CN112898462A - High-boron-content carborane-containing structural polymer and preparation method and application thereof - Google Patents
High-boron-content carborane-containing structural polymer and preparation method and application thereof Download PDFInfo
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- CN112898462A CN112898462A CN202110082373.8A CN202110082373A CN112898462A CN 112898462 A CN112898462 A CN 112898462A CN 202110082373 A CN202110082373 A CN 202110082373A CN 112898462 A CN112898462 A CN 112898462A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052796 boron Inorganic materials 0.000 claims abstract description 62
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 229910000085 borane Inorganic materials 0.000 claims abstract description 26
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- 238000002679 ablation Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- MCQRPQCQMGVWIQ-UHFFFAOYSA-N boron;methylsulfanylmethane Chemical compound [B].CSC MCQRPQCQMGVWIQ-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 4
- IUXHPSPHPKXTPA-UHFFFAOYSA-N 1-bromobut-1-ene Chemical compound CCC=CBr IUXHPSPHPKXTPA-UHFFFAOYSA-N 0.000 claims description 4
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JTWJUVSLJRLZFF-UHFFFAOYSA-N 2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},11$l^{2},12$l^{2}-decaborabicyclo[8.1.1]dodecane Chemical compound [B]1C2[B]C1[B][B][B][B][B][B][B][B]2 JTWJUVSLJRLZFF-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- -1 diborane Chemical compound 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 125000001979 organolithium group Chemical group 0.000 claims description 3
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims description 2
- CFNUZRMHHJZBOM-UHFFFAOYSA-N [B]1C2[B][B]C1[B][B][B][B][B][B][B]2 Chemical compound [B]1C2[B][B]C1[B][B][B][B][B][B][B]2 CFNUZRMHHJZBOM-UHFFFAOYSA-N 0.000 claims description 2
- 229910010277 boron hydride Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000005457 ice water Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000007792 addition Methods 0.000 description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920003237 carborane-containing polymer Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F130/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
-
- 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
- C07F5/027—Organoboranes and organoborohydrides
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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)
Abstract
The invention discloses a carborane-containing structural polymer with high boron content, and a preparation method and application thereof. The preparation method comprises the following steps: and under a protective atmosphere, reacting a mixed reaction system containing double-bond-terminated carborane derivatives, borohydride and/or borane complex and a first solvent at-10-300 ℃ for 30-72 h to obtain the carborane-containing structural polymer with high boron content. The preparation method provided by the invention is simple and convenient to operate and high in yield; meanwhile, the carborane-containing structural polymer with high boron content prepared by the invention has good organic solubility and high boron content, and has great potential application value in the fields of aerospace industry, high temperature resistance, ablation resistance, neutron irradiation shielding and the like.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a carborane-containing structural polymer with high boron content, and a preparation method and application thereof.
Background
Boron element is introduced into the polymer by adopting borane, boric acid and derivatives thereof as boron sources, and the introduction amount of the boron element is limited. Carborane is an icosahedral boron hydride compound formed by replacing two BH units with equal charges by two CH-units, and the closed cage-shaped structure has a highly symmetrical framework structure and a large volume and simultaneously shows typical properties of a plurality of aromatic structures, thermal stability and chemical stability. Therefore, the unique property and high boron content of carborane make the research of potential application of carborane attach importance to the field of polymer materials. The molecular structure with high boron content is beneficial to further application and expansion of related materials in the high-temperature ablation-resistant field such as aerospace and the like, and can greatly improve the high-temperature carbon residue rate of a resin structure and the ceramic yield of an embedded structure, so that the carborane-containing polymer with high boron content has important value in the fields of ablation-resistant materials and coatings.
Disclosure of Invention
The invention mainly aims to provide a carborane-containing structural polymer with high boron content, a preparation method and application 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 preparation method of a carborane-containing structure polymer with high boron content, which comprises the following steps:
and under a protective atmosphere, reacting a mixed reaction system containing double-bond-terminated carborane derivatives, borohydride and/or borane complex and a first solvent at-10-300 ℃ for 30-72 h to obtain the carborane-containing structural polymer with high boron content.
