CN1916003A - Method for preparing octamido phenyl silsesquixanes - Google Patents
Method for preparing octamido phenyl silsesquixanes Download PDFInfo
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- CN1916003A CN1916003A CN 200610152965 CN200610152965A CN1916003A CN 1916003 A CN1916003 A CN 1916003A CN 200610152965 CN200610152965 CN 200610152965 CN 200610152965 A CN200610152965 A CN 200610152965A CN 1916003 A CN1916003 A CN 1916003A
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- phenyl
- silsesquixanes
- octamido
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- polyhedral silsesquioxane
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 60
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- -1 aminophenyl Chemical group 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- UJXVAJQDLVNWPS-UHFFFAOYSA-N [Al].[Al].[Al].[Fe] Chemical compound [Al].[Al].[Al].[Fe] UJXVAJQDLVNWPS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910021326 iron aluminide Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
This invention discloses a method for preparing octaaminophenyl polyhedral silsesquioxane. The method comprises: (1) adding octaaminophenyl polyhedral silsesquioxane, active carbon and catalyst into a solvent; (2) adding hydrazine hydrate at 50-80 deg.C and in a certain atmosphere to hydrogenate octaaminophenyl polyhedral silsesquioxane; (3) reacting under reluxing; (4) collecting octaaminophenyl polyhedral silsesquioxane from the reaction products. The method can avoid using Pd catalyst, thus can lower the cost of the catalyst. The method has such advantages as mild reaction conditions, easy operation, good repeatability and high yield, and is suitable for mass production.
Description
Technical field
The present invention relates to a kind of preparation method of octamido phenyl silsesquixanes, the nano structured unit polymerization that it can be used as hybrid inorganic-organic enters polymkeric substance, also is the compound of versatile hybrid inorganic-organic, belongs to the field of chemical synthesis.
Technical background
Octamido phenyl silsesquixanes is the basic nano structured unit of a kind of very useful polymkeric substance, not only can directly be applied in the novel material of various excellent performances such as preparing high temperature material, fire retardant material in the resin system, also can be used for preparing multiple derivative, as phthalic imidine class, fluorenes class and Schiff bases derivative etc., and then raw material, the higly branched chain star structure of preparation Organic Light Emitting Diode and the high temperature porous templates etc. that is used for fields such as catalysis, sensing member, separation, thereby there is huge application potential.
The structural formula of octamido phenyl silsesquixanes is:
Wherein-NH
2Position or contraposition between being positioned at.
Eight aminocarbonyl phenyl clathrasil sesquialter alkane generally are to make ([1] Tamaki R, Tanaka Y, Asuncion M Z, et al.J.Am.Chem.Soc.2001,123:12416-12417 with the formic acid reduction by octaaminophenyl polyhedral silsesquioxane under the catalysis of palladium charcoal; [2] Huang Jun-chao, He Chao-bin, Xiao Yang, et al.Polymer, 2003,44 (16): 4491-4499; [3] Ni Yong, Zheng Sixun, Nie Kangming.Polymer, 2004,45 (16): 5557-5568; [4] Kim S G, Choi J, Tamaki R, Laine R M.Polymer 2005,46:4514-4524.).The weak point of this method, the use that at first is noble metal catalyst has increased raw materials cost, secondly in order to prevent poisoning of catalyst, preparation condition has been proposed very harsh requirement, and formic acid was easy to volatilization when temperature was higher in addition, and these factors have not only improved production cost, make the actually operating condition wayward simultaneously, poor repeatability influences production-scale expansion, limits its application.
Therefore, Cheap highly effective ground is reduced to eight aminocarbonyl phenyl clathrasil sesquialter alkane with octaaminophenyl polyhedral silsesquioxane, and is significant for the Application Areas of widening aromatic base clathrasil sesquioxyalkane.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing eight aminocarbonyl phenyl clathrasil sesquialter alkane by octaaminophenyl polyhedral silsesquioxane, the iron of this technology employing Cheap highly effective, aluminum compound are as catalyzer, with hydrazine hydrate as reductive agent, the reduction octaaminophenyl polyhedral silsesquioxane is an octamido phenyl silsesquixanes in the presence of gac, behind the back flow reaction appropriate time, from reaction mixture, collect target product.
