaction is preferably 10 to 60min, more preferably 10 to 50min, and most preferably 15 to 40 min. In the present invention, the process of the thermal imidization reaction is preferably: heating to 120-200 ℃ at a heating rate of 10.0-15.0 ℃/min, and heating to 200-280 ℃ at a heating rate of 10-15 ℃/min; more preferably: heating to 130-200 ℃ at a heating rate of 10.0-15.0 ℃/min, and heating to 200-260 ℃ at a heating rate of 10-15 ℃/min; most preferably: heating to 130-200 ℃ at a heating rate of 10.0-15.0 ℃/min, and then heating to 200-250 ℃ at a heating rate of 10-15 ℃/min.
In the present invention, the thermal imidization can imidize all of the remaining non-imidized polyamic acid and complete the compounding with polyphenylene ether to form a polyimide composite film.
After the thermal imidization reaction is completed, it is also preferable to include cooling stripping, and the cooling stripping is not particularly limited in the present invention and may be performed by a process well known to those skilled in the art.
In the invention, the preparation method is simple, the copolymerization and the blending are synchronously carried out, the process is optimized, the obtained slurry is uniformly mixed and effectively compounded, and the method has low raw material cost; in addition, partial imidization is carried out firstly, and then thermal imidization is carried out, so that the process is improved, the thermal imidization time is shortened, the temperature of the thermal imidization is reduced, and the energy consumption is reduced; the thermal expansion coefficient of the polyimide composite film is also reduced through process optimization.
The invention also provides the application of the polyimide composite film prepared by the technical scheme or the preparation method in the technical scheme in the communication material and flexible microelectronic packaging field. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The polyimide composite film provided by the present invention, the preparation method and the application thereof will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
4,4 '-biphenyl dianhydride (13.97g), p-phenylenediamine (5.14g), polyphenylene ether (1.01g), 3-aminopropyltrimethoxysilane (1.34g) and N, N' -dimethylacetamide (193mL, 181.08g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.02g of maleic anhydride was added to conduct end capping to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (8.85g) and acetic anhydride (12.13g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at the speed of 12 ℃/min, then continuously heating to 250 ℃ at the speed of 15 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.4Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 2
4,4 '-biphenyl dianhydride (13.24g), p-phenylenediamine (4.87g), polyphenyl ether (2.01g), 3-aminopropyl trimethoxy silane (1.34g) and N, N' -dimethyl acetamide (193mL, 181.08g) are mixed, copolymerization and blending are carried out (room temperature, nitrogen atmosphere) for 16h, and then 0.02g of maleic anhydride is added for end capping, so that polyamic acid-polyphenyl ether homogeneous solution is obtained;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (8.39g) and acetic anhydride (11.49g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 150 ℃ at the speed of 13 ℃/min, then continuously heating to 230 ℃ at the speed of 15 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.3Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 3
4,4 '-biphenyl dianhydride (13.24g), 2' -difluoro-4, 4 '-biphenyl dianhydride (1.65g), p-phenylenediamine (4.87g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (1.60g), polyphenylene ether (2.37g), 3-aminopropyltrimethoxysilane (1.58g) and N, N' -dimethylacetamide (228mL, 213.57g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then homogeneous 0.02g of maleic anhydride was added to conduct capping, to obtain a polyamic acid-polyphenylene ether solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g) to carry out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at a speed of 14 ℃/min, then continuously heating to 240 ℃ at a speed of 10 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.1Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 4
4,4 '-biphenyl dianhydride (11.77g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), p-phenylenediamine (4.33g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (3.20g), polyphenylene ether (2.51g), 3-aminopropyltrimethoxysilane (1.67g) and N, N' -dimethylacetamide (241mL, 225.99g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.02g of maleic anhydride was added to cap to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g) to carry out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at the speed of 15 ℃/min, then continuously heating to 250 ℃ at the speed of 15 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.9Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 5
