CN107459648B - Synthesis method of high-temperature-resistant carborane-containing polyimide resin - Google Patents
Synthesis method of high-temperature-resistant carborane-containing polyimide resin Download PDFInfo
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- CN107459648B CN107459648B CN201710545844.8A CN201710545844A CN107459648B CN 107459648 B CN107459648 B CN 107459648B CN 201710545844 A CN201710545844 A CN 201710545844A CN 107459648 B CN107459648 B CN 107459648B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 40
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000000034 method Methods 0.000 claims abstract description 15
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical compound CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 229940126214 compound 3 Drugs 0.000 claims description 24
- 229940125782 compound 2 Drugs 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000284 extract Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004642 Polyimide Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 11
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 229940018564 m-phenylenediamine Drugs 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229940127108 compound 5g Drugs 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- -1 phenylethynyl Chemical group 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of resin synthesis, and particularly discloses a synthesis method of high-temperature resistant carborane-containing polyimide resin, which comprises the following steps: the method comprises the following steps: 4-ethynyltoluene is synthesized into 4-carborane toluene; step two: 4-carborane toluene to synthesize 2, 6-dinitro-4-carborane toluene; step three: 2, 6-binitro-4-carborane toluene is synthesized into 2, 6-diamino-4-carborane toluene; step four: 2, 6-diamino-4-carborane toluene to synthesize modified polyimide resin. The invention adopts phenylacetylene-terminated thermosetting polyimide resin as a matrix, carries out molecular design on monomer diamine to synthesize m-phenylenediamine containing carborane boron cage structure, and then carries out polymerization reaction with anhydride and a terminating agent to finally obtain the modified polyimide resin, wherein the maximum use temperature of the polymer can reach 600 ℃, and the polymer has excellent oxidation stability.
Description
Technical Field
The invention belongs to the technical field of resin synthesis, and particularly relates to a synthesis method of high-temperature resistant carborane-containing polyimide resin.
Background
With the development of the modern industrial technical field, the traditional metal materials can not meet the application requirements of special models of aviation and aerospace, and the advanced resin matrix composite materials which have high specific strength and specific stiffness, strong designability, good fatigue resistance and corrosion resistance and special electromagnetic performance and take high-performance fibers as reinforcing agents are produced. The advanced resin-based composite material is used for replacing metal materials such as aluminum alloy and the like, so that the structural weight can be obviously reduced. Compared with the traditional structural materials such as steel, aluminum alloy and the like, the density of the resin-based composite material is about 1/5 of steel, and the density of the resin-based composite material is about 1/2 of aluminum alloy, so that the specific strength and the specific modulus of the resin-based composite material are obviously higher than those of the steel and the aluminum alloy. The development of weapon systems such as solid rocket engines, main battle tanks, satellites, strategic missiles, high-performance fighters and submarines and radomes and the like is not away from the advanced composite material technology.
Polyimide is a resin matrix of an advanced composite material with excellent performance and high temperature resistance, and is widely applied to the industrial fields of aerospace, aviation, microelectronics and the like. The thermosetting polyimide which is blocked by norbornene or phenylethynyl is mostly used, the fourth generation polyimide composite material which can resist the temperature of 450 ℃ is developed, and a high temperature resistant polyimide composite material system covering the fourth generation from 280-450 ℃ is formed. However, with the increasing requirements for materials in the aerospace field, a resin system capable of resisting high temperature of more than 450 ℃ is urgently needed to be researched.
Disclosure of Invention
The invention aims to provide a synthesis method of high-temperature resistant carborane-containing polyimide resin, which can obviously improve the temperature resistance of a polymer.