Further, the double bond-terminated carborane derivative has a structure as shown in any one of formulas (I) - (III):
wherein R is selected from CnH2nCOO, CO, Ph, NH and O, and n is more than or equal to 0 and less than or equal to 10.
Embodiments of the present invention also provide high boron content carborane-containing structural polymers prepared by the foregoing methods.
The embodiment of the invention also provides application of the carborane-containing structural polymer with high boron content in the fields of aerospace industry, high-temperature resistant materials, ablation resistant materials or neutron irradiation shielding materials.
Compared with the prior art, the invention has the beneficial effects that:
(1) the carborane-containing structural polymer with high boron content can be synthesized by a one-step method, and is simple and convenient to operate and high in yield;
(2) the cured carborane-containing structural polymer with high boron content shows extremely high thermal stability and thermal oxygen stability in argon and air atmosphere, and has obvious temperature resistance advantage;
(3) the carborane-containing structural polymer with high boron content prepared by the invention is low-viscosity liquid to resin type solid, the viscosity of the polymer can be as low as 100cp, and the polymer is easy to dissolve in various organic solvents and can be used for preparing high-temperature-resistant composite materials, ceramic precursors, high-temperature-resistant coatings or neutron irradiation shielding materials and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings 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 invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a reaction scheme for preparing high boron content carborane structure containing polymers in an exemplary embodiment of the invention;
FIG. 2 is a FT-IR plot of a high boron content carborane structure containing polymer 1 made in example 4 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum in a deuterated chloroform solvent of a high boron content carborane structure-containing polymer 1 prepared in example 4 of the present invention;
FIG. 4 is a nuclear magnetic boron spectrum in a deuterated chloroform solvent of a high boron content carborane structure-containing polymer 1 prepared in example 4 of the present invention;
FIG. 5 is a graph of TG-dTG in air atmosphere for the high boron content carborane structure-containing polymer 1 prepared in example 4 of the present invention;
FIG. 6 is a FT-IR plot of a high boron content carborane structure containing polymer 2 made in example 5 of the present invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum in a deuterated chloroform solvent of a high boron content carborane structure-containing polymer 2 prepared in example 5 of the present invention;
FIG. 8 is a nuclear magnetic boron spectrum in a deuterated chloroform solvent of a high boron content carborane structure-containing polymer 2 prepared in example 5 of the present invention;
FIG. 9 is a graph of TG-dTG in air atmosphere for the high boron content carborane structure-containing polymer 2 prepared in example 5 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 great numbers to provide a technical solution of the present invention, which mainly uses a carborane derivative terminated with double bonds and borohydride and/or borane complex as reactants to synthesize a carborane-containing structural polymer with high boron content by a one-pot method.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aspect of an embodiment of the present invention provides a method for preparing a carborane structure-containing polymer having a high boron content, including:
and under a protective atmosphere, reacting a mixed reaction system containing double-bond-terminated carborane derivatives, borohydride and/or borane complex and a first solvent at-10-300 ℃ for 30-72 h to obtain the carborane-containing structural polymer with high boron content.
In some more specific embodiments, the preparation method comprises: under a protective atmosphere, dissolving a carborane derivative containing a double-bond end capping into a first solvent, and then adding borohydride and/or borane complex into the obtained mixture at the temperature of-10-5 ℃ to form the mixed reaction system.
Further, the protective atmosphere includes an inert gas atmosphere, and is not limited thereto.
In some more specific embodiments, the double bond-terminated carborane derivative has a structure according to any one of formulas (I) - (iii):
wherein R is selected from CnH2nCOO, CO, Ph, NH and O, and n is more than or equal to 0 and less than or equal to 10.
Further, the double bond-terminated carborane derivative is a double bond-terminated carborane derivative.
Further, the borohydride and/or borane complex includes any one or a combination of two or more of borane, diborane, borane dimethylsulfide complex, borane tetrahydrofuran, and amine borane complex, but is not limited thereto.
Further, the amine borane complex includes borane ammonia complex, and is not limited thereto.
Further, the first solvent includes any one or a combination of two or more of benzene, dimethyl ether, tetrahydrofuran, toluene, and dimethylformamide, and is not limited thereto.
