CN113135950A - Diamine monomer and dianhydride monomer containing carborane structure as well as preparation methods and applications of diamine monomer and dianhydride monomer - Google Patents
Diamine monomer and dianhydride monomer containing carborane structure as well as preparation methods and applications of diamine monomer and dianhydride monomer Download PDFInfo
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- CN113135950A CN113135950A CN202010057986.1A CN202010057986A CN113135950A CN 113135950 A CN113135950 A CN 113135950A CN 202010057986 A CN202010057986 A CN 202010057986A CN 113135950 A CN113135950 A CN 113135950A
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- 239000000178 monomer Substances 0.000 title claims abstract description 116
- 150000004985 diamines Chemical class 0.000 title claims abstract description 56
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 26
- 229920001721 polyimide Polymers 0.000 claims abstract description 14
- 238000007259 addition reaction Methods 0.000 claims abstract description 12
- 239000004642 Polyimide Substances 0.000 claims abstract description 8
- 238000006396 nitration reaction Methods 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 196
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 150000001875 compounds Chemical class 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 238000005406 washing Methods 0.000 claims description 53
- -1 alkynyl compound Chemical class 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 125000000304 alkynyl group Chemical group 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 13
- 150000002828 nitro derivatives Chemical class 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 40
- 238000001035 drying Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 26
- 238000010992 reflux Methods 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 238000004821 distillation Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000009719 polyimide resin Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a diamine monomer and a dianhydride monomer containing carborane structures, and preparation methods and applications thereof. The invention also discloses high-temperature resistant polyimide containing a carborane structure, which is prepared by performing polycondensation reaction on the diamine monomer containing the carborane structure and the dianhydride monomer containing the carborane structure. Decaborane and alkyne are used as initial raw materials, a carborane structural unit is prepared through an addition reaction of decaborane and alkyne, and a diamine monomer containing a carborane structure is prepared through a nitration reaction and a reduction reaction, or a dianhydride monomer containing a carborane structure is prepared through a methyl oxidation and dehydration reaction. The method for preparing the diamine monomer or dianhydride monomer containing the carborane structure has the advantages of simple operation, wide universality, convenient and easily obtained raw materials, high yield and the like, and is convenient for large-scale production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a polyimide monomer containing a carborane structure, and a preparation method and application thereof.
Background
Polyimide resin-based composite materials are widely applied to the aerospace field because of having excellent heat resistance, low temperature resistance, solvent resistance, flame retardance and the like, and simultaneously having excellent dielectric properties and mechanical properties. With the continuous and deep development of the aerospace industry, the requirement on the temperature resistance level of the composite material is higher and higher. At present, the heat resistance limit of polyimide composite materials of all organic molecules adopted in the aerospace field is mostly below 450 ℃, and the development requirements of the aerospace field in the future cannot be met.
In order to solve the above problems, foreign researchers have reported in recent years that P2SI900HT polyimide resin containing silicon-oxygen bond has a glass transition temperature as high as 466 ℃ and can be used for a long time at 427 ℃. In addition, scholars at home and abroad also have researches on introducing carborane structures into polyimide resin, and successfully verify that the method can greatly improve the temperature resistance of the polyimide resin, the glass transition temperature of the polyimide resin can be higher than 550 ℃, and the 5% thermal weight loss of the polyimide resin is close to 600 ℃. Therefore, the carborane structure is introduced into the polyimide, and the method is a very effective method for improving the temperature resistance level of the polyimide. However, the preparation technology of the dianhydride monomer and the diamine monomer containing carborane structures in China is not mature, and the requirement of mass production cannot be met.
Disclosure of Invention
The invention mainly aims to provide a diamine monomer and a dianhydride monomer containing carborane structures, and preparation methods and applications thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a diamine monomer containing a carborane structure, which has a structure shown in any one of formulas I-V:
wherein, aB is 0 to 2, R1Any one of the following structures:
R2any one of the following structures:
R3any one of the following structures:
the embodiment of the invention also provides a preparation method of a diamine monomer containing a carborane structure, which comprises the following steps:
(1) carrying out addition reaction on a first uniform mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) enabling a second uniformly mixed reaction system containing the decaborane and acetonitrile complex, the alkynyl compound, the silver nitrate and a second solvent to react for 3-8 hours at the temperature of 80-120 ℃, and then carrying out post-treatment to obtain a compound containing a carborane structure;
(3) carrying out nitration reaction on a third uniformly mixed reaction system containing the compound containing the carborane structure, concentrated nitric acid and concentrated sulfuric acid at the temperature of 0-60 ℃ for 4-10 h to prepare a nitro compound containing the carborane structure;
(4) carrying out reduction reaction for 1-5 h at 80-120 ℃ in a fourth uniformly mixed reaction system containing the nitro compound containing the carborane structure, a reducing agent, ammonium chloride, ethanol and water, and carrying out aftertreatment to obtain a diamine monomer containing the carborane structure, wherein the diamine monomer has a structure shown in any one of formulas I-II:
wherein a and b are both 0-2, R1Any one of the following structures:
the embodiment of the invention also provides a preparation method of a diamine monomer containing a carborane structure, which comprises the following steps:
(1) carrying out addition reaction on a first mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) reacting a second mixed reaction system containing an alkynyl diamine monomer, di-tert-butyl dicarbonate and a second solvent at 25-50 ℃ for 4-10 h to prepare a tert-butoxycarbonyl protected alkynyl diamine monomer;
(3) reacting a third mixed reaction system containing the tert-butoxycarbonyl protected alkynyl diamine monomer, decaborane and acetonitrile complex, silver nitrate and a first solvent at 80-120 ℃ for 3-8 h, and performing aftertreatment to obtain a compound containing a carborane structure;
(4) enabling a fourth mixed reaction system containing the compound containing the carborane structure, a second solvent and trifluoroacetic acid to react for 0.5-3 h at room temperature to obtain a diamine monomer containing the carborane structure, wherein the diamine monomer has a structure shown in any one of formulas III-V:
wherein R is2Any one of the following structures:
R3selected from the following structuresAny one of:
the embodiment of the invention also provides a dianhydride monomer containing a carborane structure, wherein the dianhydride monomer containing the carborane structure has a structure shown in any one of a formula VI to a formula IX:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
the embodiment of the invention also provides a preparation method of the dianhydride monomer containing the carborane structure, which comprises the following steps:
(1) carrying out addition reaction on a first mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) reacting a second mixed reaction system containing alkynyl dianhydride, boron trifluoride ethyl ether and a second solvent at the temperature of 60-80 ℃ for 5-10 hours, and performing post-treatment to obtain an alkynyl-containing tetraester compound;
(3) enabling a third mixed reaction system containing the alkynyl-containing tetraester compound, a decaborane and acetonitrile complex and a first solvent to react for 3-8 hours at the temperature of 80-120 ℃, and then carrying out aftertreatment to obtain the tetraester compound containing a carborane structure;
(4) reacting a fourth mixed reaction system containing the tetra-ester compound containing the carborane structure, a sodium hydroxide solution and a third solvent at the temperature of 20-60 ℃ for 5-20 hours, and then carrying out post-treatment to obtain a tetra-acid compound containing the carborane structure;
(5) reacting a fifth mixed reaction system containing a tetra-acid compound containing a carborane structure and acetic anhydride at 120-150 ℃ for 3-10 h, and performing post-treatment to obtain a dianhydride monomer containing a carborane structure, wherein the dianhydride monomer has a structure shown in any one of formulas VI-IX:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
embodiments of the present invention also provide a dianhydride monomer containing a carborane structure prepared by the foregoing method, having a structure represented by any one of formulas vi to ix:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
the embodiment of the invention also provides high-temperature-resistant polyimide containing a carborane structure, which is prepared by performing polycondensation reaction on the diamine monomer containing the carborane structure and the dianhydride monomer containing the carborane structure.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, decaborane and alkyne are used as initial raw materials, a carborane structural unit is prepared through an addition reaction of decaborane and alkyne, and then a diamine monomer containing a carborane structure is prepared through a nitration reaction and a reduction reaction, or a dianhydride monomer containing a carborane structure is prepared through oxidation and dehydration reactions of methyl. The preparation method provided by the invention has the advantages of simple operation, wide universality, convenient and easily obtained raw materials, high yield and the like, and is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a nuclear magnetic spectrum of a carborane structure-containing compound obtained in step two of example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of a nitro compound containing a carborane structure obtained in step three of example 1 according to the present invention;
FIG. 3 is a nuclear magnetic spectrum of a diamine monomer containing a carborane structure obtained in step four of example 1 of the present invention;
FIG. 4 is a nuclear magnetic spectrum of the alkynyl-containing tetraesters obtained in step two of example 3 of the present invention;
FIG. 5 is a nuclear magnetic spectrum of a tetrabasic compound containing a carborane structure obtained in step three of example 3 according to the present invention;
FIG. 6 is a nuclear magnetic spectrum of a dianhydride monomer containing a carborane structure prepared in step five of example 3 according to the invention;
FIG. 7 is a synthesis scheme for the preparation of diamine monomers containing carborane structures according to example 1 of the present invention;
FIG. 8 is a synthesis scheme for the preparation of diamine monomers containing carborane structures according to example 2 of the present invention;
FIG. 9 is a synthesis scheme for the preparation of a dianhydride monomer containing a carborane structure according to example 3 of the present invention;
FIG. 10 is a synthesis scheme for the preparation of diamine monomers containing carborane structures according to example 4 of the present invention;
FIG. 11 is a synthesis scheme for the preparation of diamine monomers containing carborane structures according to example 5 of the present invention;
FIG. 12 is a synthesis scheme for the preparation of a dianhydride monomer containing a carborane structure according to example 6 of the present invention;
FIG. 13 is a synthesis scheme for the preparation of diamine monomers containing carborane structures according to example 7 of the present invention;
FIG. 14 is a synthesis scheme for the preparation of a dianhydride monomer containing a carborane structure according to example 8 of the present invention;
FIG. 15 is a synthesis scheme for the preparation of a carborane structure-containing dianhydride monomer of example 9 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventors of the present invention have long studied and practiced in a large number of ways to provide the technical solutions of the present invention, and the present invention adopts decaborane and alkyne as initial raw materials, prepares carborane structural units through an addition reaction of decaborane and alkyne, and then prepares diamine monomers containing carborane structures through a nitration reaction and a reduction reaction, or prepares dianhydride monomers containing carborane structures through oxidation and dehydration reactions of methyl groups.
