CN106188127A - A kind of preparation method of ring trapezoidal nitrobenzophenone silsesquioxane - Google Patents
A kind of preparation method of ring trapezoidal nitrobenzophenone silsesquioxane Download PDFInfo
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- CN106188127A CN106188127A CN201610543306.0A CN201610543306A CN106188127A CN 106188127 A CN106188127 A CN 106188127A CN 201610543306 A CN201610543306 A CN 201610543306A CN 106188127 A CN106188127 A CN 106188127A
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- silsesquioxane
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- trapezoidal
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- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Abstract
The present invention relates to the preparation method of a kind of ring trapezoidal nitrobenzophenone silsesquioxane, belong to organic-inorganic hybrid material technical field.Adding in reactor by ring trapezoidal phenyl silsesquioxane and solvent, stirring, controlling temperature of reactor is 0～10 DEG C, drips nitric acid, acetic anhydride, acetic acid successively, after being added dropwise to complete, reactor is warming up to 25～35 DEG C, and the response time is 4～8 hours, obtains reactant liquor；Reactant liquor rotation is steamed, sucking filtration, use saturated Na successively2CO3Solution, distilled water, washing with alcohol, dry filter cake, and drying temperature is 40～100 DEG C, finally obtains ring trapezoidal nitrobenzophenone silsesquioxane.The reaction condition of the present invention is gentle, reproducible, has the advantages that productivity is high, the cycle is short, simple to operate, is suitable for expanding production；Products therefrom can carry out the reaction such as ammonification, alkynyl further, synthesizes new ring trapezoidal silsesquioxane derivant.
Description
Technical field
The present invention relates to the preparation method of a kind of ring trapezoidal nitrobenzophenone silsesquioxane (PNPSQ), belong to organic and inorganic
Hybrid material scientific domain.
Background technology
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane, POSS) refers to molecule
Formula is (RSiO1.5)nPolysiloxanes, POSS molecular structure had both contained " skeleton " structure of inorganic siloxanes, can pass through again
Organic group introduced by side base.The inorganic siliceous interior nuclear energy that density is bigger suppresses its chain movement to give its good thermostability
Can, there is pusher side base then to give its good toughness and machinability accordingly, this typical Inorganic-Organic Hybrid Material is simultaneously
Possesses the basic feature of organic polymer and inorganic ceramic.There is the poly-phenyl silsesquioxane of ordered structure
(polyphenylsilsesquioxane, PPSQ) in addition to the excellent properties with POSS, also have excellent film property and
Dissolubility good in organic solvent, has been used for fire proofing, super hydrophobic material, ablation resistant material, dielectric materials, photosensitive
Material etc.
There is the phenylsilsesquioxane (CL-PPSQ) of ring trapezium structure due to the regularity of its structure, as polymer
Auxiliary agent has good enhancing, flame retardant effect.Improving PPSQ further with the organic polymer compatibility is the emphasis studied at present
One of, most important of which method i.e. prepares the derivant of PPSQ.Important for a PPSQ derivative chemical reaction is to enter phenyl ring
Row nitration reaction.
The research of existing ring trapezoidal phenyl silsesquioxane is at the early-stage, with reference to existing polyhedral oligomeric phenyl silicon sesquialter oxygen
The nitration processes of alkane, is the fuming nitric aicd using higher concentration, realizes with phenylsilsesquioxane heterogeneous with vigorous stirring
Dispersion, reaction 20～24h synthesis obtains polyhedral oligomeric nitrobenzophenone silsesquioxane, and this technique is applied to ring trapezoidal phenyl silicon times
The nitrification of half oxygen alkane can cause the fracture of ring trapezium structure.The present invention introducing by solvent, it is achieved that homodisperse, leads to simultaneously
Cross the improvement of nitrating agent, it is to avoid the use of high concentration fuming nitric aicd so that safety is greatly improved, and generated time foreshortens to 4
～8h.