The technical scheme of the invention is as follows:
a synthesis method of high temperature resistant carborane-containing polyimide resin is characterized by comprising the following steps: the method comprises the following steps:
the chemical formula is as follows:
wherein the compound 1 is 4-ethynyltoluene, the compound 2 is 4-carborane toluene, the compound 3 is 2, 6-dinitro-4-carborane toluene, and the compound 4 is 2, 6-diamino-4-carborane toluene;
the method comprises the following steps: compound 1 compound 2 is synthesized;
step two: compound 2 compound 3 is synthesized;
step three: compound 3 compound 4 was synthesized;
step four: the compound 4 is synthesized into modified polyimide resin, and the specific synthetic route is as follows:
step one, sequentially adding a compound 1 and a compound B into a three-neck flask10H12(CH3CN)2And toluene, Compounds 1 and B10H12(CH3CN)2The catalyst can be completely dissolved in toluene, and then the reaction is carried out for 20-24 h at 100-120 ℃, and then the heating is stopped, and the reaction is finished;
followed by removing toluene by distillation under reduced pressure at 60 to 90 ℃ and then adding methanol to recrystallize, thereby obtaining compound 2 as white crystals.
Placing the compound 2 in a three-neck flask, adding dichloromethane, mechanically stirring uniformly, then sequentially dropwise adding fuming nitric acid and concentrated sulfuric acid under the ice-water bath condition, after dropwise adding and uniformly stirring, placing the three-neck flask to room temperature, continuing to react for 3-6 hours, and then finishing the reaction to obtain a mixture;
pouring the mixture into ice water, separating by using a separating funnel to obtain a water phase solution and an oil phase solution, extracting the water phase solution by using dichloromethane, and then combining the water phase solution and the oil phase solution;
washing the combined solution with saturated sodium bicarbonate solution until bubbles are generated; washing the solution with saturated saline solution to neutrality, drying with anhydrous magnesium sulfate, distilling the dried solution with a rotary evaporator under reduced pressure, adding ethanol, and recrystallizing to obtain light yellow solid compound 3.
Step three, sequentially adding the compound 3 and SnCl into a three-neck flask2·2H2Stirring O, ethanol and concentrated hydrochloric acid at room temperature, reacting for 1-2 h, heating to 70-100 ℃, and reacting for 3-5 h to obtain a reaction solution;
cooling the reaction liquid to room temperature, adjusting the pH of the reaction liquid to 7-10 by using a saturated sodium bicarbonate solution to obtain a mixed solution, and extracting the mixed solution by using ethyl acetate to obtain an extraction liquid;
the obtained extract was dried over anhydrous magnesium sulfate, and then ethyl acetate in the extract was removed by distillation under reduced pressure, followed by addition of ethanol for recrystallization to obtain a white solid compound 4.
Step four, sequentially adding 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, a compound 4 and a DMAc solvent into a three-neck flask, wherein the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride and the compound 4 can be completely dissolved in the DMAc solvent; introducing nitrogen into the three-neck flask, adding a drying tube on the three-neck flask, mechanically stirring for reacting for 2-4 h, adding a terminal-blocking agent 4-phenylacetylene phthalic anhydride, and continuously reacting for 18-24 h at room temperature to obtain a viscous light yellow transparent polyamide acid solution;
adding methylbenzene into a three-neck flask, heating to 150-180 ℃, taking out the methylbenzene by azeotropic dehydration, continuing to react for 8-10 hours at 150-180 ℃, and ending the reaction to obtain a reaction solution;
and pouring the reaction liquid into ethanol for precipitation, performing suction filtration and drying the precipitate to obtain a light yellow powdery polyimide oligomer.
In the first step, Ag compound 1 and B of Bg are added10H12(CH3CN)2And C g toluene, and yielded Mg white crystalline Compound 2;
wherein A: B is 1: 1.5-1: 3, A: C is 1: 17-1: 20, and A: M is 1: 1-1: 1.5.
In the second step, Dg compound 2 and Eg dichloromethane are added to obtain Ng pale yellow solid compound 3 finally;
wherein D is 1: 1.5-1: 2, and D is N is 1: 1-1: 1.5.
In the second step, Fg fuming nitric acid and Gg concentrated sulfuric acid are added;
wherein D is F-1: 0.2-1: 0.4, and D is G-1: 1-1: 4.