Further, the molar ratio of C ═ C bonds in the double bond-terminated carborane derivative to B-H bonds in the borohydride and/or borane complex is 1:2 to 5: 1.
In some more specific embodiments, the double bond-terminated carborane derivative is prepared by a method comprising:
under the conditions of protective atmosphere and ice bath, dissolving carborane in a second solvent to form a carborane solution, then adding an organic lithium reagent, and stirring and reacting at room temperature for 0.1-5 hours to obtain carborane lithium salt;
and adding halogenated olefin/halogenated alkyne into the obtained carborane lithium salt at the temperature of 0-10 ℃, and then reacting for 0.1-5 h at the temperature of 20-100 ℃ to obtain the double-bond end-capped carborane derivative.
Further, the carborane includes any one or a combination of two or more of o-carborane, m-carborane and p-carborane, and is not limited thereto.
Further, the organolithium reagent includes any one or a combination of two of n-butyllithium and t-butyllithium, and is not limited thereto.
Further, the second solvent includes any one or a combination of two or more of anhydrous diethyl ether, anhydrous tetrahydrofuran, and anhydrous toluene, and is not limited thereto.
Further, the halogenated alkene/halogenated alkyne includes any one or a combination of two or more of bromopropene, chloropropene, bromobutene and 3-bromopropyne, and is not limited thereto.
Further, the molar ratio of the carborane, the organolithium reagent and the halogenated alkene/halogenated alkyne is 1: 1-2.4: 1 to 2.6.
Further, the molar weight ratio of the borohydride and/or borane complex to the carborane is 1: 0.1-100.
In some more specific embodiments, the preparation method further comprises: after the reaction is finished, distilling and drying the obtained mixture; preferably, the conditions of the drying treatment include: the temperature is 30-150 ℃, and the drying time is 2-5 h.
In some more specific embodiments, the method for preparing the high boron content carborane structure containing polymer specifically comprises:
adding a double-bond-terminated carborane derivative into a reaction bottle with a stirring device, replacing air in the reaction bottle to be inert atmosphere, adding a first organic solvent into the reaction bottle, then adding a certain amount of borohydride and/or borane complex at the temperature of-10-5 ℃, reacting overnight at room temperature after the addition is finished, and then carrying out rotary evaporation and drying for 2-5h to obtain the carborane-containing structural polymer with high boron content.
In some more specific embodiments, the method for preparing the carborane structure containing polymer with high boron content specifically comprises the following steps (a reaction scheme is shown in figure 1):
under protective atmosphere, carborane derivatives (CBs) and Borane (BH) containing double bond end capping3) And reacting the mixed reaction system of the first solvent for 30-72 hours at-10-300 ℃ to obtain the carborane-containing structure polymer (HBCB) with high boron content.
It is also an aspect of an embodiment of the present invention to provide high boron content carborane-containing structural polymers prepared by the foregoing methods.
Further, the viscosity of the high boron content carborane structure containing polymer may be as low as 100 cp.
Further, the high boron content carborane structure containing polymer is in the form of a bulk solid and/or a powder. In another aspect of embodiments of the present invention, there is also provided the use of the aforesaid high boron content carborane structure containing polymers in the aerospace industry, in the high temperature, ablation or neutron radiation shielding fields.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, 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
Synthesizing allyl substituted ortho carborane, wherein the selected carborane is ortho carborane; the other reaction raw materials are tert-butyl lithium and chloropropene, and anhydrous tetrahydrofuran is used as a solvent, and the preparation method comprises the following steps:
(1) adding ortho-carborane (30g, 208.02mmol) into a 500ml three-neck flask provided with a magnetic stirring, constant pressure dropping funnel and a reflux device, completely replacing the reaction system with argon gas through gas replacement, then adding 200ml of anhydrous tetrahydrofuran into a reaction bottle, and dropwise adding tert-butyl lithium (417.50mmol, 3 s/drop) under the ice-water bath condition;