To the effect that of the present invention: that octaaminophenyl polyhedral silsesquioxane, gac and catalyzer are added in the solvent, under certain gas atmosphere, 50～80 ℃ drip hydrazine hydrate down, through transfer hydrogenation reduction octaaminophenyl polyhedral silsesquioxane, behind the back flow reaction appropriate time, from reaction mixture, collect the product octamido phenyl silsesquixanes.
Said solvent can be C
1～C
3Alcohols, acetone, acetonitrile, methylene dichloride, ethylene dichloride, benzene,toluene,xylene, dioxane, tetrahydrofuran (THF) equal solvent in one or more, be preferably tetrahydrofuran (THF);
The by weight/volume of octaaminophenyl polyhedral silsesquioxane and solvent is 1: 4～10;
The mass ratio of octaaminophenyl polyhedral silsesquioxane and gac is 1: 0.05～0.30, and wherein said gac can unprocessed direct use, and preferably the gac after nitric acid removes heavy metal ion uses, or uses after the heat-activated;
Said catalyzer can be the compound of iron or aluminium, as iron oxide hydroxide, nano-sized iron oxide, iron trichloride or aluminum chloride, be preferably the mixture of iron aluminide, the mol ratio of the two is 1: 0.02～2, and the mol ratio of nitro and catalyzer is 1: 0.005～0.08 in the octaaminophenyl polyhedral silsesquioxane.
Said gas atmosphere can be air or inert gas atmosphere, preferred nitrogen atmosphere.
The mass concentration of said hydrazine hydrate is 50～100%, and the mol ratio of nitro and hydrazine hydrate is 1: 1.5～4 in the octaaminophenyl polyhedral silsesquioxane.
Said method of from reaction product, collecting octamido phenyl silsesquixanes, be meant materials such as first filtering gac, with tetrahydrofuran (THF) equal solvent washing filter residue, the filtrate that obtains is added ethyl acetate by 1: 0.3～1 volume ratio, with the salt water washing repeatedly, use distilled water wash again, use anhydrous sodium sulfate drying.Afterwards, can directly carry out underpressure distillation, vacuum-drying acquisition final product; Or pour in the inert solvent (as normal hexane) and separate out precipitation, filtration, vacuum-drying obtain final product; Or use these two kinds of methods from reaction mixture, to collect octamido phenyl silsesquixanes simultaneously
Among the preparation method of the present invention, solvent has bigger susceptibility to reaction, can select C for use
1～C
3Alcohols, acetone, acetonitrile, methylene dichloride, ethylene dichloride, benzene,toluene,xylene, dioxane, tetrahydrofuran (THF) equal solvent in one or more, be preferably tetrahydrofuran (THF).The consumption of solvent is a principle with the yield that helps successful reaction and carry out and do not influence product, and the weightmeasurement ratio of octaaminophenyl polyhedral silsesquioxane and solvent is 1: 4～10 usually.
According to the The Nomenclature Composition and Structure of Complexes characteristics of used gac, it can unprocessed direct use, perhaps uses after nitric acid removes heavy metal, or uses after the heat-activated, and the mass ratio of nitroso reaction thing and gac is 1: 0.05～0.30.Remove the harmful metal ion that may exist in the gac (as Pb
2+Ions etc.) time, 30 gram gacs are joined in the 50mL concentrated nitric acid, reflux is more than half an hour, and decompress filter, filter cake be with distilled water wash 2～3 times, 110 ℃ dry 2 hours down, can repeat said process in case of necessity to remove harmful metal ion fully; At last, gac added in the 100mL ethanol refluxed 20 minutes, decompress filter, filter cake at room temperature dries, 110 ℃ dry 3 hours down, preserve standby.During the gac heat-activated, granular active carbon can be 150 ℃ of following dryings about 5 hours, and the powdery gac can be following dry about 4 hours at 110 ℃.