4,4 '-biphenyl dianhydride (11.77g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), p-phenylenediamine (3.78g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (4.80g), polyphenylene ether (2.63g), 3-aminopropyltrimethoxysilane (1.75g) and N, N' -dimethylacetamide (253mL, 236.52g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then homogeneous 0.015g of maleic anhydride was added for capping to obtain a polyamic acid-polyphenylene ether solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 180 ℃ at the speed of 15 ℃/min, then continuously heating to 230 ℃ at the speed of 12 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.7Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 6
4,4 '-biphenyl dianhydride (11.77g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), p-phenylenediamine (3.24g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (6.40g), polyphenylene ether (2.75g), 3-aminopropyltrimethoxysilane (1.83g) and N, N' -dimethylacetamide (264mL, 247.14g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16h, and then 0.01g of maleic anhydride was added to cap to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at the speed of 15 ℃/min, then continuously heating to 250 ℃ at the speed of 13 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.5Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 7
4,4 '-biphenyl dianhydride (10.30g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), pyromellitic dianhydride (1.09g), p-phenylenediamine (3.78g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (4.8g), polyphenylene ether (2.59g), 3-aminopropyltrimethoxysilane (1.72g) and N, N' -dimethylacetamide (248mL, 232.774g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added to conduct end capping, to obtain a polyphenylene ether-polyamic acid homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at the speed of 15 ℃/min, then continuously heating to 230 ℃ at the speed of 10 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.7Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 8
4,4 '-biphenyl dianhydride (8.83g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), pyromellitic dianhydride (2.18g), p-phenylenediamine (3.78g), 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (4.8g), polyphenylene ether (2.54g), 3-aminopropyltrimethoxysilane (1.70g) and N, N' -dimethylacetamide (208mL, 228.87g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added for capping to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g) to carry out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 170 ℃ at the speed of 10 ℃/min, then continuously heating to 250 ℃ at the speed of 12 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.6Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 9
4,4 '-biphenyl dianhydride (8.83g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), pyromellitic dianhydride (1.09g), 3', 4,4 '-benzophenone tetracarboxylic dianhydride (1.61g), p-phenylenediamine (3.78g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (4.8g), polyphenylene ether (2.51g), 3-aminopropyltrimethoxysilane (1.73g) and N, N' -dimethylacetamide (250mL, 234.09g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added to conduct end capping to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 130 ℃ at the speed of 12 ℃/min, then continuously heating to 210 ℃ at the speed of 12 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.5Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 10
4,4 ' -biphenyl dianhydride (8.83g), 2 ' -difluoro-4, 4 ' -biphenyl dianhydride (3.30g), pyromellitic dianhydride (1.09g), 4 ' -thioether dianhydride (1.63g), p-phenylenediamine (3.78g), 3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (4.8g), polyphenylene ether (2.60g), 3-aminopropyltrimethoxysilane (1.74g) and N, N ' -dimethylacetamide (250mL, 234.27g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added to conduct end capping, to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at the speed of 13 ℃/min, then continuously heating to 250 ℃ at the speed of 10 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.5Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 11
4,4 '-biphenyl dianhydride (11.77g), 2' -difluoro-4, 4 '-biphenyl dianhydride (3.30g), p-phenylenediamine (3.78g), 3' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (4.8g), polyphenylene ether (2.63g), 3-aminopropyltrimethoxysilane (1.75g) and N, N' -dimethylacetamide (206mL, 192.72g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16h, and then homogeneous 0.015g of maleic anhydride was added for capping to obtain a polyamic acid-polyphenylene ether solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g) to carry out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 190 ℃ at a speed of 10 ℃/min, then continuously heating to 220 ℃ at a speed of 10 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 12 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.0Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 12
4,4 ' -biphenyl dianhydride (8.83g), 2 ' -difluoro-4, 4 ' -biphenyl dianhydride (3.30g), pyromellitic dianhydride (2.18g), p-phenylenediamine (3.24g), 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (4.8g), 4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (2.52g), polyphenylene ether (2.76g), 3-aminopropyltrimethoxysilane (1.84g) and N, N ' -dimethylacetamide (167mL, 156.57g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added for capping to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 160 ℃ at the speed of 11 ℃/min, then continuously heating to 220 ℃ at the speed of 15 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 15 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.7Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 13