In the third step, Hg compound 3 and Ig SnCl are added2·2H2O, Jg 95-98% ethanol and Kg of concentrated hydrochloric acid with the concentration of 30-40%, and finally obtaining Pg white solid compound 4;
wherein H: I is 1: 0.5-1: 1, H: J is 1: 5-1: 10, and H: K is 1: 0.5-1: 1.
In the fourth step, respectively adding Qg of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, Rg of compound 4, Sg of DMAc solvent, Vg of end-capping agent 4-phenylacetylene phthalic anhydride and Wg of toluene to finally obtain Yg of yellowish powdery polyimide oligomer;
wherein R is 1: 1-1: 2, S is 1: 3-1: 4, V is 1: 1-1: 2, and W is 1: 0.5-1: 1.
The invention has the following remarkable effects:
(1) the carborane used in the invention has an icosahedron cage structure, and the super-aromaticity and strong electron withdrawing property of a three-dimensional structure of the carborane enable the derivative of the carborane to have excellent heat resistance and oxidation stability.
(2) The collapse of the boron cage at high temperatures can absorb energy and generate large amounts of diboron trioxide, which can protect the polymer. The carborane structure is introduced into the polymer, so that the temperature resistance of the polymer can be improved by over 100 ℃, and the oxidation stability of the polymer in air can be improved.
(3) The invention adopts phenylacetylene-terminated thermosetting polyimide resin as a matrix, carries out molecular design on diamine monomer to synthesize m-phenylenediamine containing carborane boron cage structure, and then carries out polymerization reaction with anhydride and a capping agent to finally obtain the modified polyimide resin, wherein the maximum use temperature of the polymer can reach 600 ℃.
(4) The DMA test of the modified polyimide resin synthesized by the method can keep the modulus unchanged at 0-600 ℃.
Drawings
FIG. 1 is an infrared test chart of Compound 2, Compound 3 and Compound 4;
FIG. 2 is an infrared spectrum of a modified polyimide oligomer resin;
FIG. 3 is a DSC of a modified polyimide oligomer resin;
FIG. 4 is a schematic diagram of thermal weight loss in argon gas for polyimide resin after complete curing modification;
FIG. 5 is a DMA test chart of a modified polyimide resin casting.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
The invention relates to a synthesis method of high-temperature resistant carborane-containing polyimide resin, which comprises the following steps:
the chemical formula is as follows:
wherein the compound 1 is 4-ethynyltoluene, the compound 2 is 4-carborane toluene, the compound 3 is 2, 6-dinitro-4-carborane toluene, and the compound 4 is 2, 6-diamino-4-carborane toluene.
(1) Compound 1 Synthesis of Compound 2
In a three-necked flask a, Ag compound 1 and Bg B were added in this order10H12(CH3CN)2And C g toluene, Compounds 1 and B10H12(CH3CN)2The catalyst can be completely dissolved in toluene, wherein A: B is 1: 1.5-1: 3, A: C is 1: 17-1: 20, and then the reaction is stopped after the reaction is carried out for 20-24 h at 100-120 ℃, and the reaction is finished.
Then, toluene was distilled off at 60 to 90 ℃ under reduced pressure, and methanol was added thereto for recrystallization to obtain M g white crystalline compound 2, wherein a: M is 1:1 to 1: 1.5.
(2) Compound 2 synthesis compound 3 Dg compound 2 was placed in a three-neck flask b, then Eg dichloromethane was added and mechanically stirred uniformly, wherein D: E ═ 1: 1.5-1: 2. And sequentially dripping Fg fuming nitric acid and Gg concentrated sulfuric acid at the speed of 1-2 drops/second under the condition of ice-water bath, wherein D: F is 1: 0.2-1: 0.4, and D: G is 1: 1-1: 4. After the dropwise addition is finished and the stirring is uniform, placing the three-neck flask b to room temperature for continuous reaction for 3-6 h, and then finishing the reaction to obtain a mixture.
