CN113248709A - Low-shrinkage high-strength polyimide and preparation method thereof - Google Patents

Low-shrinkage high-strength polyimide and preparation method thereof Download PDF

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CN113248709A
CN113248709A CN202110691893.9A CN202110691893A CN113248709A CN 113248709 A CN113248709 A CN 113248709A CN 202110691893 A CN202110691893 A CN 202110691893A CN 113248709 A CN113248709 A CN 113248709A
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CN113248709B (en
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邓鹏飏
魏巍
史彦东
赵阳
潘利江
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Changchun Institute of Applied Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention provides polyimide, which is prepared from diamine monomers and dianhydride monomers; the diamine monomer comprises POSS diamine and diamine containing pyridine structure; the POSS diamine is represented by formula (I): (R)2SiO1.5)m(R3SiO1.5)2Formula (I); wherein m is an integer of 4-10. Compared with the prior art, the preparation method disclosed by the invention has the advantages that the POSS is modified to be liquefied, so that the dispersion characteristic and the solubility of POSS particles are improved, and the strength of polyimide is further improved; meanwhile, the pyridine structure is also included, so that the thermal expansion coefficient of the polyimide can be reduced, and the obtained polyimide has low shrinkage and high strength.

Description

Low-shrinkage high-strength polyimide and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to low-shrinkage high-strength polyimide and a preparation method thereof.
Background
Polyimide is a high-performance material, has excellent mechanical strength and high-temperature resistance, and has wide application in the fields of microelectronics, aerospace and the like.
Polyhedral oligomeric silsesquioxane (POSS) is an organic-inorganic hybrid nano filler, has a unique hollow cage structure and good molecular regulation and control capability, and can be used for improving the dielectric property, thermal stability and mechanical property of a polymer material. Since the organic-inorganic hybrid structure not only has excellent heat resistance and mechanical properties, but also can reduce the friction coefficient and wear rate of the polymer composite material, in recent years, the use of POSS to improve the properties of polyimide has attracted great interest.
Although the introduction of POSS can improve the dielectric property, thermal stability and mechanical property of the polymer, a key problem still exists in the current nano modification, namely the aggregation of the nano particles and the dispersion of the nano particles in a matrix. The ultra-small volume and the ultra-large specific surface area of the nano particles are the key points for improving the performance of the matrix material, but the nano particles cannot be dispersed in the matrix in a nano size based on the characteristics. The organic component of the POSS outer surface, while conveniently designed and functionalized to lower its surface energy and make it more compatible with the polymer matrix, can still present an inconvenience to its use.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low-shrinkage and high-strength polyimide and a preparation method thereof.
The invention provides polyimide, which is prepared from diamine monomers and dianhydride monomers;
the diamine monomer comprises POSS diamine and diamine containing pyridine structure;
the POSS diamine is represented by formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure BDA0003127110110000021
R3as shown in formula (2):
Figure BDA0003127110110000022
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is an integer of 4 to 10.
Preferably, the diamine containing pyridine structure is represented by formula (II):
Figure BDA0003127110110000023
preferably, the dianhydride monomer is selected from one or more of pyromellitic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl oxide dianhydride, 3 ', 4, 4' -diphenyl sulfide dianhydride, hexafluoro dianhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, bisphenol a type dianhydride, and 3,3 ', 4, 4' -triphenylbisether tetracarboxylic dianhydride.
Preferably, the molar ratio of the POSS diamine to the pyridine structure-containing diamine is 1: (0.5-2).
Preferably, m is 6; p is a radical of1Is 2; p is a radical of2Is 1; p is a radical of3Is 1.
The invention also provides a preparation method of the polyimide, which comprises the following steps:
s1) carrying out polymerization reaction on a diamine monomer and a dianhydride monomer in a protective atmosphere to obtain a polyamic acid solution;
s2) imidizing the polyamic acid solution in a protective atmosphere to obtain a polyimide crude product;
s3) carrying out heat treatment on the polyimide crude product to obtain polyimide;
the diamine monomer comprises POSS diamine and diamine containing pyridine structure;
the POSS diamine is represented by formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure BDA0003127110110000031
R3as shown in formula (2):
Figure BDA0003127110110000032
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is an integer of 4 to 10.