One aspect of embodiments of the present invention provides a carborane structure-containing diamine monomer having a structure as shown in any one of formulas I-V:
wherein a and b are both 0-2, R1Any one of the following structures:
R2any one of the following structures:
R3any one of the following structures:
in another aspect of the embodiments of the present invention, there is provided a method for preparing a diamine monomer containing a carborane structure, including:
(1) carrying out addition reaction on a first uniform mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) enabling a second uniformly mixed reaction system containing the decaborane and acetonitrile complex, the alkynyl compound, the silver nitrate and a second solvent to react for 3-8 hours at the temperature of 80-120 ℃, and then carrying out post-treatment to obtain a compound containing a carborane structure;
(3) carrying out nitration reaction on a third uniformly mixed reaction system containing the compound containing the carborane structure, concentrated nitric acid and concentrated sulfuric acid at the temperature of 0-60 ℃ for 4-10 h to prepare a nitro compound containing the carborane structure;
(4) carrying out reduction reaction for 1-5 h at 80-120 ℃ in a fourth uniformly mixed reaction system containing the nitro compound containing the carborane structure, a reducing agent, ammonium chloride, ethanol and water, and carrying out aftertreatment to obtain a diamine monomer containing the carborane structure, wherein the diamine monomer has a structure shown in any one of formulas I-II:
wherein a and b are both 0-2, R1Any one of the following structures:
in some more specific embodiments, the molar ratio of decaborane to acetonitrile in step (1) is from 0.1 to 1: 1.
Further, the first solvent in the step (1) includes toluene, and is not limited thereto.
In some more specific embodiments, the molar ratio of decaborane and acetonitrile complex, silver nitrate, and alkynyl compound in step (2) is (0.5-2): 0.05-0.2): 1.
Further, the alkynyl compound is a compound containing the R1A compound of structure (la), without limitation.
Further, the second solvent in the step (2) includes toluene, and is not limited thereto.
Further, the post-processing in the step (2) comprises: the mixture obtained from the reaction is concentrated, washed and recrystallized.
In some specific embodiments, the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid in the step (3) is 0.1-1: 1.
In some more specific embodiments, the molar ratio of the nitro compound containing a carborane structure, the reducing agent and the ammonium chloride in the step (4) is 1 (1-5) to (1-8).
Further, the volume ratio of the ethanol to the water in the step (4) is 1-5: 1.
Further, the reducing agent in the step (4) includes iron powder, and is not limited thereto.
The embodiment of the invention also provides a preparation method of a diamine monomer containing a carborane structure, which comprises the following steps:
(1) carrying out addition reaction on a first mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) reacting a second mixed reaction system containing an alkynyl diamine monomer, di-tert-butyl dicarbonate and a second solvent at 25-50 ℃ for 4-10 h to prepare a tert-butoxycarbonyl protected alkynyl diamine monomer;
(3) reacting a third mixed reaction system containing the tert-butoxycarbonyl protected alkynyl diamine monomer, decaborane and acetonitrile complex, silver nitrate and a first solvent at 80-120 ℃ for 3-8 h, and performing aftertreatment to obtain a compound containing a carborane structure;
(4) enabling a fourth mixed reaction system containing the compound containing the carborane structure, a second solvent and trifluoroacetic acid to react for 0.5-3 h at room temperature to obtain a diamine monomer containing the carborane structure, wherein the diamine monomer has a structure shown in any one of formulas III-V:
wherein R is2Any one of the following structures:
R3any one of the following structures:
in some more specific embodiments, the molar ratio of decaborane to acetonitrile in step (1) is from 0.1 to 1: 1.
In some more specific embodiments, step (2) specifically includes: and uniformly mixing the alkynyl-containing diamine monomer with a second solvent to form a mixture, and then dropwise adding di-tert-butyl dicarbonate into the mixture at 0-25 ℃ to form the second mixed reaction system.
Further, the molar ratio of the di-tert-butyl dicarbonate to the alkynyl-containing diamine monomer is 2-4: 1.
Further, the alkynyl diamine monomer is a monomer containing the R2And/or R3A compound of structure (la);
in some specific embodiments, the molar ratio of the t-butyloxycarbonyl-protected alkynyl diamine monomer, decaborane and acetonitrile complex, and silver nitrate in step (3) is 1 (0.5-2) to (0.05-0.2).
Further, the post-processing in the step (3) comprises: the mixture obtained from the reaction is concentrated, washed and recrystallized.
In some more specific embodiments, the volume ratio of the second solvent to trifluoroacetic acid in step (4) is 0.5-2: 1.
In some more specific embodiments, the first solvent in step (1) or (3) comprises toluene, and is not limited thereto.
Further, the second solvent in step (2) or (4) includes dichloromethane, and is not limited thereto.
