CN102140105A - Carborane and preparation method thereof - Google Patents
Carborane and preparation method thereof Download PDFInfo
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- CN102140105A CN102140105A CN2011100631946A CN201110063194A CN102140105A CN 102140105 A CN102140105 A CN 102140105A CN 2011100631946 A CN2011100631946 A CN 2011100631946A CN 201110063194 A CN201110063194 A CN 201110063194A CN 102140105 A CN102140105 A CN 102140105A
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- carborane
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Abstract
The invention discloses a carborane and a synthesis method thereof. In the method, propiolic halide is adopted as a raw material to synthesize propargyl ether containing unsaturated carbon-carbon double bond through nucleophile substitution reaction, and the alkynyl in the propargyl ether is adducted with decaborane to obtain reactive carborane in which a carbon-carbon double bond is bonded on a cage type carborane structure through an ether bond. The synthesized reactive carborane, which is liquid at normal temperature, can have an effect of a plasticizer while being used as a composite solid burning-rate catalyst of a propellant. The unsaturated group carbon-carbon double bond, which has disconjugacy and strong reactivity, contained in the carborane is expected to overcome migration through taking part in the crosslinking curing reaction with the composite solid propellant. The carborane containing unsaturated carbon-carbon double bond has low synthesis cost and simple and convenient production technique, and is beneficial for industrial production.
Description
Technical field
The invention belongs to propelling agent and synthesize the field with chemical, be to be raw material with the propiolic halide, by the synthetic propargyl ether that contains unsaturated carbon-carbon double bond of nucleophilic substitution reaction,, obtain the carborane that a class contains unsaturated carbon-carbon double bond by alkynyl in the propargyl ether structure and boron hydrogen addition in the last of the ten Heavenly stems.
Background technology
Carborane is the compound that hydroborates and alkynes class are reacted the closed form cage structure of a kind of tetrahexahedron that generates, abroad as the high burning ratemodifier of solid propellant or binding agent and broad research, and developed the carborane compound of series of stable, they can be compatible with propellant component, particularly can make compositepropellent and double-base propellent obtain good ballisticperformancess such as high combustion speed or superelevation combustion speed.As " pallas pit viper " rocket socket compositepropellent of AM General utility companies development in 1976, adopt carborane to improve the performance and the precision of weapon greatly as high burningrate catalyst.War department adopted the n-hexyl carborane to be developed into the standby high burning rate propellant of " soldier " anti-ballistic system as burning ratemodifier in 1974.
Under n-hexyl carborane and other kind such as sec.-propyl carborane, the normal-butyl carborane normal temperature such as (NBC) all is liquid, with their adding end alkyl polyhutadiene (HTPB) compositepropellents, when end is completed in basic polyhutadiene (CTPB) compositepropellent and urethane (PU) compositepropellent, consumption is 10%～13%, can play softening agent on the one hand, can make the combustion speed of propelling agent improve 2 to 3 times simultaneously again.When this class alkyl carborane derivative was applied to composite solidpropellant as plasticising type burningrate catalyst, the greatest problem of existence was to migrate to the composite solidpropellant surface propelling agent stability in storage and safety performance are worsened.
Utilize the cross-linking and curing reaction of the two keys participation of C=C propelling agent in the carborane alkene derivatives molecular structure, be expected to overcome its transport property.But, when between carborane cagelike structure and two key methyl number after a little while, C=C is reactive poor.For example, addition reaction can take place in 4-(1-carborane radical)-butylene, but the free radical addition reaction then all can not take place for allyl group, vinyl or isopropenyl carborane.Same these pairs key also not with reactions such as hydrogen peroxide, iodine bromide IBr.The specificity of this pair of key mainly is that the electrophilic effect that the carborane cagelike structure is strong greatly weakens the nucleophilicity of two keys owing to have due to the interaction of electrons between two key and carborane cagelike structure.Show all that for the UV spectrum of isopropenyl carborane, the research that molar refraction reaches the addition reaction of basic metal in liquid ammonia solution the character of this pair key is identical with conjugated double bond.