Preferably, the POSS diamines are prepared according to the following process:
A1) will (RSiO)1.5)m+2Reacting with chlorinated acyl chloride shown in formula (III) to obtain a first intermediate product (R' SiO)1.5)m+2；
A2) Subjecting the first intermediate product (R' SiO)1.5)m+2After reduction, a second intermediate product (R) is obtained1SiO1.5)m+2；
A3) Subjecting the second intermediate product (R)1SiO1.5)m+2Reacting with a compound shown as a formula (IV) to obtain a third intermediate product (R)2SiO1.5)m(R1SiO1.5)2；
A4) Subjecting the third intermediate product (R)2SiO1.5)m(R1SiO1.5)2Reacting with phenylenediamine to obtain POSS diamine;
r is represented by formula (3):
Figure BDA0003127110110000033
r' is represented by formula (4):
Figure BDA0003127110110000034
R1as shown in formula (5):
Figure BDA0003127110110000041
preferably, the step S2) is specifically:
mixing the polyimide solution with a water-carrying agent in a protective atmosphere, heating and refluxing for thermal imidization to obtain a polyimide crude product; the volume ratio of the polyimide solution to the water-carrying agent is (3-10): 1.
preferably, the temperature of the heat treatment is 200-350 ℃; the heat treatment time is 1-20 h.
The invention also provides POSS diamine which is shown in the formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure BDA0003127110110000042
R3as shown in formula (2):
Figure BDA0003127110110000043
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is an integer of 4 to 10.
The invention provides polyimide which is characterized by being prepared from diamine monomers and dianhydride monomers; the diamine monomer comprises POSS diamine and diamine containing pyridine structure; the POSS diamine is represented by formula (I): (R)2SiO1.5)m(R3SiO1.5)2Formula (I); wherein m is an integer of 4-10. Compared with the prior art, the preparation method disclosed by the invention has the advantages that the POSS is modified to be liquefied, so that the dispersion characteristic and the solubility of POSS particles are improved, and the strength of polyimide is further improved; at the same time also include pyridineThe pyridine structure can reduce the thermal expansion coefficient of the polyimide, so that the obtained polyimide has low shrinkage and high strength.
Drawings
FIG. 1 is a chart of the infrared spectrum of a liquefied POSS diamine P4 obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides POSS diamine which is shown as a formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10, preferably 4, 6, 8 or 10, and more preferably 6;
R2as shown in formula (1):
Figure BDA0003127110110000051
R3as shown in formula (2):
Figure BDA0003127110110000052
wherein p is1、p2And p3Each independently is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2; in the present invention, most preferably, p1Is 2, p2Is 1; p is a radical of3Is 1; n is an integer of 4-10; in the examples provided by the present invention, n is specifically 4, 5, 6, 7, 8, 9 or 10.
In the present invention, preferablyR is3Comprises the following steps:
Figure BDA0003127110110000061
the invention also provides a preparation method of the POSS diamine, which comprises the following steps: A1) will (RSiO)1.5)m+2Reacting with chlorinated acyl chloride shown in formula (III) to obtain a first intermediate product (R' SiO)1.5)m+2(ii) a A2) Subjecting the first intermediate product (R' SiO)1.5)m+2After reduction, a second intermediate product (R) is obtained1SiO1.5)m+2(ii) a A3) Subjecting the second intermediate product (R)1SiO1.5)m+2Reacting with a compound shown as a formula (IV) to obtain a third intermediate product (R)2SiO1.5)m(R1SiO1.5)2；
R is represented by formula (3):
Figure BDA0003127110110000062
r' is represented by formula (4):
Figure BDA0003127110110000063
R1as shown in formula (5):
Figure BDA0003127110110000064
the invention prepares the liquefied POSS diamine by a click chemical synthesis method, can improve the dispersion characteristic of POSS particles, and further can synthesize polyimide molding powder by using the POSS diamine and the diamine containing a pyridine structure.