Summary of the invention
The invention aims to propose the preparation method of a kind of ring trapezoidal nitrobenzophenone silsesquioxane, the trapezoidal nitre of ring
Base phenylsilsesquioxane is a kind of novel poly-phenyl silsesquioxane derivant, contains nitrogen, element silicon simultaneously, and simultaneously
There is the construction features of POSS molecular skeleton and nitro, can be used for preparing the multiple POSS derivant containing function group.
It is an object of the invention to be achieved through the following technical solutions.
A kind of preparation method of the ring trapezoidal nitrobenzophenone silsesquioxane of the present invention, its concrete preparation process is as follows:
1) ring trapezoidal phenyl silsesquioxane and solvent are added in reactor, stirring, utilize the cooling means such as ice-water bath
Control temperature of reactor be 0～10 DEG C, drip nitric acid, acetic anhydride, acetic acid successively, after being added dropwise to complete, reactor is warming up to 25～
35 DEG C, the response time is 4～8 hours, obtains reactant liquor；
2) by step 1) gained reactant liquor adds in frozen water, and rotation is steamed and is removed by the solvent in reactant liquor, has yellow solid to analyse
Going out, sucking filtration obtains product, uses saturated Na successively2CO3Solution, distilled water and ethanol wash, and are dried by filter cake, dry temperature
It is 40～100 DEG C, finally obtains ring trapezoidal nitrobenzophenone silsesquioxane.
Above-mentioned steps 1) in noble gas be nitrogen or argon.
Above-mentioned steps 1) in solvent be acetone, acetonitrile, dichloromethane, chloroform, dioxane, oxolane, pyrrole
One in pyridine, dimethylformamide, dimethyl acetylamide or its mixture, solvent is preferably dichloromethane；Ring trapezoidal phenyl
The ratio of silsesquioxane and solvent is 1g:2～10mL；
Above-mentioned steps 1) ratio of medium ring trapezoidal phenyl silsesquioxane and nitric acid is 1g:1～5mL；
Above-mentioned steps 1) ratio of medium ring trapezoidal phenyl silsesquioxane and acetic anhydride is 1g:2～10mL；
Above-mentioned steps 1) ratio of medium ring trapezoidal phenyl silsesquioxane and acetic acid is 1g:0.5～2.5mL；
The ring trapezoidal nitrobenzophenone silsesquioxane prepared through said method contains 10～30 nitrobenzophenones, its typical case's knot
Shown in structure formula such as formula (1), formula (2):
It is a kind of trapezoidal hybrid inorganic-organic materials of three-dimensional ring with nano-scale, and it has relatively high reaction activity
Nitrobenzophenone can react further and be changed into the chemical group such as amino, alkynyl.
Beneficial effect
The reaction condition of the present invention is gentle, reproducible, has the advantages that productivity is high, the cycle is short, simple to operate, is suitable for expanding
Big production；The structural stability of product is good, and on the basis that the complete nitrification of phenyl occurs, ring trapezium structure is maintained；
Products therefrom can carry out the reaction such as ammonification, alkynyl further.
Accompanying drawing explanation
Fig. 1 is the PPSQ-NO of embodiment 1 preparation2FT-IR spectrogram；
Fig. 2 is the PPSQ-NO of embodiment 1 preparation2's1H NMR spectra；
Fig. 3 is the PPSQ-NO of embodiment 1 preparation2XRD spectra with the PPSQ before nitrification；
Fig. 4 is the PPSQ-NO of embodiment 1 preparation2GPC spectrogram with the PPSQ before nitrification；
Detailed description of the invention
Below by example, the invention will be further described, but embodiment is not limiting as protection scope of the present invention.