On the basis of the above, the present invention's design has also prepared a kind of carborane that contains the alkene ether side chain, its carbon-carbon double bond is linked on the cage-type carborane structure via the Sauerstoffatom key, the carborane derivative that contains the alkene ether side chain that obtains has the advantage of following several respects: under (1) normal temperature is liquid, is used for composite solidpropellant and can plays softening agent; (2) boron content height can effectively improve the combustion speed of propelling agent; (3) carbon-carbon double bond does not have conjugacy, reactive strong, and the cross-linking and curing reaction that participates in propelling agent by carbon-carbon double bond can overcome its transport property; (4) be that feedstock production carborane derivative is compared with the carborane derivative, in the building-up process of the present invention, final step is that boron hydrogen addition in the last of the ten Heavenly stems generates carborane, this mainly concentrates on the cage-type carborane of boron hydrogen in the last of the ten Heavenly stems for synthetic cost, the last of the ten Heavenly stems boron hydrogen utilization ratio height, the carborane cost is low, helps its suitability for industrialized production.
Summary of the invention
The invention provides a kind of carborane and preparation method thereof, specifically be meant a kind of cage-type carborane that contains the alkene ether side chain and preparation method thereof, utilize carbon-carbon double bond participation solid propellant cross-linking and curing reaction in the alkene ether side chain, can solve the migration problem that exists when existing plasticising type carborane adds as the solid propellant combustion rate catalyzer.
Technical scheme of the present invention is as follows:
Carborane of the present invention, its structural formula is:
Wherein,
R＝(CH
2CH
2O)m(CH
2)nCH
2CH＝CH
2、(CH
2O)m(CH
2)nCH
2CH＝CH
2、
(CH
2CH
2O) mC (O) C (R
1)=CH
2Or (CH
2O) mC (O) C (R
1)=CH
2
M=0,1 or 2 wherein, the integer of n=0 or n=1～8; R
1=H or CH
3
Above-mentioned carborane preparation method comprises that nucleophilic substitution reaction prepares propargyl ether, addition reaction prepares carborane.
Step 1: nucleophilic substitution reaction prepares propargyl ether technical formula and reaction conditions
Ether solvent in the above-mentioned prescription, organic bases, nucleophilic reagent and propiolic halide are joined in the reactor successively, stir, react 3～48h down at 20～100 ℃.
Reaction is removed the salt of generation with reacting liquid filtering after finishing, and filtrate desolventizes 40～110 ℃ of distillations, gets propargyl ether.
Above-mentioned ether solvent is ether, tetrahydrofuran (THF), 1,4-dioxane, glycol dimethyl ether or ethylene glycol diethyl ether and any two or more mixture thereof, and weight ratio is 0.2～5: 1 during mixing.
Above-mentioned organic bases is pyridine, triethylamine or diethylamine.
Related nucleophilic reagent is vinyl carbinol, butenol, hexenol, ethylene glycol allyl ethers, a condensed ethandiol allyl ethers, hydroxy methyl methacrylate or hydroxyethyl methylacrylate etc.
Related propiolic halide is propargyl bromide, iodine propine or propargyl chloride.
Step 2: addition reaction prepares carborane technical formula and reaction conditions
The composition weight ratio
Acetonitrile 5～30
The last of the ten Heavenly stems, boron hydrogen 1
Propargyl ether 1～5
With a kind of the joining successively in the reactor in the prepared propargyl ether of the solvent acetonitrile in the above-mentioned prescription, last of the ten Heavenly stems boron hydrogen and step 1, stir, at 50～100 ℃ of reaction 6～48h down.Reaction is cooled to the room temperature after-filtration with reaction solution after finishing, and filtrate is distilled down at 50～100 ℃ and desolventized, and gets carbon-carbon double bond and is connected in the structural carborane that contains unsaturated group of cage-type carborane by the ehter bond key.
The invention has the beneficial effects as follows that under the synthetic carborane normal temperature be liquid, can play softening agent simultaneously as the composite solidpropellant burningrate catalyst.Compare with conventional art, synthetic carborane of the present invention institute carbon-carbon double bonds does not have conjugacy, reactive strong, is expected to overcome by the cross-linking and curing reaction that participates in propelling agent the transport property of burningrate catalyst.Easy, the synthetic cost of the carborane production technique that contains unsaturated group is low, helps suitability for industrialized production.