The invention provides polyimide, which is prepared from diamine monomers and dianhydride monomers;
the diamine monomer comprises POSS diamine and diamine containing pyridine structure;
the POSS diamine is represented by formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10, preferably 4, 6, 8 or 10, and more preferably 6;
R2as shown in formula (1):
Figure BDA0003127110110000071
R3as shown in formula (2):
Figure BDA0003127110110000072
wherein p is1、p2And p3Each independently is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2; in the present invention, most preferably, p1Is 2, p2Is 1; p is a radical of3Is 1; n is an integer of 4-10; in the examples provided by the present invention, n is specifically 4, 5, 6, 7, 8, 9 or 10.
In the present invention, preferably, R is3Comprises the following steps:
Figure BDA0003127110110000073
the diamine monomer also comprises diamine containing pyridine structure besides POSS diamine; the diamine containing the pyridine structure is preferably shown as a formula (II), and more preferably 2, 5-bis (4-aminophenyl) pyridine.
Figure BDA0003127110110000074
The molar ratio of POSS diamine to pyridine structure-containing diamine is preferably 1: (0.5 to 2), more preferably 1: (0.8 to 1.5), and more preferably 1: (0.8 to 1.2), most preferably 1: 1.
according to the present invention, the dianhydride monomer is preferably one or more of pyromellitic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 3 ', 4, 4' -diphenyl oxide dianhydride, 3 ', 4, 4' -diphenyl sulfide dianhydride, hexafluoro dianhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, bisphenol a type dianhydride, and 3,3 ', 4, 4' -triphenylbisethertetracarboxylic dianhydride.
According to the invention, through modification of POSS, the POSS is liquefied, so that the dispersion characteristic and solubility of POSS particles are improved, and the strength of polyimide is further improved; meanwhile, the pyridine structure is also included, so that the thermal expansion coefficient of the polyimide can be reduced, and the obtained polyimide has low shrinkage and high strength.
The invention also provides a preparation method of the polyimide, which comprises the following steps: s1) carrying out polymerization reaction on a diamine monomer and a dianhydride monomer in a protective atmosphere to obtain a polyamic acid solution; s2) imidizing the polyamic acid solution in a protective atmosphere to obtain a polyimide crude product; s3) carrying out heat treatment on the polyimide crude product to obtain polyimide; the diamine monomer comprises POSS diamine and diamine containing pyridine structure; the POSS diamine is represented by formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure BDA0003127110110000081
R3as shown in formula (2):
Figure BDA0003127110110000082
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is an integer of 4 to 10.
The invention has no special limitation on the sources of all the raw materials, and the raw materials are available on the market; the diamine monomer and the dianhydride monomer are the same as those described above, and are not described in detail herein.
In a protective atmosphere, carrying out polymerization reaction on a diamine monomer and a dianhydride monomer to obtain a polyamic acid solution; the protective atmosphere is preferably nitrogen; the molar ratio of dianhydride monomer to dianhydride monomer is preferably 1: (1-1.03); the polymerization reaction is preferably carried out in an organic solvent; the organic solvent is not particularly limited as long as it is well known to those skilled in the art, but in the present invention, N-dimethylacetamide is preferable; the molar ratio of the diamine monomer in the reaction system is preferably 0.01-0.1 mol/L, more preferably 0.02-0.08 mol/L, still more preferably 0.02-0.06 mol/L, and most preferably 0.03-0.05 mol/L; the time of the polymerization reaction is preferably 4-20 h; in order to ensure that the obtained product is a polyamic acid solution, for example, the mole number of the dianhydride monomer is less than that of the diamine monomer, preferably, after the polymerization reaction is finished, benzoic anhydride is added to continue the reaction to obtain the polyamic acid solution; the continuous reaction time is preferably 1-10 h.