(2) after the dropwise addition is completed, removing the ice-water bath to react for 2 hours at room temperature, then placing the mixture in the ice-water bath for cooling, dropwise adding chloropropene (588mmol), and reacting for 5 hours at 20 ℃ after the dropwise addition is completed;
(3) after the reaction is finished, adding 50ml of deionized water to quench the reaction, and then carrying out rotary evaporation to obtain a crude product; selecting normal hexane as an eluent, and purifying the normal hexane by using a silica gel chromatographic column to obtain a colorless transparent product, thereby obtaining a carborane derivative with a double-bond end capping, namely allyl substituted ortho carborane;
example 2
Synthesizing allyl substituted meta-carborane, wherein the selected carborane is meta-carborane; the other reaction raw materials are n-butyllithium and bromopropylene, and anhydrous ether is used as a solvent, and the preparation method comprises the following steps:
(1) adding m-carborane (30g, 208.02mmol) into a 500ml three-neck flask provided with a magnetic stirring, constant pressure dropping funnel and a reflux device, completely replacing the reaction system with argon gas through gas replacement, then adding 200ml of anhydrous ether into a reaction bottle, and dropwise adding n-butyl lithium (167ml, 417.50mmol, 3 s/drop) under the ice-water bath condition;
(2) after the dropwise addition is completed, removing the ice-water bath to react for 2 hours at room temperature, then placing the mixture in the ice-water bath for cooling, dropwise adding bromopropylene (71.14g, 588mmol), and reacting for 3 hours at 50 ℃ after the dropwise addition is completed;
(3) after the reaction is finished, adding 50ml of deionized water to quench the reaction, and then carrying out rotary evaporation to obtain a crude product; n-hexane is selected as an eluent, and the mixture is purified by a silica gel chromatographic column to obtain 41.1g of colorless transparent product, so that the carborane derivative with the end capped by double bonds, namely the allyl substituted meta-carborane is obtained.
Example 3
Synthesizing alkenyl substituted para-carborane, wherein the selected carborane is para-carborane; the other reaction raw materials are n-butyllithium and bromobutene, and anhydrous toluene is used as a solvent, and the preparation method comprises the following steps:
(1) adding para-carborane (208.02mmol) into a 500ml three-neck flask provided with a magnetic stirring, constant-pressure dropping funnel and a reflux device, completely replacing the reaction system with argon through gas replacement, then adding 200ml of anhydrous toluene into the reaction flask, and dropwise adding n-butyl lithium (417.50mmol, 3 s/drop) under the ice-water bath condition;
(2) after the dropwise addition is completed, removing the ice-water bath to react for 2 hours at room temperature, then placing the mixture in the ice-water bath for cooling, dropwise adding bromobutene (588mmol), and reacting for 0.5 hour at 100 ℃ after the dropwise addition is completed;
(3) after the solution is cooled to room temperature, 50ml of deionized water is added for quenching reaction on the next day, and then the crude product is obtained by rotary evaporation; and (3) selecting normal hexane as an eluent, and purifying the normal hexane by using a silica gel chromatographic column to obtain a colorless and transparent product, so as to obtain the carborane derivative with the end capped by the double bond, namely the alkenyl substituted para-carborane.
Example 4
Selecting the allyl substituted meta-carborane and borane dimethyl sulfide complex prepared in the embodiment 2 as raw materials, and taking tetrahydrofuran as a solvent; the raw materials can be obtained by the commercial route and the like, and the preparation method of the carborane structure-containing polymer with high boron content comprises the following steps:
(1) to a 50ml Schlenk flask equipped with a magnetic stirring, constant pressure dropping funnel device was added allyl-substituted metacarborane (0.6783g, 6mmol), the entire reaction system was replaced with argon gas by gas replacement, and then 30ml of tetrahydrofuran was added through the dropping funnel, and borane dimethylsulfide complex (1ml, 2mmol) was added dropwise under ice-water bath conditions.
(2) After the dropwise addition of the borane dimethyl sulfide complex, the reaction is carried out at room temperature overnight, after the reaction is finished, the reaction product is subjected to rotary evaporation and is dried for 5 hours in a vacuum drying oven at the temperature of 150 ℃, and an off-white reaction product 0.6863g, namely the carborane-containing structural polymer 1 with high boron content is obtained.