The embodiment of the invention also provides a dianhydride monomer containing a carborane structure, wherein the dianhydride monomer containing the carborane structure has a structure shown in any one of a formula VI to a formula IX:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
the embodiment of the invention also provides a preparation method of the dianhydride monomer containing the carborane structure, which is characterized by comprising the following steps:
(1) carrying out addition reaction on a first mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) reacting a second mixed reaction system containing alkynyl dianhydride, boron trifluoride ethyl ether and a second solvent at the temperature of 60-80 ℃ for 5-10 hours, and performing post-treatment to obtain an alkynyl-containing tetraester compound;
(3) enabling a third mixed reaction system containing the alkynyl-containing tetraester compound, a decaborane and acetonitrile complex and a first solvent to react for 3-8 hours at the temperature of 80-120 ℃, and then carrying out aftertreatment to obtain the tetraester compound containing a carborane structure;
(4) reacting a fourth mixed reaction system containing the tetra-ester compound containing the carborane structure, a sodium hydroxide solution and a third solvent at the temperature of 20-60 ℃ for 5-20 hours, and then carrying out post-treatment to obtain a tetra-acid compound containing the carborane structure;
(5) reacting a fifth mixed reaction system containing a tetra-acid compound containing a carborane structure and acetic anhydride at 120-150 ℃ for 3-10 h, and performing post-treatment to obtain a dianhydride monomer containing a carborane structure, wherein the dianhydride monomer has a structure shown in any one of formulas VI-IX:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
in some more specific embodiments, the molar ratio of decaborane to acetonitrile in step (1) is from 0.1 to 1: 1.
In some more specific embodiments, the molar equivalent ratio of the alkynyl dianhydride to boron trifluoride diethyl etherate in step (2) is 0.1 to 5: 1.
Further, the alkynyl dianhydride is the one containing the R1A compound of structure (la), without limitation.
Further, the second solvent in the step (2) includes methanol, and is not limited thereto.
In some specific embodiments, the molar ratio of the alkynyl-containing tetraesters, decaborane and acetonitrile complex and silver nitrate in step (3) is 1 (0.5-2) to (0.05-0.2).
Further, the post-processing in the step (3) comprises: and (3) concentrating, washing and recrystallizing the mixture obtained by the reaction.
And in some more specific embodiments, the first solvent in step (1) or (3) comprises toluene, and is not limited thereto.
In some more specific embodiments, the post-treatment in step (4) comprises: and filtering, boiling with hydrochloric acid and washing the obtained mixture.
Further, the third solvent in the step (4) includes tetrahydrofuran, and is not limited thereto.
Further, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution in the step (4) is 10-50 wt%.
Embodiments of the present invention also provide a dianhydride monomer containing a carborane structure prepared by the foregoing method, having a structure represented by any one of formulas vi to ix:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
the embodiment of the invention also provides high-temperature-resistant polyimide containing a carborane structure, which is prepared by performing polycondensation reaction on the diamine monomer containing the carborane structure and the dianhydride monomer containing the carborane structure.
The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, heating reflux is carried out for 4h at 80 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: adding tolane (160.4g), decaborane and acetonitrile complex (0.99mol) obtained in the step one, and silver nitrate (0.45mol) into 1.5L of toluene, mixing, heating and refluxing at 100 ℃ for 8h, after the reaction is finished, carrying out reduced pressure distillation, washing (sequentially using methanol for 2 times, hydrochloric acid for 2 times, and water for 3 times), and drying to obtain a white solid (219.1g, 0.73mol, and the yield is 81%) which is a compound containing a carborane structure (a nuclear magnetic spectrum is shown in figure 1);
step three: adding the compound (0.5mol) containing the carborane structure obtained in the step two into a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:2, stirring and reacting for 5 hours at room temperature, and filtering, washing and drying to obtain a white solid (0.43mol, wherein the yield is 86%) which is the nitro compound containing the carborane structure (shown in a nuclear magnetic spectrum figure 2);
step four: and (3) adding the nitro compound containing the carborane structure (0.4mol), iron powder (1.6mol) and ammonium chloride (2mol) obtained in the step three into 1L of mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 1:1), heating and refluxing for 4h at 100 ℃, filtering, concentrating, extracting (extracting for 3 times by ethyl acetate), and distilling to obtain a white solid (0.37mol, the yield is 92%) which is the diamine monomer containing the carborane structure (a nuclear magnetic spectrum is shown in figure 3).
In this example, the synthesis route of the diamine monomer containing a carborane structure is shown in fig. 7.
Example 2
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, then heating reflux is carried out for 4h at 120 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: in an ice-water bath, slowly dropwise adding di-tert-butyl dicarbonate (523.8g) into a dichloromethane solution containing alkynyl diamine compound (222.3g), stirring at room temperature for reaction for 10 hours after dropwise adding, and distilling and washing to obtain a white solid (0.99mol, yield 99%) which is the alkynyl diamine compound containing Boc protection;
step three: adding the Boc-protected alkynediamine compound (380.3g) obtained in the third step, the decaborane and acetonitrile complex (199.8g) obtained in the first step and silver nitrate (15.3g) into 1.5L of toluene, heating and refluxing for 6h at 100 ℃, and after the reaction is finished, carrying out reduced pressure distillation, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times), and drying to obtain a white solid (438.3g, 0.70mol, yield 78%) which is the Boc-protected amino compound containing a carborane structure;
step four: and (3) adding the Boc protected amino compound containing the carborane structure (0.5mol) obtained in the third step into 1L of a mixed solution of trifluoroacetic acid and dichloromethane (the volume ratio of the trifluoroacetic acid to the dichloromethane is 1:1), stirring and reacting for 2h at room temperature, and washing, distilling and drying to obtain a white solid (167.9g, 0.49mol, the yield is 98%) which is the diamine monomer containing the carborane structure.