Imidizing the polyamic acid solution in a protective atmosphere; the protective atmosphere is preferably nitrogen; the imidization treatment method can be thermal imidization or chemical imidization; when the method of the imidization treatment is thermal imidization, the step is preferably embodied as: mixing the polyimide solution with a water-carrying agent in a protective atmosphere, heating and refluxing for thermal imidization to obtain a polyimide crude product; the water-carrying agent is preferably xylene; the volume ratio of the polyimide solution to the water-carrying agent is preferably (3-10): 1, more preferably (3-8): 1, and preferably (4-6): 1, most preferably (4-5): 1; the time for thermal imidization is preferably 6-24 h, more preferably 6-18 h, still more preferably 6-12 h, and most preferably 6-10 h; when the method of the imidization treatment is chemical imidization, it is preferable to add an acid anhydride and an amine; the acid anhydride is preferably acetic anhydride; the amine is preferably a secondary amine.
After the imidization treatment is finished, preferably filtering, washing and drying to obtain a crude polyimide product; the washing is preferably ethanol; the drying temperature is preferably 80-90 ℃, and more preferably 85 ℃; the drying time is preferably 5-15 hours, and more preferably 8-10 hours.
Carrying out heat treatment on the polyimide crude product to obtain polyimide; in the present invention, the heat treatment is preferably performed under vacuum; the temperature of the heat treatment is preferably 200-350 ℃, more preferably 250-350 ℃, and further preferably 300 ℃; the time of the heat treatment is preferably 1-20 h, more preferably 2-15 h, still more preferably 2-10 h, and most preferably 4-6 h.
After the heat treatment, preferably, cooling and pulverizing, a polyimide molding powder is obtained, which can be molded by press molding; the compression molding temperature is preferably 300-500 ℃, more preferably 350-450 ℃, and further preferably 400 ℃; the compression molding pressure is preferably 40-60 MPa, more preferably 45-55 MPa, and still more preferably 50 MP.
To further illustrate the present invention, the present invention provides a low shrinkage, high strength polyimide and a method for preparing the same, which will be described in detail with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
1.1 dissolving 13.45g of T8 POSS (shown in formula A) and 11.20g of chlorinated acyl chloride (shown in formula B) in 500mL of dichloromethane, adding 0.21g of lithium perchlorate, stirring at room temperature for reaction for 2 hours, adding 0.74g of Raney nickel, and reacting at 60 ℃ for 1 hour under the protection of nitrogen to obtain a liquefied second intermediate product;
1.2 dissolve 22.41g of the second intermediate in 200ml of DMF, add 0.86g of potassium iodide and 0.86g of triethylamine and then drop 6.43g of benzylamine in 50ml of DMF into a three-necked flask via a constant-pressure dropping funnel. The reaction mixture was heated at 60 ℃ for 6h under nitrogen, then 2.17g P-phenylenediamine was added and heated at 80 ℃ for 3h under nitrogen, and the solvent and redundant triethylamine were removed by rotary evaporation to give a liquefied POSS diamine (n is 4, as shown in formula C) as P4.
Figure BDA0003127110110000101
The liquefied POSS diamine obtained in example 1 was analyzed by infrared spectroscopy to provide an infrared spectrum as shown in fig. 1.
