CN112457439A - Carbon-functionalized o-carborane-benzyl ethylene polymer and preparation method thereof - Google Patents
Carbon-functionalized o-carborane-benzyl ethylene polymer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 25
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
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- 239000002904 solvent Substances 0.000 claims abstract description 14
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- 238000001035 drying Methods 0.000 claims abstract description 12
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- 238000005406 washing Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
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- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
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- 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 25
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 239000012044 organic layer Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
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- 238000010791 quenching Methods 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 7
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
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- 239000000919 ceramic Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
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- 229910018944 PtBr2 Inorganic materials 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
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- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 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
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- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a carbon functionalized o-carborane-benzyl ethylene polymer and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a 1-benzyl ethylene-o-carborane monomer; adding a 1-benzyl ethylene-o-carborane monomer, an initiator azodiisobutyronitrile and a solvent benzene into a dry reaction vessel, vacuumizing in an ice water bath, introducing argon for more than 3 times, replacing gas in the system, and heating in an oil bath for reaction; and adding a small amount of tetrahydrofuran into a reaction container after reaction to dilute and dissolve the polymer, precipitating white flocculent solid in n-hexane, washing with the n-hexane, and drying the washed solid in a vacuum drying oven to obtain white polymer solid, namely the carbon functionalized o-carborane-benzyl ethylene polymer. The invention breaks through the technical bottleneck of o-carborane-benzyl ethylene monomer free radical polymerization, and prepares a poly (o-carborane-benzyl ethylene) precursor with higher molecular weight, excellent high temperature resistance and a brand new structure.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and relates to a carbon-functionalized o-carborane-benzyl ethylene polymer and a preparation method thereof.
Background
The boron carbide ceramic has low density, high Young modulus, larger neutron capture cross section and excellent thermoelectric property, has important application value in the aspects of wear-resistant materials, ceramic weapons, neutron moderators of nuclear reactors and power generation devices of external space spacecraft, and has important physical significance based on the low atomic number of the boron carbide ceramic especially in the research of Inertial Confinement Fusion (ICF) targets.
Boron carbide exists in the form of solid solution in a certain carbon content range (8.9 at% to 24.3 at% C), however, due to the high covalent bond content (> 93%) and poor plasticity, the boron carbide ceramic material has great difficulty in preparing boron carbide ceramic materials with special morphology. The precursor body cracking and converting ceramic process makes full use of the characteristic that organic high molecular polymer is easy to form, and the precursor is thermally treated to prepare the material with specific morphology.
In 1998, 6-hexenylsebaborane (6-HB) was first synthesized by the Sneddon group (Design, syntheses and applications of chemical precursors to advanced Ceramic materials in nanostructured forms, Journal of the European Ceramic Society,2005, 25, 91-97) and utilized Cp2ZrMe2/B(C6F5)3The system achieved its polymerization but only a low molecular weight poly (6-hexenyl decaborane) precursor (Mn ═ 3000) was obtained in 10% yield. In 2014, the prior art (Platinum catalyzed sequential hydrogenation of a surface a poly (alkali) with a surface in the main chemical Communications,2014,50,4585-4587.) utilized PtBr2The poly (6-hexenyl decaborane) precursor containing the decaborane main chain structure is synthesized for the first time by catalytic continuous hydroboration addition polymerization, the carbon residue rate is up to 82%, but the polymer has larger brittleness and slightly insufficient processing and forming capability.
The o-carborane is a boron carbon molecular cluster with an icosahedron structure, and has important application in the field of high-temperature resistant polymers such as modified polysiloxane. However, the preparation of boron carbide ceramics using o-carborane as the boron source was preceded byBody drive has been rarely reported. In recent years, polystyrene has made an important progress as a general polymer material with good processability in the field of inertial confinement fusion plastic targets, and the preparation process of microspheres is becoming mature. Because o-carborane is an electron-deficient boron carbon molecular cluster, the polymerization activity of benzyl ethylene can be reduced after the o-carborane is introduced into benzyl ethylene, and a free radical polymerization method for the monomer is not reported at present. Therefore, the o-carborane is expected to be introduced into the branched chain structure of the polystyrene by utilizing the characteristic of good processability of the polystyrene so as to prepare an o-carborane modified polystyrene precursor with good process performance, namely inertial confinement fusion B4Controlled preparation of the C target provides candidate materials.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a carbon-functionalized o-carborane-benzyl ethylene polymer characterized by the general structural formula:
wherein, R is any one of H, Me, Ph and n-Bu, and n is 1-1000.