Embodiment 1
1) 4g ring trapezoidal phenyl silsesquioxane (PPSQ) and 20mL dichloromethane are joined band reflux condensing tube, constant voltage
In the 250mL there-necked flask of the protection of Dropping funnel, temperature regulating device, nitrogen and magnetic agitation, stirring, ice-water bath temperature control is 0 DEG C, depends on
Secondary 20mL 80% nitric acid, 40mL acetic anhydride and the 10mL acetic acid of being slowly added dropwise, drips off, is warming up to 30 after dropping for about 1 hour
DEG C, react 6 hours, obtain reactant liquor.
2) by step 1) reactant liquor that obtains pours in 50mL frozen water, and mixed liquor rotation is evaporated off dichloromethane, separates out yellow
Solid, sucking filtration, obtain filter cake, use saturated Na successively2CO3Solution washing to filter cake bubble-free, distilled water wash to filtrate in
Property, washing with alcohol, filter cake is placed in 50 DEG C of vacuum drying ovens be dried 10 hours, finally obtain ring trapezoidal nitrobenzophenone silicon sesquialter oxygen
Alkane, productivity is about 92.8%；Fig. 1 is the FT-IR spectrogram of ring trapezoidal nitrobenzophenone silsesquioxane, 1530 and 1350cm-1For nitre
The distinctive absworption peak of base, 1595,1484,1434cm-1For phenyl ring skeletal vibration absworption peak, 1078cm-1It it is Si-O-Si key chattering
Absworption peak.Fig. 2 is ring trapezoidal nitrobenzophenone silsesquioxane1H NMR spectra, due to-NO2Electron attraction make phenyl ring hydrogen
To low field displacement, and ortho position Displacement Ratio meta is big, and at 7.5～8.0ppm, vibration peak is the vibration of nitro meta Hydrogen Proton on phenyl ring
Peak, at 8.0～8.5ppm, vibration peak is the vibration peak of nitro ortho-hydrogens proton on phenyl ring.Both are about 1:1 at area ratio, it was demonstrated that
The each phenyl ring of product on containing nitro, and major part nitrification occurs at-SiO1.5Para-position.
Wherein spectral data is:
FT-IR (KBr, cm-1): 1530,1350 (-NO2), 1595,1484,1434 (benzene), 1078 (Si-O-Si)；1H
NMR(Acetone-d6, δ, ppm, TMS): 7.5～8.0 (1H, nitro metas H on phenyl ring), 8.0～8.5 (1H, nitros on phenyl ring
Ortho position H)；Anal.calcd for(NO2C6H4SiO1.5)2n: C (41.34%)；H (2.30%)；N (8.04%)；Found:C
(41.30%)；H (2.41%)；N (7.89%).
Fig. 3 is the XRD spectra of ring trapezoidal nitrobenzophenone silsesquioxane, and 2 θ=7.3 ° are trapezoidal two main chains of its PPSQ ring
Between diffraction maximum corresponding to width.It is 1.22nm according to width between Bragg equation calculated main chain, it was demonstrated that it has receives
The three dimensional structure of meter ruler cun.Ring trapezoidal nitrobenzophenone silsesquioxane shows with the GPC result of ring trapezoidal phenyl silsesquioxane,
The number-average molecular weight of raw material is about 3053, and polydispersity coefficient is 1.362, and the number-average molecular weight of nitration product is 4110, many points
Scattered coefficient is 1.472, it is seen that the isostructural destruction of chain rupture does not occurs, and degree of nitration is the highest.
Embodiment 2
1) 8g ring trapezoidal phenyl silsesquioxane (PPSQ) and 40mL dichloromethane are joined band reflux condensing tube, constant voltage
In the 500mL there-necked flask of the protection of Dropping funnel, temperature regulating device, nitrogen and magnetic agitation, stirring, ice-water bath temperature control is 0 DEG C, depends on
Secondary 40mL80% nitric acid, 80mL acetic anhydride and the 20mL acetic acid of being slowly added dropwise, drips off, is warming up to 30 after dropping for about 1 hour
DEG C, react 7 hours, obtain reactant liquor.