In the hydrazine hydrate reduction reaction of above-mentioned transfer hydrogenation, catalyzer can be the compound of palladium charcoal, Raney nickel, iron and aluminium.And in order to reduce manufacturing cost, preferably select the compound of iron and aluminium, as ironic hydroxide, nano-sized iron oxide, iron trichloride or aluminum chloride, be preferably the mixture of iron aluminide, the mol ratio of the two is 1: 0.02～2, and the mol ratio of nitro and catalyzer is 1: 0.005～0.08 in the octaaminophenyl polyhedral silsesquioxane.
Consider in the above-mentioned hydrazine hydrate reduction reaction process and can constantly generate nitrogen, therefore according to the constructional feature of reactor and the specification of quality of product, gas atmosphere can be air or inert gas atmosphere.And, guarantee quality product for the generation of the oxidizing reaction that reduces amido, reaction is preferably in carries out preferred nitrogen atmosphere in the inert atmosphere.
When the mass concentration of used hydrazine hydrate increased in the above-mentioned reaction, reduction reaction speed can correspondingly be accelerated, but can increase raw materials cost simultaneously.Should consider its influence when therefore, selecting the hydrazine hydrate mass concentration to production cost.Usually, the mass concentration of hydrazine hydrate is between 50～100%, and the mol ratio of nitro and hydrazine hydrate is 1: 1.5～4 in the octaaminophenyl polyhedral silsesquioxane.
It is closely related with above-mentioned various factors that above-mentioned reaction required time is finished in influence, generally between 1.5～12 hours, can determine to finish the Best Times that reacts by the composition of chromatography detection reaction mixture in the reaction process.
After reaction finishes, in order from reaction mixture, to collect the target product octamido phenyl silsesquixanes, material such as filtering gac at first, wash filter residue with the tetrahydrofuran (THF) equal solvent then, merging filtrate, the volume ratio by 1: 0.3～1 is added ethyl acetate in filtrate, with the salt water washing repeatedly, use distilled water wash again, behind anhydrous sodium sulfate drying, can directly carry out underpressure distillation and obtain final product through vacuum-drying; Or pour in a large amount of inert solvents (as normal hexane) and separate out post precipitation, filtration once more, vacuum-drying obtain final product; Or after first underpressure distillation removes most of solvent, pour into again in a large amount of inert solvents and separate out precipitation, suction filtration and vacuum-drying obtain final product.
Compare with the catalytic formic acid reduction method of palladium charcoal, prepare octamido phenyl silsesquixanes with method of the present invention, the cost of catalyzer is obviously reduced, simultaneously its catalytic activity is subjected to that the influence degree of impurity and reaction atmosphere also weakens greatly in the reaction raw materials, the selectivity of reduction reaction increases, and reaction conditions is gentle and be easy to control, good reproducibility, the yield height is easy to expand the scale of production.
Description of drawings:
A kind of eight aminocarbonyl phenyl clathrasil sesquialter alkane preparation methods' of Fig. 1 reaction expression.
Wherein-NO
2With-NH
2Position or contraposition between being positioned at.
Embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
Take by weighing the 5g octaaminophenyl polyhedral silsesquioxane; add in the 200mL there-necked flask of taking back stream prolong, constant pressure funnel, magnetic agitation and nitrogen protection; dissolve with the 40mL tetrahydrofuran (THF); add the 0.9g gac then, 0.3g iron trichloride, 0.05g aluminum chloride; heat temperature raising to 62 ℃; begin slow Dropwise 5 mL 80% hydrazine hydrate, after being added dropwise to complete, refluxed 7 hours.Suction filtration, with 30mL tetrahydrofuran (THF) washing precipitation and suction filtration in batches, merging filtrate adds the 40mL ethyl acetate in the filtrate, with saturated common salt water washing 4 times, use distilled water wash again 1 time, use anhydrous sodium sulfate drying, directly carry out underpressure distillation, vacuum-drying, get the 3.6g octamido phenyl silsesquixanes, yield is 87.2%.