4,4 ' -biphenyl dianhydride (8.83g), 2 ' -difluoro-4, 4 ' -biphenyl dianhydride (3.30g), pyromellitic dianhydride (2.18g), p-phenylenediamine (2.70g), 3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl (4.8g), 4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (5.04g), polyphenylene ether (2.98g), 3-aminopropyltrimethoxysilane (1.99g) and N, N ' -dimethylacetamide (180mL, 169.04g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added to conduct end capping, to obtain a polyamic acid-homogeneous polyphenylene ether solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene ether homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 130 ℃ at the speed of 12 ℃/min, then continuously heating to 240 ℃ at the speed of 13 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 15 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.7Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 14
4,4 ' -biphenyl dianhydride (8.83g), 2 ' -difluoro-4, 4 ' -biphenyl dianhydride (3.30g), pyromellitic dianhydride (2.18g), p-phenylenediamine (2.70g), 2, 5-bis (trifluoromethyl) -p-phenylenediamine (3.66g), 4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (5.04g), polyphenylene ether (2.90g), 3-aminopropyltrimethoxysilane (1.90g) and N, N ' -dimethylacetamide (265mL, 257.13g) were mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16 hours, and then 0.015g of maleic anhydride was added to conduct end capping, to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (9.31g) and acetic anhydride (12.76g) to carry out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 150 ℃ at the speed of 12 ℃/min, then continuously heating to 200 ℃ at the speed of 10 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 5.6Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 15
4,4 '-biphenyl dianhydride (13.24g), p-phenylenediamine (4.87g), polyphenylene ether (3.20g), 3-aminopropyltrimethoxysilane (1.42g) and N, N' -dimethylacetamide (205mL, 191.79g) are mixed, copolymerized and blended (room temperature, nitrogen atmosphere) for 16h, and then 0.02g of maleic anhydride is added for end capping to obtain a polyamic acid-polyphenylene ether homogeneous solution;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (8.39g) and acetic anhydride (11.49g), and carrying out chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 200 ℃ at the speed of 14 ℃/min, then continuously heating to 250 ℃ at the speed of 12 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.2Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Example 16
4,4 '-biphenyl dianhydride (13.24g), p-phenylenediamine (4.87g), polyphenyl ether (2.01g), 3-aminopropyl trimethoxy silane (1.34g) and N, N' -dimethyl acetamide (193mL, 181.08g) are mixed, copolymerization and blending are carried out (room temperature, nitrogen atmosphere) for 16h, and then 0.02g of maleic anhydride is added for end capping, so that polyamic acid-polyphenyl ether homogeneous solution is obtained;
mixing the polyamic acid-polyphenylene ether homogeneous solution, 4-methylpyridine (6.28g) and acetic anhydride (11.49g), and carrying out chemical imidization (10 ℃, 60min) to obtain a partially imidized polyamic acid-polyphenylene ether homogeneous solution;
at room temperature, casting and coating the partially imidized polyamic acid-polyphenylene oxide homogeneous solution on silicate glass with the thickness of 3mm, and drying (90 ℃, 70min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 180 ℃ at the speed of 15 ℃/min, then continuously heating to 250 ℃ at the speed of 10 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.3Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
Comparative example 1
4,4 '-biphenyl dianhydride (14.71g), p-phenylenediamine (5.41g) and N, N' -dimethylacetamide (193mL, 181.08g) were mixed and copolymerized (room temperature, nitrogen atmosphere) for 12 hours, and then 0.03g of maleic anhydride was added to seal the end, thereby obtaining a polyamic acid solution;
mixing the polyamic acid solution, 4-methylpyridine (8.52g) and acetic anhydride (11.68g), and performing chemical imidization (10 ℃, 25min) to obtain a partially imidized polyamic acid solution;
at room temperature, casting and coating the partially imidized polyamic acid solution on silicate glass with the thickness of 3mm, and drying (65 ℃, 45min) to obtain a partially imidized polyimide composite film;
carrying out thermal imidization on the partially imidized polyimide composite film (heating to 130 ℃ at a speed of 10 ℃/min, then continuously heating to 200 ℃ at a speed of 15 ℃/min, and carrying out thermal imidization for 30min), cooling and stripping to obtain a polyimide composite film (25 mu m);
mixing the polyamide acid solution with a dimethylacetamide solution with a solid content of 10 wt%, and testing the dynamic viscosity at 25 ℃, wherein the dynamic viscosity is 6.5Pa & s;
the polyimide composite film was tested for dielectric properties, moisture absorption properties and dimensional stability, and the test results are shown in table 1.