Preferably, n is 200-.
The invention also provides a method for preparing a carbon-functionalized o-carborane-benzyl ethylene polymer, which comprises the following steps:
adding o-carborane or an o-carborane derivative into a dry reaction vessel, adding a dehydrated solvent ethylene glycol dimethyl ether under the protection of argon, dissolving, and stirring for 8-15 min in an ice-water bath; after the temperature of the system is reduced to 0 ℃, adding n-butyllithium, removing the ice water bath after 30-45 min, and reacting at room temperature for 1-2 h; cooling the system to 0 ℃ by using ice water bath again, adding 4-chloromethyl styrene after 8-15 min, reacting for 30-45 min, removing the ice water bath, reacting for 1.8-2.5 h at room temperature, heating and refluxing the system by using an oil bath for 6-10 h, and stopping the reaction;
step two, adding deionized water into the system reacted in the step one to quench the reaction, adding ethyl acetate to extract the reaction, washing the system with saturated sodium bicarbonate, saturated ammonium chloride and saturated saline solution respectively, collecting an organic layer, drying the organic layer with a small amount of anhydrous sodium sulfate, filtering, distilling the collected solution under reduced pressure, removing the redundant solvent, separating the obtained yellow oily liquid by column chromatography, and obtaining a monomer by using petroleum ether as an eluent;
adding a monomer, an initiator azodiisobutyronitrile and a solvent benzene into a dry reaction container, vacuumizing in an ice-water bath, introducing argon for more than 3 times, replacing gas in the system, and heating in an oil bath for reaction for 3-5 days;
step four, adding a small amount of tetrahydrofuran into the reaction container after the reaction in the step three to dilute and dissolve the polymer, precipitating white flocculent solid in n-hexane, washing the flocculent solid for more than 3 times by using the n-hexane, placing the washed solid in a vacuum drying oven, and drying the solid for 4-5 hours at the temperature of 60-70 ℃ to obtain white polymer solid, namely the carbon functionalized o-carborane-benzyl ethylene polymer.
Preferably, in the first step, the molar ratio of the o-carborane or the o-carborane derivative to the 4-chloromethylstyrene and the n-butyllithium is 1:1.2: 1.2; the mass-volume ratio of the o-carborane or the o-carborane derivative to the ethylene glycol dimethyl ether is 1g: 20-30 mL.
Preferably, in the second step, the volume ratio of the deionized water to the ethyl acetate is 1: 1; the mass-volume ratio of the o-carborane or the o-carborane derivative to the ethyl acetate is 1g: 8-12 mL.
Preferably, in the first step, the oil bath is heated to 80-85 ℃; in the second step, the temperature of reduced pressure distillation is 40-45 ℃; in the third step, the heating reaction temperature is 80-90 ℃.
Preferably, in the third step, the molar ratio of the monomer to the initiator azobisisobutyronitrile is 100: 1.9; the mass volume ratio of the monomer to the solvent benzene is 0.25-0.35 g:0.8 mL.
Preferably, the o-carborane derivative is any one of 2-methyl-o-carborane, 2-phenyl-o-carborane, and 2-butyl-o-carborane.