FTIR(cm
-1)：3436.6、3358.6(NH
2)，1118.5(Si-O-Si)。
1H?NMR(acetone-d
6，ppm)：7.7-6.0，5.0-2.9。
13C?NMR(acetone-d
6，ppm)：148.2、136.4、132.0、129.3、125.7、123.7、121.0、117.5、114.3。
29Si NMR (solid, ppm) :-77.09 ,-67.9.(down together.)
Embodiment 2
Take by weighing the 20g octaaminophenyl polyhedral silsesquioxane; add in the 500mL there-necked flask of taking back stream prolong, constant pressure funnel, magnetic agitation and nitrogen protection; dissolve with the 150mL tetrahydrofuran (THF); add the 3.5g gac then, 1.2g iron trichloride, 0.2g aluminum chloride; heat temperature raising to 60 ℃; beginning slowly drips 23mL 80% hydrazine hydrate, after being added dropwise to complete, refluxes 9 hours.Suction filtration is used 80mL tetrahydrofuran (THF) washing precipitation and suction filtration in batches, merging filtrate, add the 120mL ethyl acetate in the filtrate, with saturated common salt water washing 4 times, use distilled water wash again 1 time, use anhydrous sodium sulfate drying, in the impouring 1500mL normal hexane, separate out white or slightly latericeous throw out, suction filtration, vacuum-drying, get the 13.7g octamido phenyl silsesquixanes, yield is 82.6%.
Embodiment 3
Take by weighing the 40g octaaminophenyl polyhedral silsesquioxane; add in the 500mL there-necked flask of taking back stream prolong, constant pressure funnel, magnetic agitation and nitrogen protection; dissolve with the 320mL tetrahydrofuran (THF); add the 6g gac then, 2.0g iron trichloride, 0.2g aluminum chloride; heat temperature raising to 61 ℃; beginning slowly drips 42mL 80% hydrazine hydrate, after being added dropwise to complete, refluxes 8 hours.Suction filtration is used 140mL tetrahydrofuran (THF) washing precipitation and suction filtration in batches, merging filtrate, add the 250mL ethyl acetate in the filtrate,, use distilled water wash again 1 time with saturated common salt water washing 4 times, use anhydrous sodium sulfate drying, a large amount of solvents are removed in underpressure distillation, in the impouring 600mL normal hexane, separate out white or slightly latericeous throw out, suction filtration, vacuum-drying gets the 30.8g octamido phenyl silsesquixanes, and yield is 93%.
Claims (8)
1, a kind of preparation method of octamido phenyl silsesquixanes, it is characterized in that: octaaminophenyl polyhedral silsesquioxane, gac and catalyzer are added in the solvent, under certain gas atmosphere, 50～80 ℃ drip hydrazine hydrate down, through transfer hydrogenation reduction octaaminophenyl polyhedral silsesquioxane, behind the back flow reaction appropriate time, from reaction mixture, collect the product octamido phenyl silsesquixanes; Reaction expression is:
Wherein-NO
2With-NH
2Position or contraposition between being positioned at.
2, the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1 is characterized in that: said solvent can be C
1～C
3Alcohols, acetone, acetonitrile, methylene dichloride, ethylene dichloride, benzene,toluene,xylene, dioxane, tetrahydrofuran (THF) equal solvent in one or more, preferred tetrahydrofuran (THF).
3, according to the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1～2, it is characterized in that: the by weight/volume of octaaminophenyl polyhedral silsesquioxane and solvent is 1: 4～10.
4, according to the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1～3, it is characterized in that: the mass ratio of octaaminophenyl polyhedral silsesquioxane and gac is 1: 0.05～0.30, wherein said gac can unprocessed direct use, preferably gac uses after nitric acid removes heavy metal ion, or uses after the heat-activated.