Description of drawings
Fig. 1 is the infrared spectrogram of the allyl oxygen methyl carborane of the embodiment of the invention 1 preparation.
Fig. 2 is the infrared spectrogram of the acryloyl-oxy ethoxymethyl carborane of the embodiment of the invention 4 preparations.
Fig. 3 is the infrared spectrogram of the methacryloxypropyl ethoxymethyl carborane of the embodiment of the invention 5 preparations.
Among the figure: prepared product is all at 2580～2595cm
-1Between and 1020cm
-1Near two strong infrared absorption peaks have appearred, these two absorption peaks correspond respectively to the stretching vibration absorption peak of B-H key and B-B key.1634～1645cm
-1Between the two key stretching vibration absorption peaks of C=C of medium tenacity have appearred, confirm that product is the carborane that contains the unsaturated group carbon-carbon double bond.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1: the preparation of allyl oxygen methyl carborane
In the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, add the 200g ether, 70.1g pyridine and 20.6g vinyl carbinol under the stirring at room, add the 50.8g propargyl bromide.Add the back insulation and stir 12h for 30 ℃.After reaction finishes, remove by filter the salt of generation, filtrate is distilled down at 40～45 ℃ and is desolventized, and gets the faint yellow transparent oily liquid allyl group of 25.0g propargyl ether, purity 99.0%, productive rate 74.2%.
Add 12.4g boron in last of the ten Heavenly stems hydrogen in the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, 19.2g allyl group propargyl ether and 70g acetonitrile stir, reflux, reaction 16h.After finishing reaction, reaction solution is cooled to room temperature, filters, filtrate is distilled down at 70～75 ℃ and is desolventized, and obtains 16.1g water white transparency thick liquid product allyl oxygen methyl carborane, and the product structure formula is as follows:
Reaction yield 50.9%.Product structure characterizes:
1H NMR (CDCl
3, δ): 4.74 (2H), 4.20 (m, 2H), 3.12 (s, 1H), 3.01 (s, 2H), 2.08～2.06 (m, 10H), ppm.FT-IR(v)：3218(C-H)，2586(B-H)，1641(C＝C)，1470(CH
2)，1133(C-O-C)，1018(B-B)cm
-1。
Embodiment 2: the preparation of allyl oxygen ethoxymethyl carborane
In the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, add the 150g tetrahydrofuran (THF), 35.5g pyridine and 36.3g ethylene glycol allyl ether under the stirring at room, add the 26.7g propargyl chloride.Add the back insulation and stir 18h for 65 ℃.After reaction finishes, remove by filter the salt of generation, filtrate is distilled down at 65～70 ℃ and is desolventized, and gets the faint yellow transparent oily liquid allyl of 26.8g oxygen oxyethyl group alkynes propyl ether, purity 98.9%, productive rate 54.6%.
Add 6.2g boron in last of the ten Heavenly stems hydrogen in the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, 14.1g allyl oxygen oxyethyl group alkynes propyl ether and 125g acetonitrile stir, reflux, reaction 16h.After finishing reaction, reaction solution is cooled to room temperature, filters, filtrate is distilled down at 70～75 ℃ and is desolventized, and obtains 9.8g water white transparency thick liquid product, and the product structure formula is as follows:
Reaction yield 48.0%.Product structure characterizes:
1H NMR (CDCl
3, δ): 4.56 (2H), 4.11 (m, 2H), 3.12 (s, 1H), 2.96 (s, 2H), 2.86～2.75 (m, 4H), 2.01～2.16 (m, 10H) ppm.FT-IR(v)：3215，2986(C-H)，2580(B-H)，1640(C＝C)，1471(CH
2)，1128，1106(C-O-C)，1015(B-B)cm
-1。
Embodiment 3: the preparation of hexene oxygen methyl carborane
In the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, add the 280g tetrahydrofuran (THF), 33.5g pyridine and 37.6g 5-thiazolinyl hexanol under the stirring at room, add the 50.8g propargyl bromide.Add the back insulation and stir 16h for 65 ℃.After reaction finishes, remove by filter the salt of generation, filtrate is distilled down at 65～70 ℃ and is desolventized, and gets the faint yellow transparent oily liquid allyl of 28.3g oxygen oxyethyl group alkynes propyl ether, purity 97.6%, productive rate 57.7%.