2) by step 1) reactant liquor that obtains pours in 100mL frozen water, and mixed liquor rotation is evaporated off dichloromethane, separates out yellow
Solid, sucking filtration, obtain filter cake, use saturated Na successively2CO3Solution washing to filter cake bubble-free, distilled water wash to filtrate in
Property, washing with alcohol, filter cake is placed in 50 DEG C of vacuum drying ovens be dried 10 hours, finally obtain ring trapezoidal nitrobenzophenone silicon sesquialter oxygen
Alkane, productivity is about 91.7%.
Embodiment 3
1) 8g ring trapezoidal phenyl silsesquioxane (PPSQ) and 60mL dichloromethane are joined band reflux condensing tube, constant voltage
In the 500mL there-necked flask of the protection of Dropping funnel, temperature regulating device, nitrogen and magnetic agitation, stirring, ice-water bath temperature control is 0 DEG C, depends on
Secondary 40mL 75% nitric acid, 80mL acetic anhydride and the 20mL acetic acid of being slowly added dropwise, drips off, is warming up to 35 after dropping for about 1 hour
DEG C, react 6 hours, obtain reactant liquor.
2) by step 1) reactant liquor that obtains pours in 100mL frozen water, and mixed liquor rotation is evaporated off dichloromethane, separates out yellow
Solid, sucking filtration, obtain filter cake, use saturated Na successively2CO3Solution washing to filter cake bubble-free, distilled water wash to filtrate in
Property, washing with alcohol, filter cake is placed in 50 DEG C of vacuum drying ovens be dried 12 hours, finally obtain ring trapezoidal nitrobenzophenone silicon sesquialter oxygen
Alkane, productivity is about 90.2%.
Embodiment 4
1) 12g ring trapezoidal phenyl silsesquioxane (PPSQ) and 80mL dichloromethane are joined band reflux condensing tube, perseverance
In the 500mL there-necked flask of pressure Dropping funnel, temperature regulating device, nitrogen protection and magnetic agitation, stirring, ice-water bath temperature control is 0 DEG C,
It is slowly added dropwise 50mL 75% nitric acid, 100mL acetic anhydride and 30mL acetic acid successively, within about 1.5 hours, drips off, rise after dropping
Temperature, to 30 DEG C, is reacted 8 hours, is obtained reactant liquor.
2) by step 1) reactant liquor that obtains pours in 150mL frozen water, and mixed liquor rotation is evaporated off dichloromethane, separates out yellow
Solid, sucking filtration, obtain filter cake, use saturated Na successively2CO3Solution washing to filter cake bubble-free, distilled water wash to filtrate in
Property, washing with alcohol, filter cake is placed in 50 DEG C of vacuum drying ovens be dried 16 hours, finally obtain ring trapezoidal nitrobenzophenone silicon sesquialter oxygen
Alkane, productivity is about 92.1%.
Embodiment 5
1) 12g ring trapezoidal phenyl silsesquioxane (PPSQ) and 100mL dichloromethane are joined band reflux condensing tube, perseverance
In the 500mL there-necked flask of pressure Dropping funnel, temperature regulating device, nitrogen protection and magnetic agitation, stirring, ice-water bath temperature control is 0 DEG C,
It is slowly added dropwise 60mL 85% nitric acid, 120mL acetic anhydride and 30mL acetic acid successively, within about 2 hours, drips off, heat up after dropping
To 35 DEG C, react 8 hours, obtain reactant liquor.
2) by step 1) reactant liquor that obtains pours in 200mL frozen water, and mixed liquor rotation is evaporated off dichloromethane, separates out yellow
Solid, sucking filtration, obtain filter cake, use saturated Na successively2CO3Solution washing to filter cake bubble-free, distilled water wash to filtrate in
Property, washing with alcohol, filter cake is placed in 60 DEG C of vacuum drying ovens be dried 12 hours, finally obtain ring trapezoidal nitrobenzophenone silicon sesquialter oxygen
Alkane, productivity is about 93.2%.