The synthesis route of the diamine monomer containing carborane structure prepared in this example is shown in FIG. 8.
Example 3
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, heating reflux is carried out for 4h at 100 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: adding 1mol of alkynyl-containing dianhydride and 2mol of boron trifluoride ether into 1.5L of methanol, mixing, stirring at 60 ℃ for reaction for 10 hours, and distilling, washing and drying after the reaction is finished to obtain a white solid (402.2g, 0.98mol and 98% yield), namely the alkynyl-containing tetraester compound (shown in a nuclear magnetic spectrum figure 4);
step three: adding the alkynyl-containing tetraester compound (0.8mol) obtained in the step two, the decaborane and acetonitrile complex (0.99mol) obtained in the step one and silver nitrate (0.09mol) into 1.5L of toluene, mixing, heating and refluxing for 7h at 100 ℃, and distilling, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times) and drying after the reaction is finished to obtain a white solid (350.3g, 0.66mol and 82% of yield), namely the tetraester compound containing the carborane structure (a nuclear magnetic spectrum is shown in figure 5);
step four: preparing sodium hydroxide solution from sodium hydroxide (3mol) and 200mL of water, adding the sodium hydroxide solution into 1L of tetrahydrofuran solution containing the tetrabasic ester compound containing the carborane structure (0.5mol) obtained in the step III, stirring and reacting at room temperature for 12h, filtering, putting filter residues into 1L of hydrochloric acid (the concentration is 37%), heating and refluxing for 5h, and filtering and washing to obtain a white solid (232.6g, 0.49mol, the yield is 98%) which is the tetrabasic acid containing the carborane structure;
step five: and (3) adding the tetracarboxylic acid (0.4mol) containing the carborane structure obtained in the step four into 1L of acetic anhydride, heating and refluxing for 3h at 150 ℃, cooling, filtering, washing with water, and drying to obtain a white solid (171.1g, 0.39mol, the yield is 98%) which is the dianhydride monomer containing the carborane structure (shown in a nuclear magnetic spectrum figure 6).
The synthesis route of the dianhydride monomer containing a carborane structure prepared in this example is shown in FIG. 9.
Example 4
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, heating reflux is carried out for 6h at 120 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: adding an alkynyl-containing compound (97.3g), the decaborane and acetonitrile complex (0.99mol) obtained in the step one and silver nitrate (0.45mol) into 1.5L of toluene, mixing, heating and refluxing for 4h at 120 ℃, and after the reaction is finished, carrying out reduced pressure distillation, washing (sequentially using methanol for 2 times, hydrochloric acid for 2 times and water for 3 times), and drying to obtain a white solid (121.9g, 0.36mol, yield 80%) which is the compound containing the carborane structure;
step three: adding the compound (0.25mol) containing the carborane structure obtained in the step two into a mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:2, stirring and reacting for 10 hours at room temperature, and filtering, washing and drying to obtain a white solid (0.21mol, wherein the yield is 85%) which is the nitro compound containing the carborane structure;
step four: and (3) adding the nitro compound containing the carborane structure (0.2mol), the iron powder (0.8mol) and the ammonium chloride (1mol) obtained in the step three into 1L of mixed liquor of ethanol and water (the volume ratio of the ethanol to the water is 1:1), heating and refluxing for 1h at 120 ℃, and filtering, concentrating, extracting (extracting for 3 times by ethyl acetate), and distilling to obtain a white solid (0.18mol, wherein the yield is 90%) to obtain the diamine monomer containing the carborane structure.
In this example, the synthesis route of the diamine monomer containing a carborane structure is shown in FIG. 10.
Example 5
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, then the mixture is heated and refluxed for 6h at 80 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: in an ice-water bath, slowly dropwise adding di-tert-butyl dicarbonate (523.8g) into a dichloromethane solution containing an alkynyl diamine compound (224..3g), stirring at room temperature for reacting for 4 hours after dropwise adding is finished, and distilling and washing to obtain a white solid (0.99mol, yield 99%) which is the alkynyl diamine compound containing Boc protection;
step three: adding the Boc-protected alkynediamine compound (382.1g) obtained in the third step, the decaborane and acetonitrile complex (199.8g) obtained in the first step and silver nitrate (15.3g) into 1.5L of toluene, heating and refluxing for 3h at 120 ℃, and after the reaction is finished, carrying out reduced pressure distillation, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times), and drying to obtain a white solid (427.1g, 0.68mol, yield 75%) which is the Boc-protected amino compound containing a carborane structure;
step four: and (3) adding the Boc protected amino compound containing the carborane structure obtained in the third step (0.5mol) into 1L of mixed solution of trifluoroacetic acid and dichloromethane (the volume ratio of the trifluoroacetic acid to the dichloromethane is 1:1), stirring and reacting for 3h at room temperature, and washing, distilling and drying to obtain a white solid (168.9g, 0.49mol, the yield is 98%) which is the diamine monomer containing the carborane structure.