Example 2
Adding 0.05mol (129.326g) of P4 (namely liquefied POSS diamine) and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine (3000ml) into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.0695mol (15.159g) of maleic anhydride, stirring for reacting for 20 hours, adding 0.001mol (0.148g) of benzoic anhydride, reacting for 10 hours to obtain a polyamide acid solution, adding xylene (725ml), heating under nitrogen protection, stirring and refluxing for 6 hours to precipitate yellow powder, cooling, filtering and collecting a filter cake, washing the filter cake with ethanol for 3 times, drying the filtered resin in a blowing drying oven at 85 ℃ for 10 hours, then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
The obtained polyimide molding powder is molded by compression, the molding temperature is 400 ℃, and the molding pressure is 50 MPa. The 5 wt.% thermal weight loss temperature of the polyimide molded article was 543 ℃, the glass transition temperature was 376 ℃ and the impact strength was 126KJ/m2。
Example 3
Adding 0.05mol (N is 5, 143.526g) of P5 (namely liquefied POSS diamine) and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.07mol (15.159g) of polyanhydride, stirring and reacting for 15 hours to obtain a polyamic acid solution, adding xylene (600ml), heating under nitrogen protection, stirring and refluxing for 6 hours to precipitate yellow powder, filtering after cooling, collecting a filter cake, washing 3 times with ethanol, drying the filtered resin in a blast drying oven at 85 ℃ for 10 hours, then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
Example 4
Adding 0.05mol (N is 6, 130.726g) of P6 (namely liquefied POSS diamine) and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.07mol (15.159g) of polyanhydride, stirring and reacting for 12 hours to obtain a polyamic acid solution, adding dimethylbenzene (725ml), heating under the protection of nitrogen, stirring and refluxing for 6 hours to precipitate yellow powder, filtering after cooling, collecting a filter cake, washing 3 times with ethanol, drying the filtered resin in a forced air drying oven at 85 ℃ for 10 hours, and then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
Example 5
Adding 0.05mol (N is 7, 131.426g) of P7 namely liquefied POSS diamine and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.07mol (15.159g) of polyanhydride, stirring and reacting for 12 hours to obtain a polyamic acid solution, adding dimethylbenzene (725ml), heating under the protection of nitrogen, stirring and refluxing for 6 hours to precipitate yellow powder, filtering after cooling, collecting a filter cake, washing 3 times with ethanol, drying the filtered resin in a forced air drying oven at 85 ℃ for 10 hours, then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
Example 6
Adding 0.05mol (N is 8, 132.026g) of P8 (namely liquefied POSS diamine) and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.07mol (15.159g) of polyanhydride, stirring and reacting for 20 hours to obtain a polyamide acid solution, adding xylene (725ml), heating under the protection of nitrogen, stirring and refluxing for 6 hours to precipitate yellow powder, filtering after cooling, collecting a filter cake, washing 3 times with ethanol, drying the filtered resin in a forced air drying oven at 85 ℃ for 10 hours, then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
Example 7
Adding 0.05mol (N is 9, 132.626g) of P9 (namely liquefied POSS diamine) and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.07mol (15.159g) of polyanhydride, stirring and reacting for 8 hours to obtain a polyamide acid solution, adding xylene (725ml), heating under the protection of nitrogen, stirring and refluxing for 6 hours to precipitate yellow powder, filtering after cooling, collecting a filter cake, washing 3 times with ethanol, drying the filtered resin in a forced air drying oven at 85 ℃ for 10 hours, then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
Example 8
Adding 0.05mol (N is 10, 133.226g) of P10 (namely liquefied POSS diamine) and 0.05mol (13.066g) of 2, 5-bis (4-aminophenyl) pyridine into N, N '-dimethylacetamide (3000ml) with nitrogen protection at room temperature, stirring, then adding 0.03mol (8.827g) of 3, 4' -biphenyl dianhydride and 0.07mol (15.159g) of polyanhydride, stirring and reacting for 12 hours to obtain a polyamic acid solution, adding dimethylbenzene (725ml), heating under the protection of nitrogen, stirring and refluxing for 6 hours to precipitate yellow powder, filtering after cooling, collecting a filter cake, washing 3 times with ethanol, drying the filtered resin in a forced air drying oven at 85 ℃ for 10 hours, and then carrying out heat treatment at 300 ℃ for 4 hours in vacuum, and crushing to obtain the polyimide molding powder.
The properties of the polyimide molding powders obtained in examples 2 to 8 were measured, and the tensile strength was measured with reference to GB-T-1040.1-2006-Plastic-measurement of tensile Properties-part 1: a total rule; the dielectric constant was measured using an Agilent 4294A precision impedance analyzer at room temperature and 1 kHz; testing the thermal weight loss temperature of the polyimide provided by the invention at 5 mass percent by using a thermogravimetric analyzer, and under the protection of nitrogen, wherein the heating rate is 10 ℃/min; the linear thermal expansion coefficient test is carried out according to the standard DIN51909-2009, and the heating rate is 10 ℃/min; the results are shown in Table 1.