Pouring the mixture into ice water, and separating by using a separating funnel to obtain a water phase solution and an oil phase solution; the aqueous solution was extracted with dichloromethane and then combined with the oil phase solution. Washing the combined solution with saturated sodium bicarbonate solution until bubbles are generated; the solution was washed with saturated brine to neutrality, and then dried over anhydrous magnesium sulfate. And (3) distilling the dried solution under reduced pressure by using a rotary evaporator, adding ethanol for recrystallization, and finally obtaining N g light yellow solid compound 3, wherein D: N is 1: 1-1: 1.5.
(3) Compound 3 Synthesis of Compound 4
Hg compound 3 and Ig SnCl were added in sequence to a three-necked flask c2·2H2O, Jg 95-98% of ethanol and Kg of concentrated hydrochloric acid with the concentration of 30-40%, wherein H: I is 1: 0.5-1: 1, H: J is 1: 5-1: 10, and H: K is 1: 0.5-1: 1; stirring and reacting for 1-2 h at room temperature, and then heating to 70-100 ℃ to react for 3-5 h to obtain a reaction solution.
Cooling the reaction solution to room temperature, adjusting the pH of the reaction solution to 7-10 with a saturated sodium bicarbonate solution to obtain a mixed solution, and extracting the mixed solution with ethyl acetate to obtain an extract. The obtained extract was dried over anhydrous magnesium sulfate, and then ethyl acetate in the extract was removed by distillation under reduced pressure, followed by addition of ethanol for recrystallization to obtain P g as a white solid compound 4.
(4) Synthesis of modified polyimide resin from Compound 4
The specific synthetic route is as follows:
q g of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, R g of compound 4 and S g of DMAc solvent are added in sequence into a three-necked flask d, so that the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride and the compound 4 can be completely dissolved in the DMAc solvent; and introducing nitrogen into the three-neck flask d, adding a drying tube to the three-neck flask d, mechanically stirring to react for 2-4 h, adding a capping agent Vg 4-phenylacetylene phthalic anhydride, and continuously reacting at room temperature for 18-24 h to obtain a viscous light yellow transparent polyamide acid solution, wherein Q: R is 1: 1-1: 2, Q: S is 1: 3-1: 4, and Q: V is 1: 1-1: 2.
And adding Wg of toluene into the three-neck flask d, heating to 150-180 ℃, taking out the toluene by azeotropic dehydration, continuing to react at 150-180 ℃ for 8-10 h, and ending the reaction to obtain a reaction solution. And pouring the reaction liquid into ethanol for precipitation, performing suction filtration, and drying the precipitate to obtain light yellow powdery polyimide oligomer Yg, wherein Q and W are 1: 0.5-1: 1.
Example 1
In a 250mL three-necked flask, 5.2g of 4-ethynyltoluene and 14.8g of B were sequentially added10H12(CH3CN)2And 100g of toluene, and the reaction was terminated after 20 hours at 110 ℃. Toluene was distilled off under reduced pressure at 70 ℃ and then methanol was added to recrystallize, yielding 5.6g of compound 2 as white crystals.
5.6g of Compound 2 was placed in a 100mL three-necked flask, 10g of methylene chloride was added thereto, and the mixture was mechanically stirred to homogeneity. And then, sequentially dropwise adding 2g of fuming nitric acid and 20g of concentrated sulfuric acid at the speed of 1 drop/second under the condition of ice-water bath, continuing to react for 3 hours at room temperature after dropwise adding is finished, and finishing the reaction to obtain a mixture. Pouring the mixture into ice water, separating by using a separating funnel to obtain an aqueous phase solution and an oil phase solution, extracting the aqueous phase solution by using dichloromethane, combining with the oil phase solution, and washing the solution by using saturated sodium bicarbonate until bubbles are generated; the solution was washed with saturated brine to neutrality, and then dried over anhydrous magnesium sulfate. The dried solution was distilled under reduced pressure using a rotary evaporator, and then recrystallized by adding ethanol to obtain 6.9g of compound 3 as a pale yellow solid.