Claims (5)
1. the preparation method of a ring trapezoidal nitrobenzophenone silsesquioxane, it is characterised in that preparation method is as follows:
1) ring trapezoidal phenyl silsesquioxane and solvent are added in reactor, stirring, utilize the cooling means such as ice-water bath to control
Temperature of reactor is 0～10 DEG C, drips nitric acid, acetic anhydride, acetic acid successively, and reactor is warming up to after being added dropwise to complete 25～35
DEG C, the response time is 4～8 hours, obtains reactant liquor；
2) by step 1) gained reactant liquor adds in frozen water, and rotation is steamed and is removed by the solvent in reactant liquor, has yellow solid to separate out, takes out
Filter obtains product, uses saturated Na successively2CO3Solution, distilled water and ethanol wash, by filter cake dry, dry temperature be 40～
100 DEG C, finally obtain ring trapezoidal nitrobenzophenone silsesquioxane.
Above-mentioned steps 1) ratio of medium ring trapezoidal phenyl silsesquioxane and solvent is 1g:2～10mL；Ring trapezoidal phenyl silicon sesquialter oxygen
The ratio of alkane and nitric acid is 1g:5mL；The ratio of ring trapezoidal phenyl silsesquioxane and acetic anhydride is 1g:10mL；Ring trapezoidal phenyl silicon times
The ratio of half oxygen alkane and acetic acid is 1g:2.5mL；
Above-mentioned steps 1) in solvent be acetone, acetonitrile, dichloromethane, chloroform, dioxane, oxolane, pyridine, two
One in methylformamide, dimethyl acetylamide or its mixture；
The ring trapezoidal nitrobenzophenone silsesquioxane prepared through said method contains 10～30 nitrobenzophenones, and its general structure is such as
Shown in formula (1), formula (2):
。
The preparation method of a kind of ring the most according to claim 1 trapezoidal nitrobenzophenone silsesquioxane, it is characterised in that: step
Rapid 1) reactor in is with temperature regulating device, condensation reflux unit, inert gas shielding and magnetic stirring apparatus.
The preparation method of a kind of ring the most according to claim 2 trapezoidal nitrobenzophenone silsesquioxane, it is characterised in that: lazy
Property gas is nitrogen or argon.
The preparation method of a kind of ring the most according to claim 1 trapezoidal nitrobenzophenone silsesquioxane, it is characterised in that: adopt
Concentration of nitric acid be 65%～85%.
The preparation method of a kind of ring the most according to claim 1 trapezoidal nitrobenzophenone silsesquioxane, it is characterised in that: molten
Agent is dichloromethane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109503845A (en) * | 2018-11-06 | 2019-03-22 | 北京理工大学 | A kind of preparation method of controllable degree of functionality cage modle nitrobenzophenone silsesquioxane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648130A (en) * | 2004-01-19 | 2005-08-03 | 北京化工大学 | Amino phenyl cage type sesqui siloxane and its preparing method |
| CN1844126A (en) * | 2006-05-19 | 2006-10-11 | 北京化工大学 | Process for preparing amino phenyl silsesquioxane |
-
2016
- 2016-07-11 CN CN201610543306.0A patent/CN106188127B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648130A (en) * | 2004-01-19 | 2005-08-03 | 北京化工大学 | Amino phenyl cage type sesqui siloxane and its preparing method |
| CN1844126A (en) * | 2006-05-19 | 2006-10-11 | 北京化工大学 | Process for preparing amino phenyl silsesquioxane |
Non-Patent Citations (2)
| Title |
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| 周发岐: "《炸药合成化学》", 30 June 1984, 国防工业出版社 * |
| 范海波等: "多面体低聚八氨基苯基硅倍半氧烷合成方法改进及其表征", 《化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109503845A (en) * | 2018-11-06 | 2019-03-22 | 北京理工大学 | A kind of preparation method of controllable degree of functionality cage modle nitrobenzophenone silsesquioxane |
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