The invention at least comprises the following beneficial effects: the invention breaks through the technical bottleneck of o-carborane-benzyl ethylene monomer free radical polymerization, and prepares a poly (o-carborane-benzyl ethylene) precursor with higher molecular weight, excellent high temperature resistance and a brand new structure.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a TGA profile of poly (1-benzylidene-o-carborane) prepared according to example 1 of the present invention;
FIG. 2 is a drawing of poly (1-benzylidene-o-carborane) prepared according to an example of the present invention1HNMR spectrogram;
FIG. 3 is a chemical reaction scheme for the preparation of a carbon-functionalized o-carborane-benzyl ethylene polymer of the present invention; wherein black dots in the structural formula represent C.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a carbon-functionalized o-carborane-benzyl ethylene polymer having the formula:
the preparation method comprises the following steps:
step one, adopting a Schlenk technology, taking a 250mL round-bottom flask as a reaction vessel, and sequentially connecting a condensation tube, a gas guide head and a double-row tube. Firstly, vacuumizing the system under heating and introducing argon for more than 3 times to exhaust water and air in a reaction container, and replacing the argon; adding 2.00g o-carborane into a round-bottom flask under the protection of argon, adding 50mL of dried ethylene glycol dimethyl ether by using a dried syringe, stirring to dissolve, placing the round-bottom flask into an ice-water bath, and adding 8.6mL of n-butyllithium (1.6M, n-hexane solution) by using the dried syringe after the temperature of a system is reduced to 0 ℃; reacting at room temperature for 2h, placing the round-bottom flask in an ice-water bath again, and adding 2mL of 4-chloromethyl-styrene by using a dry syringe after 10 min; after reacting for 2 hours at room temperature, placing the flask in an oil bath, heating to 80 ℃, and carrying out reflux reaction for 8 hours;
step two, after the reaction in the step one is finished, adding 20mL of deionized water to quench the reaction, adding 20mL of ethyl acetate to extract the reaction, washing the reaction product by using a proper amount of saturated ammonium chloride, saturated sodium bicarbonate and saturated saline solution in sequence, standing the reaction product for 10min, collecting an organic layer solution, drying the organic layer solution by using anhydrous sodium sulfate, filtering the organic layer solution, distilling the filtrate at 40 ℃ under reduced pressure to remove redundant solvent, performing column chromatography separation, and using petroleum ether as an eluent to obtain 1.89g of white solid, namely 1-benzyl ethylene-o-carborane, wherein the yield is 52%;
the chemical reaction formula is as follows:
step three, adding 260mg (1mmol) of 1-benzyl ethylene-o-carborane, 3.2mg of recrystallized azobisisobutyronitrile and 0.8mL of redistilled benzene into a dry 20mL anaerobic bottle in sequence; sealing the anaerobic bottle, vacuumizing in ice-water bath, introducing argon gas for 3 times to exhaust air in the system, placing the anaerobic bottle in oil bath at 85 deg.C for reaction for 4 days,
after the reaction is stopped in the fourth step and the third step, 1mL of tetrahydrofuran is added by a dropper, after stirring and dissolving, 50mL of n-hexane is added into a 100mL beaker, the polymer solution is dropwise added into the beaker under the stirring state to precipitate a white solid, and after filtering, the white solid is dried in a vacuum drying oven at 40 ℃ for 4 hours to obtain 234mg of the white solid, namely the poly (1-benzyl ethylene-o-carborane), wherein the yield is 90%;
the chemical reaction formula is as follows:
FIG. 1 is a TGA profile of poly (1-benzylidene-o-carborane) prepared according to example 1 of the present invention; as can be seen from the figure, the 5% thermal weight loss temperature T5346.44 ℃ and 10% of thermal weight loss temperature T10387.24 ℃, the maximum degradation rate temperature of 425.22 ℃ and the carbon residue rate of 7.62 percent.
FIG. 2 is a drawing of poly (1-benzylidene-o-carborane) prepared in example 1 of the present invention1HNMR spectrogram;1the solvent used in the H NMR test is deuterated acetone, and as shown in the figure, 3 and 4 are two groups of hydrocarbon peaks on a benzene ring, 5 is a hydrocarbon peak of a benzyl group, 6 is a hydrocarbon peak on a carborane cage, and the hydrocarbon peaks at the 1 and 2 positions are overlapped in a boron hydrogen peak of carborane (chemical shift is 1.2-2.8 ppm).