In a 250mL three-necked flask, 6.9g of Compound 3 and 5g of SnCl were added in this order2·2H2O, 50g of 98% ethanol and 5g of 35% concentrated hydrochloric acid, stirring at room temperature for reaction for 1 hour, heating to 80 ℃, reacting for 3 hours, and then finishing the reaction to obtain a reaction solution. After the reaction solution was cooled to room temperature, the reaction solution was adjusted to pH 9 with a saturated sodium bicarbonate solution to obtain a mixed solution, and the mixed solution was extracted with ethyl acetate to obtain an extract. The obtained extract was dried over anhydrous magnesium sulfate, and then ethyl acetate in the extract was removed by distillation under reduced pressure, followed by addition of ethanol for recrystallization to obtain 5.3g of compound 4 as a white solid.
In a 250mL three-necked flask were charged 5.3g of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 8.6g of compound 4, and 20g of DMAc solvent in that order. Then introducing nitrogen into the three-neck flask, adding a drying tube on the three-neck flask, mechanically stirring for reaction for 2 hours, adding 8.1g of end-capping reagent 4-phenylacetylene phthalic anhydride, and continuing to react for 20 hours at room temperature to obtain a viscous light yellow transparent polyamic acid solution. Then 5g of toluene is added into a three-neck flask, the temperature is raised to 170 ℃, the toluene is taken out by azeotropic dehydration, and the reaction is finished after the reaction is continued for 9 hours at 170 ℃ to obtain a reaction solution. Pouring the reaction liquid into enough ethanol for precipitation, performing suction filtration and drying the precipitate to obtain a light yellow powdery polyimide oligomer. The specific synthesis steps are as follows:
example 2
In a 500mL three-necked flask, 11g of 4-ethynyltoluene and 20g of B were sequentially added10H12(CH3CN)2And 200g of toluene, and the reaction was terminated after 24 hours at 110 ℃. Toluene was distilled off under reduced pressure at 80 ℃ and then methanol was added to conduct recrystallization, to obtain 12g of Compound 2 as white crystals.
12g of Compound 2 was placed in a 200mL three-necked flask, and 20g of methylene chloride was added thereto and mechanically stirred to homogeneity. And then, under the condition of ice-water bath, sequentially dropwise adding 3g of fuming nitric acid and 25g of concentrated sulfuric acid at the speed of 2 drops/second, continuing to react for 5 hours at room temperature after dropwise adding is finished, and finishing the reaction to obtain a mixture. Pouring the mixture into ice water, separating by using a separating funnel to obtain an aqueous phase solution and an oil phase solution, extracting the aqueous phase solution by using dichloromethane, combining with the oil phase solution, and washing the solution by using saturated sodium bicarbonate until bubbles are generated; the solution was washed with saturated brine to neutrality, then dried over anhydrous magnesium sulfate, and the dried solution was distilled under reduced pressure using a rotary evaporator, and recrystallized by adding ethanol to obtain 15g of a pale yellow solid compound 3.
In a 500mL three-necked flask, 15g of Compound 3 and 10g of SnCl were sequentially added2·2H2O, 100g of 99% ethanol and 10g of 30% diluted hydrochloric acid, stirring the mixture at room temperature to react for 1 hour, heating the mixture to 90 ℃ to react for 4 hours, and then finishing the reaction to obtain a reaction solution. The reaction solution was cooled to room temperature, and then dissolved in saturated sodium bicarbonateThe reaction solution was adjusted to pH 9 to obtain a mixed solution, and the mixed solution was extracted with ethyl acetate to obtain an extract. The obtained extract was dried over anhydrous magnesium sulfate, and then ethyl acetate in the extract was removed by distillation under reduced pressure, followed by addition of ethanol for recrystallization to obtain 12g of compound 4 as a white solid.
In a 500mL three-necked flask were charged 12g of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 20g of compound 4, and 40g of DMAc solvent in this order. And introducing nitrogen into the three-neck flask, adding a drying tube on the three-neck flask, mechanically stirring to react for 3 hours, adding 20g of end-capping reagent 4-phenylacetylene phthalic anhydride, and continuously reacting for 20 hours at room temperature to obtain a viscous light yellow transparent polyamide acid solution. Then 10g of toluene was added into a three-necked flask, the temperature was raised to 170 ℃ to take out the toluene by azeotropic dehydration, and the reaction was continued at 170 ℃ for 9 hours to terminate the reaction, thereby obtaining a reaction solution. Pouring the reaction liquid into enough ethanol for precipitation, performing suction filtration and drying the precipitate to obtain a light yellow powdery polyimide oligomer.