The synthesis route of the diamine monomer containing carborane structure prepared in this example is shown in FIG. 11.
Example 6
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, heating reflux is carried out for 3h at 120 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: adding 1mol of alkynyl-containing dianhydride and 2mol of boron trifluoride diethyl etherate into 1.5L of methanol for mixing, stirring at 80 ℃ for reaction for 5 hours, and after the reaction is finished, distilling, washing and drying to obtain a white solid (430.5g, 0.96mol, the yield is 96%) which is the alkynyl-containing tetraester compound;
step three: adding the alkynyl-containing tetraester compound (0.8mol) obtained in the step two, the decaborane and acetonitrile complex (0.99mol) obtained in the step one and silver nitrate (0.09mol) into 1.5L of methylbenzene, mixing, heating and refluxing for 3h at 120 ℃, and distilling, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times) after the reaction is finished, and drying to obtain a white solid (440.7g, 0.64mol, yield 80%) which is the tetraester compound containing the carborane structure;
step four: preparing sodium hydroxide solution from sodium hydroxide (3mol) and 200mL of water, adding the sodium hydroxide solution into 1L of tetrahydrofuran solution containing the tetrabasic ester compound containing the carborane structure (0.5mol) obtained in the step III, stirring and reacting at room temperature for 20h, filtering, putting filter residues into 1L of hydrochloric acid (the concentration is 37%), heating and refluxing for 10h, and filtering and washing to obtain a white solid (303.6g, 0.48mol, the yield is 96%) which is the tetrabasic acid containing the carborane structure;
step five: and (3) adding the tetracarboxylic acid containing the carborane structure (0.4mol) obtained in the step four into 1L of acetic anhydride, heating and refluxing for 10h at 120 ℃, cooling, filtering, washing with water, and drying to obtain a white solid (226.7g, 0.38mol, yield 95%) which is the dianhydride monomer containing the carborane structure.
The synthesis route of the dianhydride monomer containing a carborane structure prepared in this example is shown in FIG. 12.
Example 7
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, then the mixture is heated and refluxed for 3h at 100 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: in an ice-water bath, slowly dropwise adding di-tert-butyl dicarbonate (523.8g) into a dichloromethane solution containing alkynyl diamine compound (158.2g), stirring at room temperature for reaction for 6 hours after dropwise adding, and distilling and washing to obtain a white solid (0.99mol, yield 99%) which is the alkynyl diamine compound containing Boc protection;
step three: adding the Boc-protected alkynediamine compound (322.6g) containing the carborane structure obtained in the third step, the decaborane and acetonitrile complex (199.8g) obtained in the first step and silver nitrate (15.3g) into 1.5L of toluene, heating and refluxing for 8h at 80 ℃, and after the reaction is finished, carrying out reduced pressure distillation, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times), and drying to obtain a white solid (404.6g, 0.72mol and the yield of 80%), namely the Boc-protected amino compound containing the carborane structure;
step four: and (3) adding the Boc protected amino compound containing the carborane structure obtained in the third step (0.5mol) into 1L of mixed solution of trifluoroacetic acid and dichloromethane (the volume ratio of the trifluoroacetic acid to the dichloromethane is 1:1), stirring and reacting for 0.5h at room temperature, washing, distilling and drying to obtain a white solid (136.5g, 0.49mol and the yield of 98%) which is the diamine monomer containing the carborane structure.
The synthetic route of the diamine monomer containing a carborane structure prepared in this example is shown in FIG. 13.
Example 8
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, heating reflux is carried out for 6h at 80 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: adding 1mol of alkynyl-containing dianhydride and 2mol of boron trifluoride diethyl etherate into 1.5L of methanol for mixing, stirring at 70 ℃ for reaction for 7h, and after the reaction is finished, distilling, washing and drying to obtain a white solid (398.1g, 0.97mol, yield 97%) which is the alkynyl-containing tetraester compound;
step three: adding the alkynyl-containing tetraester compound (0.8mol) obtained in the step two, the decaborane and acetonitrile complex (0.99mol) obtained in the step one and silver nitrate (0.09mol) into 1.5L of methylbenzene, mixing, heating and refluxing for 8h at 80 ℃, and distilling, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times) after the reaction is finished to obtain a white solid (344.8g, 0.65mol and the yield of 81%) which is the tetraester compound containing the carborane structure;
step four: preparing sodium hydroxide solution from sodium hydroxide (3mol) and 200mL of water, adding the sodium hydroxide solution into 1L of tetrahydrofuran solution containing the tetrabasic ester compound containing the carborane structure (0.5mol) obtained in the step III, stirring and reacting at room temperature for 5h, filtering, putting filter residues into 1L of hydrochloric acid (the concentration is 37%), heating and refluxing for 20h, and filtering and washing to obtain a white solid (227.7g, 0.48mol, the yield is 96%) which is the tetrabasic acid containing the carborane structure;
step five: and (3) adding the tetracarboxylic acid (0.4mol) containing the carborane structure obtained in the step four into 1L of acetic anhydride, heating and refluxing for 8h at 130 ℃, cooling, filtering, washing with water, and drying to obtain a white solid (166.6g, 0.38mol, the yield is 95%) which is the dianhydride monomer containing the carborane structure.