Example 2:
a carbon-functionalized o-carborane-benzyl ethylene polymer having the formula:
the preparation method comprises the following steps:
the method comprises the following steps of firstly, adopting a Schlenk technology, taking a 100mL round-bottom flask as a reaction vessel, and sequentially connecting a condensation pipe, a gas guide head and a double-row pipe; firstly, vacuumizing the system under heating and introducing argon for more than 3 times to exhaust water and air in a reaction container, and replacing the argon; 632.88mg (4mmol) of 2-methyl-o-carborane is added into a round-bottom flask under the protection of argon, 20mL of dried tetrahydrofuran is added by a dried syringe and is stirred to be dissolved, the round-bottom flask is placed in an ice-water bath, and 2.63mL of n-butyllithium (1.6M, n-hexane solution) is added by the dried syringe after the temperature of the system is reduced to 0 ℃; reacting at room temperature for 2h, placing the round-bottom flask in an ice-water bath again, and adding 0.60mL of 4-chloromethyl-styrene by using a dry syringe after 10 min; after reacting for 2 hours at room temperature, placing the flask in an oil bath, heating to 80 ℃, and carrying out reflux reaction for 8 hours;
the chemical reaction formula is as follows:
step two, after the reaction in the step one is finished, adding 10mL of deionized water to quench the reaction, adding 20mL of ethyl acetate to extract the reaction, washing the reaction product by using a proper amount of saturated ammonium chloride, saturated sodium bicarbonate and saturated saline solution in sequence, standing the reaction product for 10min, collecting an organic layer solution, drying the organic layer solution by using anhydrous sodium sulfate, filtering the organic layer solution, distilling the filtrate at 40 ℃ under reduced pressure to remove redundant solvent, performing column chromatography separation, and using petroleum ether as an eluent to obtain 828.58mg of white solid, namely 1-benzyl ethylene-2-methyl-o-carborane, wherein the yield is 76%;
step three, 274mg (1mmol) of 1-benzyl ethylene-o-carborane, 3.2mg of recrystallized azobisisobutyronitrile and 0.8ml of redistilled benzene are sequentially added into a dry 20ml anaerobic bottle; sealing the anaerobic bottle, vacuumizing and introducing argon for 3 times in an ice-water bath to exhaust air in the system, and placing the anaerobic bottle in an oil bath at 85 ℃ for reaction for 4 days;
step four and step three, after the reaction is stopped, adding 1mL of tetrahydrofuran by a dropper, stirring and dissolving, adding 50mL of n-hexane into a 100mL beaker, dropwise adding the polymer solution into the beaker under the stirring state to precipitate a white solid, filtering, and drying in a vacuum drying oven at 40 ℃ for 4 hours to obtain 225mg of the white solid, namely the poly (1-benzyl ethylene-2-methyl-o-carborane), wherein the yield is 82%;
the chemical reaction formula is as follows:
example 3:
a carbon-functionalized o-carborane-benzyl ethylene polymer having the formula:
the preparation method comprises the following steps:
the method comprises the following steps of firstly, adopting a Schlenk technology, taking a 100mL round-bottom flask as a reaction vessel, and sequentially connecting a condensation pipe, a gas guide head and a double-row pipe; firstly, vacuumizing the system under heating and introducing argon for more than 3 times to exhaust water and air in a reaction container, and replacing the argon; 884.88mg (4mmol) of 2-phenyl-o-carborane was added to a round bottom flask under argon, 20mL of dried tetrahydrofuran was added by a dry syringe, the mixture was dissolved by stirring, the round bottom flask was placed in an ice-water bath, and after the temperature of the system was lowered to 0 ℃, 2.63mL of n-butyllithium (1.6M, n-hexane solution) was added by a dry syringe. Reacting at room temperature for 2h, placing the round-bottom flask in an ice-water bath again, and adding 0.60mL of 4-chloromethyl-styrene by using a dry syringe after 10 min; after reacting for 2 hours at room temperature, placing the flask in an oil bath, heating to 80 ℃, and carrying out reflux reaction for 8 hours;