TABLE 1 Properties of polyimide composite films obtained in examples 1 to 16 and comparative example 1
Figure BDA0002391368870000251
As can be seen from Table 1, the polyimide composite film obtained by the invention has the performances of high dielectric, excellent dimensional stability, low moisture absorption and the like, specifically, the dielectric constant can be as low as 2.55(10GHz), the dielectric loss can be as low as 0.003(10GHz), the thermal expansion coefficient can be as low as 13.5 ppm/DEG C, and the moisture absorption rate can be as low as 0.1%. In addition, the polyimide composite film obtained by the invention has the performances of high heat resistance, low moisture absorption expansion and the like, and particularly, the initial thermal decomposition temperature can reach 504 ℃, and the moisture absorption amplification of the dielectric constant 40% R.H. can reach 0.1% at least. In conclusion, the polyimide composite film obtained by the invention has excellent comprehensive performance and low preparation cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (9)

1. A polyimide composite film is composed of polyimide and polyphenyl ether, wherein the polyimide has a structure shown in a formula I:
Figure FDA0003593556900000011
wherein, when n is 0, R is H, R 1 Is H;
when n ≠ 0, R is H or F, R 1 Is H, R 3 Is composed of
Figure FDA0003593556900000012
Figure FDA0003593556900000013
One or more of the above;
R 4 is composed of
Figure FDA0003593556900000014
Figure FDA0003593556900000015
One or more of R 5 Is H or CH 3 ；
The mass ratio of the polyimide to the polyphenylene oxide is (75-100): (0 to 25), and the mass of the polyphenylene ether is not 0.
2. The method for preparing the polyimide composite film according to claim 1, comprising the steps of:
mixing aromatic diamine, aromatic dianhydride, polyphenyl ether, a homogeneous promoter and an organic solvent, copolymerizing and blending, and adding a capping reagent for capping to obtain polyamic acid-polyphenyl ether homogeneous slurry;
mixing the polyimide-polyphenyl ether homogeneous phase slurry with an imidizing reagent, and carrying out chemical imidization to obtain a partially imidized polyamic acid-polyphenyl ether homogeneous phase solution; the imidization rate of the partially imidized polyamic acid-polyphenyl ether homogeneous solution is 20 to 50 percent;
carrying out tape casting coating on the partially imidized polyamic acid-polyphenyl ether homogeneous solution, and drying to obtain a partially imidized polyimide composite film; the imidization rate of the partially imidized polyimide composite film is 50-90 percent;
carrying out thermal imidization reaction on the partially imidized polyimide composite film to obtain a polyimide composite film;
the aromatic diamine comprises a first aromatic diamine and a second aromatic diamine; the first aromatic diamine is p-phenylenediamine or 4, 4' -benzidine; the second aromatic diamine is one or more of 3,3 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 2, 5-bis (trifluoromethyl) -p-phenylenediamine and 4,4 ' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl;
the aromatic dianhydrides comprise a first aromatic dianhydride and a second aromatic dianhydride; the first aromatic dianhydride is biphenyl tetracarboxylic dianhydride and/or 2,2 '-difluoro-4, 4' -biphenyl dianhydride; the second aromatic dianhydride is one or more of pyromellitic dianhydride, 3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride and 4,4 ' -thioether dianhydride.
3. The method of claim 2, wherein the molar ratio of the aromatic diamine to the aromatic dianhydride is from 1: (1-1.1).
4. The method according to claim 2, wherein the molar ratio of the first aromatic diamine to the second aromatic diamine is (1 to 10): (10-1);
the molar ratio of the first aromatic dianhydride to the second aromatic dianhydride is (10-0): (0-10);
the dosage of the first aromatic dianhydride and the second aromatic dianhydride is not 0 at the same time.
5. The method according to claim 2, wherein the mass ratio of the total mass of the aromatic dianhydride and the aromatic diamine to the polyphenylene ether is (80 to 100): (0-20);
and the polyphenylene ether is not 0 by mass.
6. The method according to claim 2 or 5, wherein the mass ratio of the aromatic diamine to the imidizing agent is (11 to 20): (39-95);
the mass ratio of the aromatic diamine to the end-capping reagent is (16-23): (0.04-0.18);
the homogeneous phase promoter is a silane coupling agent;
the mass ratio (20-80) of the total mass of the polyphenyl ether, the aromatic diamine and the aromatic dianhydride to the homogeneous phase accelerator is as follows: (1-5).
7. The method according to claim 2, wherein the chemical imidization is carried out at a temperature of-10 to 30 ℃ for 10 to 80 min.
8. The method according to claim 2, wherein the temperature of the thermal imidization reaction is 120 to 280 ℃ and the time of the thermal imidization reaction is 10 to 60 min.
9. The polyimide composite film as claimed in claim 1 or the polyimide composite film prepared by the preparation method as claimed in any one of claims 2 to 8, and the application of the polyimide composite film in the fields of communication materials and flexible microelectronic packaging.
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