TABLE 1 polyimide Molding powder Property test results
Figure BDA0003127110110000121
Figure BDA0003127110110000131
As can be seen from the test results in Table 1, the polyimides obtained in examples 2-8 have excellent dielectric properties, high strength and low shrinkage.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The polyimide is characterized by being prepared from a diamine monomer and a dianhydride monomer;
the diamine monomer comprises POSS diamine and diamine containing pyridine structure;
the POSS diamine is represented by formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure FDA0003127110100000011
R3as shown in formula (2):
Figure FDA0003127110100000012
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is 4 to 10An integer number.
2. The polyimide of claim 1, wherein the diamine containing a pyridine structure is represented by formula (II):
Figure FDA0003127110100000013
3. the polyimide according to claim 1, wherein the dianhydride monomer is selected from one or more of pyromellitic dianhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 3 ', 4, 4' -diphenoxyether dianhydride, 3 ', 4, 4' -diphenyl sulfide dianhydride, hexafluoro dianhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, bisphenol a dianhydride, and 3,3 ', 4, 4' -triphenylbisether tetracarboxylic dianhydride.
4. The polyimide of claim 1, wherein the molar ratio of POSS diamine to pyridine structure-containing diamine is from 1: (0.5-2).
5. The polyimide of claim 1, wherein m is 6; p is a radical of1Is 2; p is a radical of2Is 1; p is a radical of3Is 1.
6. A method for preparing polyimide, comprising:
s1) carrying out polymerization reaction on a diamine monomer and a dianhydride monomer in a protective atmosphere to obtain a polyamic acid solution;
s2) imidizing the polyamic acid solution in a protective atmosphere to obtain a polyimide crude product;
s3) carrying out heat treatment on the polyimide crude product to obtain polyimide;
the diamine monomer comprises POSS diamine and diamine containing pyridine structure;
the POSS diamine is represented by formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure FDA0003127110100000021
R3as shown in formula (2):
Figure FDA0003127110100000022
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is an integer of 4 to 10.
7. The method of claim 6, wherein the POSS diamine is prepared according to the following method:
A1) will (RSiO)1.5)m+2Reacting with chlorinated acyl chloride shown in formula (III) to obtain a first intermediate product (R' SiO)1.5)m+2；
A2) Subjecting the first intermediate product (R' SiO)1.5)m+2After reduction, a second intermediate product (R) is obtained1SiO1.5)m+2；
A3) Subjecting the second intermediate product (R)1SiO1.5)m+2Reacting with a compound shown as a formula (IV) to obtain a third intermediate product (R)2SiO1.5)m(R1SiO1.5)2；
A4) Subjecting the third intermediate product (R)2SiO1.5)m(R1SiO1.5)2Reacting with phenylenediamine to obtain POSS diamine;
r is represented by formula (3):
Figure FDA0003127110100000031
r' is represented by formula (4):
Figure FDA0003127110100000032
R1as shown in formula (5):
Figure FDA0003127110100000033
8. the preparation method according to claim 6, wherein the step S2) is specifically:
mixing the polyimide solution with a water-carrying agent in a protective atmosphere, heating and refluxing for thermal imidization to obtain a polyimide crude product; the volume ratio of the polyimide solution to the water-carrying agent is (3-10): 1.
9. the method according to claim 6, wherein the temperature of the heat treatment is 200 to 350 ℃; the heat treatment time is 1-20 h.
10. A POSS diamine of formula (I):
(R2SiO1.5)m(R3SiO1.5)2formula (I)
Wherein m is an integer of 4-10;
R2as shown in formula (1):
Figure FDA0003127110100000041
R3as shown in formula (2):
Figure FDA0003127110100000042
wherein p is1、p2And p3Each independently is an integer of 1 to 5; n is an integer of 4 to 10.
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