And (3) performance characterization:
the FT-IR chart of the carborane structure-containing polymer 1 with a high boron content prepared in this example is shown in FIG. 2; the nuclear magnetic hydrogen spectrum in the deuterated chloroform solvent is shown in figure 3; the nuclear magnetic boron spectrum in the deuterated chloroform solvent is shown in figure 4; the graph of TG-dTG in air is shown in FIG. 5, and it can be seen that the carborane structure-containing polymer 1 with high boron content is prepared to have extremely high thermal stability and thermal oxygen stability.
Example 5
The allyl substituted meta-carborane and borane dimethyl sulfide complex prepared in the embodiment 2 are selected as raw materials, and toluene is used as a solvent; the raw materials can be obtained by the commercial route and the like, and the preparation method of the carborane structure-containing polymer with high boron content comprises the following steps:
(1) to a 100ml Schlenk flask equipped with a magnetic stirring, constant pressure dropping funnel device was added allyl-substituted meta-carborane (12mmol), the entire reaction system was replaced with argon gas by gas replacement, and then 30ml of toluene was added to the reaction flask via the dropping funnel, and borane dimethylsulfide complex (3ml, 6mmol) was added dropwise under ice-water bath conditions.
(2) And after the dropwise addition of the borane dimethyl sulfide complex is finished, continuously stirring for 20min, reacting at room temperature overnight, after the reaction is finished, performing rotary evaporation, and drying in a vacuum drying oven at 150 ℃ for 5h to obtain 1.3858g of milky viscous solid, namely the carborane-containing polymer 2 with high boron content.
The FT-IR chart of the carborane structure-containing polymer 2 with a high boron content prepared in this example is shown in FIG. 6; the nuclear magnetic hydrogen spectrum in the deuterated chloroform solvent is shown in figure 7; the nuclear magnetic boron spectrum in the deuterated chloroform solvent is shown in figure 8; the graph of TG-dTG in air is shown in FIG. 9, and it can be seen that the carborane structure-containing polymer 2 with high boron content is prepared to have extremely high thermal stability and thermo-oxidative stability.
Example 6
The allyl substituted meta-carborane and borane ammonia complex prepared in the embodiment 2 are selected as raw materials, and dimethyl ether is used as a solvent; the raw materials can be obtained by the commercial route and the like, and the preparation method of the carborane structure-containing polymer with high boron content comprises the following steps:
(1) adding allyl substituted meta-carborane (12mmol) into a 50ml Schlenk bottle provided with a magnetic stirring and constant pressure dropping funnel device, completely replacing the reaction system with argon gas through gas replacement, then adding 30ml of dimethyl ether into the reaction bottle through the dropping funnel, and dropwise adding borane ammonia complex (0.2058g, 90 percent and 6mmol) under the condition of ice-water bath;
(2) after the dropwise addition of the borane-ammonia complex, the reaction is carried out for 48h at 80 ℃, after the reaction is finished, the reaction product is subjected to rotary evaporation and is dried for 5h in a vacuum drying oven at 30 ℃, and a milky white reaction product 1.2661g, namely the carborane-containing structural polymer with high boron content is obtained.
Example 7
The allyl substituted ortho carborane and borane tetrahydrofuran prepared in the embodiment 1 are selected as raw materials, and dimethylformamide is selected as a solvent; the raw materials can be obtained by the commercial route and the like, and the preparation method of the carborane structure-containing polymer with high boron content comprises the following steps:
(1) adding allyl substituted ortho-carborane (12mmol) into a 50ml Schlenk bottle provided with a magnetic stirring and constant pressure dropping funnel device, completely replacing the reaction system with argon through gas replacement, then adding 30ml of dimethylformamide into the reaction bottle through the dropping funnel, and dropwise adding borane tetrahydrofuran (6mmol) under the condition of ice-water bath;
(2) after the dropping of the borane-ammonia complex is finished, reacting for 30h at 100 ℃, after the reaction is finished, performing rotary evaporation, and drying for 2h in a vacuum drying oven at 150 ℃ to obtain a milky white reaction product, namely the carborane-containing structural polymer with high boron content.