Add 12.2g boron in last of the ten Heavenly stems hydrogen in the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, 28.0g allyl oxygen oxyethyl group alkynes propyl ether and 300g acetonitrile stir, reflux, reaction 20h.After the end reaction, reaction solution is cooled to room temperature, filters, filtrate is distilled down at 70～75 ℃ and is desolventized, and gets 17.2g water white transparency thick liquid product hexene oxygen methyl carborane, and the product structure formula is as follows:
Reaction yield 42.8%.Product structure characterizes:
1H NMR (CDCl
3, δ): 4.30 (2H), 4.22 (m, 2H), 3.12 (s, 1H), 2.86 (s, 2H), 2.65～2.75 (m, 6H), 2.02～2.26 (m, 10H) ppm.FT-IR(v)：2977，2922(C-H)，2578(B-H)，1636(C＝C)，1470(CH
2)，1110(C-O-C)，1017(B-B)cm
-1。
Embodiment 4: the preparation of acryloyl-oxy ethoxymethyl carborane
In the 100g there-necked flask of reflux condensing tube, thermometer and constant pressure funnel is housed, add the 200g tetrahydrofuran (THF), 45.9g pyridine and 48.0g Hydroxyethyl acrylate under the stirring at room, add the 59.0g propargyl bromide, are incubated 70 ℃ of stirring reaction 15h.After reaction finishes, remove by filter the salt of generation, filtrate is distilled down at 68～75 ℃ and is desolventized, and gets colourless transparent oil liquid acrylyl oxy-ethyl propargyl ether 25.2g, productive rate 36.0%, purity 97.3%.
Add 6.2g boron in last of the ten Heavenly stems hydrogen in the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, 15.4g acrylyl oxy-ethyl propargyl ether and 50g acetonitrile stir, reflux, reaction 16h.After finishing reaction, reaction solution is cooled to room temperature, filters, filtrate is distilled down at 70～75 ℃ and is desolventized, and obtains 13.4g water white transparency thick liquid product, and the product structure formula is as follows:
Reaction yield 62.0%.Product structure characterizes:
1H NMR (CDCl
3, δ): δ 6.50 (s, 1H, CH=C), 6.19～6.26 (m, 2H, C=CH
2), 6.08 (m, 2H, CH
2O), 4.71～4.80 (m, 4H, CH
2CH
2), 2.01～3.18 (m, 10H, BH), ppm.FT-IR(v)：2592(B-H)，1735(C＝O)，1634(C＝C)，1296，1254，1172，1063，1019(B-B)cm
-1。
Embodiment 5: the preparation of methacryloxypropyl ethoxymethyl carborane
In the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, add 320g1, the 4-dioxane, 80.2g triethylamine and 52.0g hydroxyethyl methylacrylate under the stirring at room, add the 59.0g propargyl bromide, are incubated 85 ℃ of stirring reaction 20h.After reaction finishes, remove by filter the salt of generation, filtrate is distilled down at 95～100 ℃ and is desolventized, and gets colourless transparent oil liquid methylacryoyloxyethyl propargyl ether 34.0g, productive rate 40.5%, purity 97.7%.