step two, after the reaction in the step one is finished, adding 10mL of deionized water to quench the reaction, adding 20mL of ethyl acetate to extract the reaction, washing the reaction product with a proper amount of saturated ammonium chloride, saturated sodium bicarbonate and saturated saline solution in sequence, standing the reaction product for 10min, collecting an organic layer solution, drying the organic layer solution by using anhydrous sodium sulfate, filtering the organic layer solution, distilling the filtrate at 40 ℃ under reduced pressure to remove redundant solvent, performing column chromatography separation, and using petroleum ether as an eluent to obtain 1.01g of white solid, namely 1-benzyl ethylene-2-phenyl-o-carborane, wherein the yield is 75%;
the chemical reaction formula is as follows:
step three, 337mg (1mmol) of 1-benzyl ethylene-o-carborane, 3.2mg of recrystallized azobisisobutyronitrile and 0.8mL of redistilled benzene are sequentially added into a dry 20mL anaerobic bottle; sealing the anaerobic bottle, vacuumizing and introducing argon for 3 times in an ice-water bath to exhaust air in the system, and placing the anaerobic bottle in an oil bath at 85 ℃ for reaction for 4 days;
and step four and step three, after the reaction is stopped, adding 1mL of tetrahydrofuran by a dropper, stirring and dissolving, adding 50mL of n-hexane into a 100mL beaker, dropwise adding the polymer solution into the beaker under the stirring state to precipitate a white solid, filtering, and drying in a vacuum drying oven at 40 ℃ for 4 hours to obtain 295mg of the white solid, namely the poly (1-benzyl ethylene-2-phenyl-o-carborane), wherein the yield is 88%.
The chemical reaction formula is as follows:
example 4:
a carbon-functionalized o-carborane-benzyl ethylene polymer having the formula:
the preparation method comprises the following steps:
step one, adopting a Schlenk technology, taking a 250mL round-bottom flask as a reaction vessel, and sequentially connecting a condensation tube, a gas guide head and a double-row tube. Firstly, vacuumizing the system under heating and introducing argon for more than 3 times to exhaust water and air in a reaction container, and replacing the argon; under the protection of argon, 800.88mg (4mmol) of 2-butyl-o-carborane is added into a round-bottom flask, 20mL of dried ethylene glycol dimethyl ether is added by a dry syringe, the mixture is stirred and dissolved, the round-bottom flask is placed in an ice-water bath, and after the temperature of a system is reduced to 0 ℃, 2.63mL of n-butyllithium (1.6M, n-hexane solution) is added by the dry syringe; reacting at room temperature for 2h, placing the round-bottom flask in an ice-water bath again, and adding 0.60mL of 4-chloromethyl-styrene by using a dry syringe after 10 min; after reacting for 2 hours at room temperature, placing the flask in an oil bath, heating to 80 ℃, and carrying out reflux reaction for 8 hours;
step two, after the reaction is finished, adding 10mL of deionized water to quench the reaction, adding 20mL of ethyl acetate to extract the reaction, washing the reaction product with a proper amount of saturated ammonium chloride, saturated sodium bicarbonate and saturated saline solution in sequence, standing the reaction product for 10min, collecting an organic layer solution, drying the solution with anhydrous sodium sulfate, filtering the solution, distilling the filtrate at 40 ℃ under reduced pressure to remove redundant solvent, performing column chromatography separation, and using petroleum ether as an eluent to obtain 405.74mg of colorless liquid, namely 1-benzyl ethylene-2-butyl-o-carborane, wherein the yield is 32%;
the chemical reaction formula is as follows:
step three, adding 316mg (1mmol) of 1-benzyl ethylene-o-carborane, 3.2mg of recrystallized azobisisobutyronitrile and 0.8mL of redistilled benzene into a dry 20mL anaerobic bottle in sequence; sealing the anaerobic bottle, vacuumizing and introducing argon for 3 times in an ice-water bath to exhaust air in the system, and placing the anaerobic bottle in an oil bath at 85 ℃ for reaction for 4 days; after the reaction is stopped, adding 1mL of tetrahydrofuran by using a dropper, stirring and dissolving, adding 50mL of n-hexane into a 100mL beaker, dropwise adding the polymer solution into the beaker while stirring to precipitate a white solid, filtering, and drying in a vacuum drying oven at 40 ℃ for 4 hours to obtain 248mg of the white solid, namely the poly (1-benzyl ethylene-2-butyl-o-carborane) with the yield of 79%;
the chemical reaction formula is as follows:
table 1 shows the molecular weight distributions of the polymers prepared in examples 1 to 4;
TABLE 1
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (8)
1. A carbon-functionalized o-carborane-benzyl ethylene polymer having the general structural formula:
wherein, R is any one of H, Me, Ph and n-Bu, and n is 1-1000.