The synthesis route of the dianhydride monomer containing a carborane structure prepared in this example is shown in FIG. 14.
Example 9
The method comprises the following steps: decaborane (122.3g) and acetonitrile (82.1g) are added into 1L of toluene and mixed, heating reflux is carried out for 5h at 100 ℃, and after the reaction is finished, white solid (0.99mol, the yield is 99%) obtained by reduced pressure distillation, washing (cyclohexane washing for 2 times) and drying is complex compound of decaborane and acetonitrile;
step two: adding 1mol of alkynyl-containing dianhydride and 2mol of boron trifluoride diethyl etherate into 1.5L of methanol, mixing, stirring at 70 ℃ for reaction for 8h, and distilling, washing and drying after the reaction is finished to obtain a white solid (426.0g, 0.95mol, yield 95%) which is the alkynyl-containing tetraester compound;
step three: adding the alkynyl-containing tetraester compound (0.8mol) obtained in the step two, the decaborane and acetonitrile complex (0.99mol) obtained in the step one and silver nitrate (0.09mol) into 1.5L of toluene, mixing, heating and refluxing for 6h at 100 ℃, and after the reaction is finished, distilling, washing (methanol for 2 times, hydrochloric acid for 2 times and water for 3 times), and drying to obtain a white solid (427g, 0.62mol, yield 78%) which is the tetraester compound containing the carborane structure;
step four: preparing sodium hydroxide solution from sodium hydroxide (3mol) and 200mL of water, adding the sodium hydroxide solution into 1L of tetrahydrofuran solution containing the tetrabasic ester compound containing the carborane structure (0.5mol) obtained in the step III, stirring and reacting at room temperature for 15h, filtering, putting filter residues into 1L of hydrochloric acid (the concentration is 37%), heating and refluxing for 12h, and filtering and washing to obtain a white solid (297.3g, 0.47mol, the yield is 94%) which is the tetrabasic acid containing the carborane structure;
step five: and (3) adding the tetracarboxylic acid (0.4mol) containing the carborane structure obtained in the step four into 1L of acetic anhydride, heating and refluxing for 5h at 140 ℃, cooling, filtering, washing with water, and drying to obtain a white solid (220.7g, 0.37mol, and the yield is 92%) which is the dianhydride monomer containing the carborane structure.
The synthesis route of the dianhydride monomer containing a carborane structure prepared in this example is shown in FIG. 15.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A carborane structure-containing diamine monomer having a structure according to any one of formulas I-V:
wherein a and b are both 0-2, R1Any one of the following structures:
R2any one of the following structures:
R3any one of the following structures:
2. a method for preparing diamine monomer containing carborane structure is characterized by comprising the following steps:
(1) carrying out addition reaction on a first uniform mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) enabling a second uniformly mixed reaction system containing the decaborane and acetonitrile complex, the alkynyl compound, the silver nitrate and a second solvent to react for 3-8 hours at the temperature of 80-120 ℃, and then carrying out post-treatment to obtain a compound containing a carborane structure;
(3) carrying out nitration reaction on a third uniformly mixed reaction system containing the compound containing the carborane structure, concentrated nitric acid and concentrated sulfuric acid at the temperature of 0-60 ℃ for 4-10 h to prepare a nitro compound containing the carborane structure;
(4) carrying out reduction reaction for 1-5 h at 80-120 ℃ in a fourth uniformly mixed reaction system containing the nitro compound containing the carborane structure, a reducing agent, ammonium chloride, ethanol and water, and carrying out aftertreatment to obtain a diamine monomer containing the carborane structure, wherein the diamine monomer has a structure shown in any one of formulas I-II:
wherein a and b are both 0-2, R1Any one of the following structures:
3. the method of claim 2, wherein: the molar ratio of decaborane to acetonitrile in the step (1) is 0.1-1: 1; preferably, the first solvent in step (1) comprises toluene;
and/or the molar ratio of the decaborane to the complex of acetonitrile, silver nitrate and alkynyl compound in the step (2) is (0.5-2): 0.05-0.2): 1; preferably, said alkynyl compound is a compound comprising said R1A compound of structure (la); preferably, the second solvent in step (2) comprises toluene;
preferably, the post-treatment in step (2) comprises: concentrating, washing and recrystallizing the mixture obtained by the reaction;
and/or the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid in the step (3) is 0.1-1: 1;
and/or the molar ratio of the nitro compound containing the carborane structure, the reducing agent and the ammonium chloride in the step (4) is 1 (1-5) to (1-8); preferably, the volume ratio of the ethanol to the water in the step (4) is 1-5: 1; preferably, the reducing agent in step (4) comprises iron powder.