Claims (10)
1. A synthesis method of high temperature resistant carborane-containing polyimide resin is characterized by comprising the following steps: the method comprises the following steps:
the chemical formula is as follows:
wherein the compound 1 is 4-ethynyltoluene, the compound 2 is 4-carborane toluene, the compound 3 is 2, 6-dinitro-4-carborane toluene, and the compound 4 is 2, 6-diamino-4-carborane toluene;
the method comprises the following steps: compound 1 compound 2 is synthesized;
step two: compound 2 compound 3 is synthesized;
step three: compound 3 compound 4 was synthesized;
step four: the compound 4 is synthesized into modified polyimide resin, and the specific synthetic route is as follows:
2. the method for synthesizing high temperature resistant carborane-containing polyimide resin as claimed in claim 1, wherein: step one, sequentially adding a compound 1 and a compound B into a three-neck flask10H12(CH3CN)2And toluene, Compounds 1 and B10H12(CH3CN)2The catalyst can be completely dissolved in toluene, and then the reaction is carried out for 20-24 h at 100-120 ℃, and then the heating is stopped, and the reaction is finished;
followed by removing toluene by distillation under reduced pressure at 60 to 90 ℃ and then adding methanol to recrystallize, thereby obtaining compound 2 as white crystals.
3. The method for synthesizing high temperature resistant carborane-containing polyimide resin as claimed in claim 1, wherein: placing the compound 2 in a three-neck flask, adding dichloromethane, mechanically stirring uniformly, then sequentially dropwise adding fuming nitric acid and concentrated sulfuric acid under the ice-water bath condition, after dropwise adding and uniformly stirring, placing the three-neck flask to room temperature, continuing to react for 3-6 hours, and then finishing the reaction to obtain a mixture;
pouring the mixture into ice water, separating by using a separating funnel to obtain a water phase solution and an oil phase solution, extracting the water phase solution by using dichloromethane, and then combining the water phase solution and the oil phase solution;
washing the combined solution with saturated sodium bicarbonate solution until bubbles are generated; washing the solution with saturated saline solution to neutrality, drying with anhydrous magnesium sulfate, distilling the dried solution with a rotary evaporator under reduced pressure, adding ethanol, and recrystallizing to obtain light yellow solid compound 3.
4. The method for synthesizing high temperature resistant carborane-containing polyimide resin as claimed in claim 1, wherein: step three, sequentially adding the compound 3 and SnCl into a three-neck flask2·2H2O, ethanol and concentrated hydrochloric acid,stirring and reacting for 1-2 h at room temperature, and then heating to 70-100 ℃ to react for 3-5 h to obtain a reaction solution;
cooling the reaction liquid to room temperature, adjusting the pH of the reaction liquid to 7-10 by using a saturated sodium bicarbonate solution to obtain a mixed solution, and extracting the mixed solution by using ethyl acetate to obtain an extraction liquid;
the obtained extract was dried over anhydrous magnesium sulfate, and then ethyl acetate in the extract was removed by distillation under reduced pressure, followed by addition of ethanol for recrystallization to obtain a white solid compound 4.
5. The method for synthesizing high temperature resistant carborane-containing polyimide resin as claimed in claim 1, wherein: step four, sequentially adding 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, a compound 4 and a DMAc solvent into a three-neck flask, wherein the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride and the compound 4 can be completely dissolved in the DMAc solvent; introducing nitrogen into the three-neck flask, adding a drying tube on the three-neck flask, mechanically stirring for reacting for 2-4 h, adding a terminal-blocking agent 4-phenylacetylene phthalic anhydride, and continuously reacting for 18-24 h at room temperature to obtain a viscous light yellow transparent polyamide acid solution;
adding methylbenzene into a three-neck flask, heating to 150-180 ℃, taking out the methylbenzene by azeotropic dehydration, continuing to react for 8-10 hours at 150-180 ℃, and ending the reaction to obtain a reaction solution;
and pouring the reaction liquid into ethanol for precipitation, performing suction filtration and drying the precipitate to obtain a light yellow powdery polyimide oligomer.