Add 12.3g boron in last of the ten Heavenly stems hydrogen in the there-necked flask that reflux condensing tube, thermometer and constant pressure funnel are housed, 33.6g methylacryoyloxyethyl propargyl ether and 100g acetonitrile stir, reflux, reaction 18h.After finishing reaction, reaction solution is cooled to room temperature, filters, filtrate is distilled down at 70～75 ℃ and is desolventized, and obtains 16.5g water white transparency thick liquid product, and the product structure formula is as follows:
Reaction yield 71.80%.Product structure characterizes:
1H NMR (CDCl
3, δ): 6.18 (s, 2H, C=CH
2), 5.79 (m, 2H, CH
2), 4.79 (m, 2H, O-CH
2-C), 3.87 (m, 2H), 2.05～3.14 (m, 10H, BH), 1.95 (s, 3H, CH
3) ppm.FT-IR(v)：2584(B-H)，1726(C＝O)，1637(C＝C)，1317，1293，1149，1086，1020(B-B)cm
-1。
Claims (2)
1. carborane is characterized in that its structural formula is:
Wherein,
R＝(CH
2CH
2O)m(CH
2)nCH
2CH＝CH
2、(CH
2O)m(CH
2)nCH
2CH＝CH
2、
(CH
2CH
2O) mC (O) C (R
1)=CH
2Or (CH
2O) mC (O) C (R
1)=CH
2
M=0,1 or 2 wherein, the integer of n=0 or n=1～8; R
1=H or CH
3
2. the preparation method of the described carborane of claim 1 comprises that nucleophilic substitution reaction prepares propargyl ether and addition reaction prepares carborane, it is characterized in that following steps,
Step 1: nucleophilic substitution reaction prepares propargyl ether technical formula and reaction conditions
Ether solvent in the above-mentioned prescription, organic bases, nucleophilic reagent and propiolic halide are joined in the reactor successively, stir, react 3～48h down at 20～100 ℃;
Reaction is removed the salt of generation with reacting liquid filtering after finishing, and filtrate desolventizes 40～110 ℃ of distillations, gets propargyl ether;
Above-mentioned ether solvent is ether, tetrahydrofuran (THF), 1,4-dioxane, glycol dimethyl ether or ethylene glycol diethyl ether and any two or more mixture thereof, and weight ratio is 1～5: 5～1 during mixing;
Above-mentioned organic bases is pyridine, triethylamine or diethylamine;
Related nucleophilic reagent is vinyl carbinol, butenol, hexenol, ethylene glycol allyl ethers, a condensed ethandiol allyl ethers, hydroxy methyl methacrylate or hydroxyethyl methylacrylate;
Related propiolic halide is propargyl bromide, iodine propine or propargyl chloride;
Step 2: addition reaction prepares carborane technical formula and reaction conditions
The composition weight ratio
Acetonitrile 5～30
The last of the ten Heavenly stems, boron hydrogen 1
Propargyl ether 1～5
With a kind of the joining successively in the reactor in the prepared propargyl ether of the solvent acetonitrile in the above-mentioned prescription, last of the ten Heavenly stems boron hydrogen and step 1, stir, at 50～100 ℃ of reaction 6～48h down; After reacting end, reaction solution is cooled to room temperature, filters, filtrate is distilled down at 50～100 ℃ and is desolventized, and gets C=C pair of keys and is connected in the structural carborane that contains unsaturated group of cage-type carborane by the ehter bond key.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585936A (en) * | 2012-02-17 | 2012-07-18 | 栗伟鹤 | Energy-containing combustion-supporting catalyst and application thereof |
| CN106866324A (en) * | 2015-09-23 | 2017-06-20 | 苏州大学 | A kind of application of carborane radical ammonium perchlorate |
| CN105906658B (en) * | 2016-04-28 | 2018-10-16 | 苏州大学 | A kind of carborane organic silicon monomer and preparation method thereof |
| CN108840966A (en) * | 2018-05-25 | 2018-11-20 | 北京航空航天大学 | A kind of high-content boron hydrogen olefin polymer and its application |
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| CN101994252A (en) * | 2010-10-20 | 2011-03-30 | 苏州大学 | Anti-ultraviolet true silk and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585936A (en) * | 2012-02-17 | 2012-07-18 | 栗伟鹤 | Energy-containing combustion-supporting catalyst and application thereof |
| CN102585936B (en) * | 2012-02-17 | 2013-11-27 | 栗伟鹤 | Energy-containing combustion-supporting catalyst and application thereof |
| CN106866324A (en) * | 2015-09-23 | 2017-06-20 | 苏州大学 | A kind of application of carborane radical ammonium perchlorate |
| CN106866324B (en) * | 2015-09-23 | 2019-06-25 | 苏州大学 | A kind of application of carborane radical ammonium perchlorate |
| CN105906658B (en) * | 2016-04-28 | 2018-10-16 | 苏州大学 | A kind of carborane organic silicon monomer and preparation method thereof |
| CN108840966A (en) * | 2018-05-25 | 2018-11-20 | 北京航空航天大学 | A kind of high-content boron hydrogen olefin polymer and its application |
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Application publication date: 20110803 |