5, according to the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1～4, it is characterized in that: catalyzer can be the compound of iron or aluminium, as iron oxide hydroxide, nano-sized iron oxide, iron trichloride or aluminum chloride, the mixture of preferred iron aluminide, the mol ratio of the two is 1: 0.02～2, and the mol ratio of nitro and catalyzer is 1: 0.005～0.08 in the octaaminophenyl polyhedral silsesquioxane.
6, according to the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1～5, it is characterized in that: said gas atmosphere can be air or inert gas atmosphere, is preferably nitrogen atmosphere.
7, according to the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1～6, it is characterized in that: the mass concentration of said hydrazine hydrate is 50～100%, and the mol ratio of nitro and hydrazine hydrate is 1: 1.5～4 in the octaaminophenyl polyhedral silsesquioxane.
8, according to the preparation method of the described a kind of octamido phenyl silsesquixanes of claim 1～7, it is characterized in that: said method of from reaction product, collecting eight aminophenyl clathrasil sesquioxyalkanes, be meant materials such as first filtering gac, with tetrahydrofuran (THF) equal solvent washing filter residue, the filtrate that obtains is added ethyl acetate by 1: 0.3～1 volume ratio, with the salt water washing repeatedly, use distilled water wash again, use anhydrous sodium sulfate drying.Afterwards, can directly carry out underpressure distillation, vacuum-drying acquisition final product; Or pour in the inert solvent (as normal hexane) and separate out precipitation, filtration, vacuum-drying obtain final product; Or use these two kinds of methods from reaction mixture, to collect octamido phenyl silsesquixanes simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101529658A CN100430406C (en) | 2006-09-21 | 2006-09-21 | Method for preparing octamido phenyl silsesquixanes |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391303A (en) * | 2011-10-24 | 2012-03-28 | 北京理工大学 | Preparation method of cage-type oligomeric octa(aminophenyl) polyhedral silsesquioxane (OAPS) |
| CN104817584A (en) * | 2015-03-19 | 2015-08-05 | 中科院广州化学有限公司 | Semi-cage tetrapolysilsesquioxane containing aminophenyl group, and preparation method and application thereof |
| CN108285536A (en) * | 2018-02-27 | 2018-07-17 | 同济大学 | A kind of super-hydrophobic fire proofing of organosilicon and preparation method thereof |
| CN114316273A (en) * | 2021-11-18 | 2022-04-12 | 国科广化精细化工孵化器(南雄)有限公司 | Schiff base containing cage type silsesquioxane as well as preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060083925A1 (en) * | 2000-10-27 | 2006-04-20 | Laine Richard M | Well-defined nanosized building blocks for organic/inorganic nanocomposites |
| CN1332963C (en) * | 2004-01-19 | 2007-08-22 | 北京化工大学 | Amino phenyl cage type sesqui siloxane and its preparing method |
| CN100412077C (en) * | 2006-05-19 | 2008-08-20 | 北京化工大学 | Process for preparing amino phenyl silsesquioxane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391303A (en) * | 2011-10-24 | 2012-03-28 | 北京理工大学 | Preparation method of cage-type oligomeric octa(aminophenyl) polyhedral silsesquioxane (OAPS) |
| CN104817584A (en) * | 2015-03-19 | 2015-08-05 | 中科院广州化学有限公司 | Semi-cage tetrapolysilsesquioxane containing aminophenyl group, and preparation method and application thereof |
| CN104817584B (en) * | 2015-03-19 | 2017-12-26 | 中科院广州化学有限公司 | One kind contains the polysilsesquioxane of half cage modle of aminophenyl four and preparation method and application |
| CN108285536A (en) * | 2018-02-27 | 2018-07-17 | 同济大学 | A kind of super-hydrophobic fire proofing of organosilicon and preparation method thereof |
| CN114316273A (en) * | 2021-11-18 | 2022-04-12 | 国科广化精细化工孵化器(南雄)有限公司 | Schiff base containing cage type silsesquioxane as well as preparation method and application thereof |
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| CN100430406C (en) | 2008-11-05 |
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