6. The method for synthesizing high temperature carborane-containing polyimide resin as claimed in claim 2, wherein: in the first step, Ag compound 1 and B of Bg are added10H12(CH3CN)2And C g toluene, and yielded Mg white crystalline Compound 2;
wherein A: B is 1: 1.5-1: 3, A: C is 1: 17-1: 20, and A: M is 1: 1-1: 1.5.
7. The method for synthesizing high temperature carborane-containing polyimide resin as claimed in claim 3, wherein: in the second step, Dg compound 2 and Eg dichloromethane are added to obtain Ng pale yellow solid compound 3 finally;
wherein D is 1: 1.5-1: 2, and D is N is 1: 1-1: 1.5.
8. The method of synthesizing a high temperature carborane-containing polyimide resin as claimed in claim 7, wherein: in the second step, Fg fuming nitric acid and Gg concentrated sulfuric acid are added;
wherein D is F-1: 0.2-1: 0.4, and D is G-1: 1-1: 4.
9. The method for synthesizing high temperature carborane-containing polyimide resin as claimed in claim 4, wherein: in the third step, Hg compound 3 and Ig SnCl are added2·2H2O, Jg 95-98% ethanol and Kg of concentrated hydrochloric acid with the concentration of 30-40%;
wherein H: I is 1: 0.5-1: 1, H: J is 1: 5-1: 10, and H: K is 1: 0.5-1: 1.
10. The method for synthesizing high temperature carborane-containing polyimide resin as claimed in claim 5, wherein: in the fourth step, respectively adding Qg of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, Rg of compound 4, Sg of DMAc solvent, Vg of end capping agent 4-phenylacetylene phthalic anhydride and Wg of toluene;
wherein R is 1: 1-1: 2, S is 1: 3-1: 4, V is 1: 1-1: 2, and W is 1: 0.5-1: 1.
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| CN109400635A (en) * | 2018-11-15 | 2019-03-01 | 北京航空航天大学 | A kind of asymmetric double degree of functionality carborane derivative and preparation method and application |
| CN113135950A (en) * | 2020-01-19 | 2021-07-20 | 中国科学院宁波材料技术与工程研究所 | Diamine monomer and dianhydride monomer containing carborane structure as well as preparation methods and applications of diamine monomer and dianhydride monomer |
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| CN114790289B (en) * | 2022-04-24 | 2023-08-11 | 中国船舶重工集团公司第七一八研究所 | Preparation method of high-temperature-resistant polyimide resin |
| CN115160568B (en) * | 2022-07-25 | 2023-03-24 | 波米科技有限公司 | Hyperbranched polyimide, preparation method thereof, polyimide film and polyimide product |
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| US3850820A (en) * | 1971-09-16 | 1974-11-26 | B Mgeladze | Antifriction structural material produced from composition comprising carborane-containing polymer binders and solid lubricant |
| CN103881091A (en) * | 2014-03-15 | 2014-06-25 | 西南石油大学 | Preparation method of polyimide containing carborane structure |
| CN104945627A (en) * | 2015-07-28 | 2015-09-30 | 中国工程物理研究院总体工程研究所 | Method for preparing ultra-high heat resistant polyimide polymer |
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| US3850820A (en) * | 1971-09-16 | 1974-11-26 | B Mgeladze | Antifriction structural material produced from composition comprising carborane-containing polymer binders and solid lubricant |
| CN103881091A (en) * | 2014-03-15 | 2014-06-25 | 西南石油大学 | Preparation method of polyimide containing carborane structure |
| CN104945627A (en) * | 2015-07-28 | 2015-09-30 | 中国工程物理研究院总体工程研究所 | Method for preparing ultra-high heat resistant polyimide polymer |
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