Example 8
The alkenyl-substituted para-carborane and diborane prepared in the embodiment 3 are selected as raw materials, and dimethylbenzene is used as a solvent; the raw materials can be obtained by the commercial route and the like, and the preparation method of the carborane structure-containing polymer with high boron content comprises the following steps:
(1) adding alkenyl substituted para-carborane (12mmol) into a 50ml Schlenk bottle provided with a magnetic stirring and constant pressure dropping funnel device, completely replacing the reaction system with argon gas through gas replacement, then adding 30ml of dimethylbenzene into the reaction bottle through the dropping funnel, and introducing diborane (6mmol) under the condition of ice-water bath;
(2) after the introduction of diborane is finished, reacting for 72h at the temperature of minus 10 ℃, after the reaction is finished, performing rotary evaporation, and drying for 2h in a vacuum drying oven at the temperature of 150 ℃ to obtain a milky white reaction product, namely the carborane-containing structure polymer with high boron content.
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 method for preparing a carborane structure-containing polymer with high boron content is characterized by comprising the following steps:
and under a protective atmosphere, reacting a mixed reaction system containing double-bond-terminated carborane derivatives, borohydride and/or borane complex and a first solvent at-10-300 ℃ for 30-72 h to obtain the carborane-containing structural polymer with high boron content.
2. The production method according to claim 1, characterized by comprising:
under a protective atmosphere, dissolving a carborane derivative containing a double-bond end capping into a first solvent, and then adding borohydride and/or borane complex into the obtained mixture at the temperature of-10-5 ℃ to form the mixed reaction system.
3. The method according to claim 1, wherein the double bond-terminated carborane derivative has a structure represented by any one of formulas (I) to (III):
wherein R is selected from CnH2nCOO, CO, Ph, NH, OAny one of the above, and n is more than or equal to 0 and less than or equal to 10;
and/or the double bond terminated carborane derivative is a double bond terminated carborane derivative.
4. The method of claim 1, wherein: the boron hydride and/or borane complex comprises any one or the combination of more than two of borane, diborane, borane dimethyl sulfide complex, borane tetrahydrofuran and amine borane complex; preferably, the amine borane complex comprises a borane ammonia complex;
and/or the first solvent comprises any one or the combination of more than two of benzene, dimethylbenzene, dimethyl ether, tetrahydrofuran, toluene and dimethylformamide.
5. The method of claim 1, wherein: the molar ratio of C ═ C bonds in the double-bond-terminated carborane derivative to B-H bonds in the borohydride and/or borane complex is 1: 2-5: 1.
6. The method of claim 1, wherein the double bond-terminated carborane derivative is prepared by a method comprising:
under the conditions of protective atmosphere and ice bath, dissolving carborane in a second solvent to form a carborane solution, then adding an organic lithium reagent, and stirring and reacting at room temperature for 0.1-5 hours to obtain carborane lithium salt;
and adding halogenated olefin/halogenated alkyne into the obtained carborane lithium salt at the temperature of 0-10 ℃, and then reacting for 0.1-5 h at the temperature of 20-100 ℃ to obtain the double-bond end-capped carborane derivative.
7. The preparation method according to claim 6, wherein the carborane comprises any one or a combination of two or more of o-carborane, m-carborane and p-carborane;
and/or, the organolithium reagent comprises n-butyllithium and/or t-butyllithium;
and/or the second solvent comprises one or the combination of more than two of anhydrous diethyl ether, anhydrous tetrahydrofuran and anhydrous toluene;
and/or the halogenated olefin/halogenated alkyne comprises any one or a combination of more than two of bromopropene, chloropropene, bromobutene and 3-bromopropyne;
and/or the molar ratio of the carborane to the organic lithium reagent to the halogenated olefin/halogenated alkyne is 1: 1-2.4: 1-2.6;
and/or the molar weight ratio of the borohydride and/or borane complex to the carborane is 1: 0.1-100.
8. The method of claim 1, further comprising: after the reaction is finished, distilling and drying the obtained mixture; preferably, the conditions of the drying treatment include: the temperature is 30-150 ℃, and the drying time is 2-5 h.
9. A high boron content carborane structure containing polymer made by the method of any one of claims 1-8;
preferably, the high boron content carborane structure containing polymer is in the form of a bulk solid and/or a powder.
10. Use of the high boron content carborane structure containing polymer according to claim 9 in the field of aerospace industry, high temperature resistant materials, ablation resistant materials or neutron radiation shielding materials.
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