4. A method for preparing diamine monomer containing carborane structure is characterized by comprising the following steps:
(1) carrying out addition reaction on a first mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) reacting a second mixed reaction system containing an alkynyl diamine monomer, di-tert-butyl dicarbonate and a second solvent at 25-50 ℃ for 4-10 h to prepare a tert-butoxycarbonyl protected alkynyl diamine monomer;
(3) reacting a third mixed reaction system containing the tert-butoxycarbonyl protected alkynyl diamine monomer, decaborane and acetonitrile complex, silver nitrate and a first solvent at 80-120 ℃ for 3-8 h, and performing aftertreatment to obtain a compound containing a carborane structure;
(4) enabling a fourth mixed reaction system containing the compound containing the carborane structure, a second solvent and trifluoroacetic acid to react for 0.5-3 h at room temperature to obtain a diamine monomer containing the carborane structure, wherein the diamine monomer has a structure shown in any one of formulas III-V:
wherein R is2Any one of the following structures:
R3any one of the following structures:
5. the preparation method according to claim 4, wherein the molar ratio of decaborane to acetonitrile in step (1) is 0.1-1: 1;
and/or, the step (2) specifically comprises the following steps: uniformly mixing a diamine monomer containing alkynyl with a second solvent to form a mixture, and then dropwise adding di-tert-butyl dicarbonate into the mixture at 0-25 ℃ to form a second mixed reaction system; preferably, the molar ratio of the di-tert-butyl dicarbonate to the alkynyl-containing diamine monomer is 2-4: 1; preferably, the alkynyl diamine monomer comprises the R2And/or R3StructuringA compound;
and/or the molar ratio of the tert-butoxycarbonyl protected alkynyl diamine monomer, decaborane and acetonitrile complex and silver nitrate in the step (3) is 1 (0.5-2) to (0.05-0.2); preferably, the post-treatment in step (3) comprises: concentrating, washing and recrystallizing the mixture obtained by the reaction;
and/or the volume ratio of the second solvent to the trifluoroacetic acid in the step (4) is 0.5-2: 1;
and/or, the first solvent in step (1) or (3) comprises toluene;
and/or, the second solvent in step (2) or (4) comprises dichloromethane.
6. A carborane structure-containing dianhydride monomer having a structure represented by any one of formulas VI to IX:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
7. a preparation method of dianhydride monomer containing carborane structure is characterized by comprising the following steps:
(1) carrying out addition reaction on a first mixed reaction system containing decaborane, acetonitrile and a first solvent at the temperature of 80-120 ℃ for 3-6 h to prepare a complex of decaborane and acetonitrile;
(2) reacting a second mixed reaction system containing alkynyl dianhydride, boron trifluoride ethyl ether and a second solvent at the temperature of 60-80 ℃ for 5-10 hours, and performing post-treatment to obtain an alkynyl-containing tetraester compound;
(3) enabling a third mixed reaction system containing the alkynyl-containing tetraester compound, a decaborane and acetonitrile complex and a first solvent to react for 3-8 hours at the temperature of 80-120 ℃, and then carrying out aftertreatment to obtain the tetraester compound containing a carborane structure;
(4) reacting a fourth mixed reaction system containing the tetra-ester compound containing the carborane structure, a sodium hydroxide solution and a third solvent at the temperature of 20-60 ℃ for 5-20 hours, and then carrying out post-treatment to obtain a tetra-acid compound containing the carborane structure;
(5) reacting a fifth mixed reaction system containing a tetra-acid compound containing a carborane structure and acetic anhydride at 120-150 ℃ for 3-10 h, and performing post-treatment to obtain a dianhydride monomer containing a carborane structure, wherein the dianhydride monomer has a structure shown in any one of formulas VI-IX:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
8. the preparation method according to claim 7, wherein the molar ratio of decaborane to acetonitrile in step (1) is 0.1-1: 1;
and/or the molar equivalent ratio of the alkynyl dianhydride to boron trifluoride diethyl etherate in the step (2) is 0.1-5: 1; preferably, the alkynyl dianhydride comprises the R1A compound of structure (la); preferably, the second solvent in step (2) comprises methanol;
and/or the molar ratio of the alkynyl-containing tetraester compound, the decaborane-acetonitrile complex and the silver nitrate in the step (3) is 1 (0.5-2) to (0.05-0.2); preferably, the post-treatment in step (3) comprises: concentrating, washing and recrystallizing the mixture obtained by the reaction;
and/or, the first solvent in step (1) or (3) comprises toluene;
and/or, the post-treatment in the step (4) comprises: filtering, boiling with hydrochloric acid and washing the mixture obtained by the reaction; preferably, the third solvent in step (4) comprises tetrahydrofuran; preferably, the mass fraction of sodium hydroxide in the sodium hydroxide aqueous solution in the step (4) is 10-50 wt%.
9. A carborane structure containing dianhydride monomer prepared by the process of any of claims 7 to 8 having a structure according to any of formulas vi to ix:
wherein a and b are both 0-2, R1Comprising any one of the following structures:
10. a carborane structure-containing high-temperature resistant polyimide, which is prepared by performing polycondensation reaction on a carborane structure-containing diamine monomer according to claim 1 and a carborane structure-containing dianhydride monomer according to claim 6.
Priority Applications (1)
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