2. The carbon-functionalized o-carborane-benzyl ethylene polymer of claim 1, wherein n is 200-.
3. A process for the preparation of a carbon functionalized o-carborane-benzyl ethylene polymer comprising the steps of:
adding o-carborane or an o-carborane derivative into a dry reaction vessel, adding a dehydrated solvent ethylene glycol dimethyl ether under the protection of argon, dissolving, and stirring for 8-15 min in an ice-water bath; after the temperature of the system is reduced to 0 ℃, adding n-butyllithium, removing the ice water bath after 30-45 min, and reacting at room temperature for 1-2 h; cooling the system to 0 ℃ by using ice water bath again, adding 4-chloromethyl styrene after 8-15 min, reacting for 30-45 min, removing the ice water bath, reacting for 1.8-2.5 h at room temperature, heating and refluxing the system by using an oil bath for 6-10 h, and stopping the reaction;
step two, adding deionized water into the system reacted in the step one to quench the reaction, adding ethyl acetate to extract the reaction, washing the system with saturated sodium bicarbonate, saturated ammonium chloride and saturated saline solution respectively, collecting an organic layer, drying the organic layer with a small amount of anhydrous sodium sulfate, filtering, distilling the collected solution under reduced pressure, removing the redundant solvent, separating the obtained yellow oily liquid by column chromatography, and obtaining a monomer by using petroleum ether as an eluent;
adding a monomer, an initiator azodiisobutyronitrile and a solvent benzene into a dry reaction container, vacuumizing in an ice-water bath, introducing argon for more than 3 times, replacing gas in the system, and heating in an oil bath for reaction for 3-5 days;
step four, adding a small amount of tetrahydrofuran into the reaction container after the reaction in the step three to dilute and dissolve the polymer, precipitating white flocculent solid in n-hexane, washing the flocculent solid for more than 3 times by using the n-hexane, placing the washed solid in a vacuum drying oven, and drying the solid for 4-5 hours at the temperature of 60-70 ℃ to obtain white polymer solid, namely the carbon functionalized o-carborane-benzyl ethylene polymer.
4. The process for the preparation of a carbofunctional o-carborane-benzyl ethylene polymer of claim 3, wherein in step one, the molar ratio of o-carborane or o-carborane derivative to 4-chloromethylstyrene, n-butyllithium is 1:1.2: 1.2; the mass-volume ratio of the o-carborane or the o-carborane derivative to the ethylene glycol dimethyl ether is 1g: 20-30 mL.
5. The method of preparing a carbon-functionalized o-carborane-benzyl ethylene polymer of claim 3, wherein in step two, the volume ratio of deionized water to ethyl acetate is 1: 1; the mass-volume ratio of the o-carborane or the o-carborane derivative to the ethyl acetate is 1g: 8-12 mL.
6. The method of claim 3, wherein in step one, the carbon-functionalized o-carborane-benzyl ethylene polymer is heated to 80-85 ℃ in an oil bath; in the second step, the temperature of reduced pressure distillation is 40-45 ℃; in the third step, the heating reaction temperature is 80-90 ℃.
7. The method of preparing a carbon-functionalized o-carborane-benzyl ethylene polymer of claim 3, wherein in step three, the molar ratio of monomer to initiator azobisisobutyronitrile is 100: 1.9; the mass volume ratio of the monomer to the solvent benzene is 0.25-0.35 g:0.8 mL.
8. The method of making a carbon-functionalized o-carborane-benzyl ethylene polymer of claim 3, wherein the o-carborane derivative is any one of 2-methyl-o-carborane, 2-phenyl-o-carborane, and 2-butyl-o-carborane.
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