CN104761580B - Nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane and preparation method and application - Google Patents
Nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane and preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of organosilicon/inorganic nano-hybrid nano material, discloses a kind of nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane and preparation method and application.(1) preparation of the polysilsesquioxane sodium salt of half cage modle of phenyl four；(2) preparation of the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four；(3) the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and the bonded generation tetranitro phenyl tetraphenyl dimethoxy derivatives of phenyl trichlorosilane monomer heterogeneous reaction；(4) condensation reaction obtains nitrobenzophenone and benzene key difunctionality base cage-type silsesquioxane under the ethylbenzene dimethoxy derivatives acidic catalysis conditions of tetranitro phenyl four.Above-mentioned nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane can be applied to prepare the precursor raw material of beading POSS base polymeric materials.Preparation technology of the present invention is simpler, easy to operate, suitable for industrialized production.
Description
Technical field
The invention belongs to the technical field of organosilicon/inorganic nano-hybrid nano material, and in particular to a kind of nitrobenzene-containing base and
Phenyl difunctionality base cage-type silsesquioxane and preparation method and application.
Background technology
It is that one kind has similar lantern structure that cage-type silsesquioxane (POSS), which is also known as polyhedral oligomeric silsesquioxane,
Silsesquioxane general name.Cubic silsesquioxane is one kind of cage-type silsesquioxane, its compound with regular structure, highly right
Claim, be T8Structure.With going deep into POSS molecular studies field, POSS species is gradually enriched, the substitution on POSS molecules
Base develops into various specific functional groups from relatively common methyl, phenyl, epoxy radicals, hydrogen-based, vinyl, amino etc..POSS official
The POSS based high molecular materials for developing into the new functionalization of synthesis of energyization research provide wide space.The hair of material science
Exhibition causes the performance requirement more and more higher to material, and simple organic or inorganic material can not meet some special performances
It is required that.Wherein, with nanostructure size polyhedral oligomeric silsesquioxane (POSS)-polymer be exactly typically it is organic/
Inorganic hybrid material.POSS is a kind of compound of nanostructured, including inorganic and organic 2 parts, and silicon and oxygen form inorganic
Structure centre, this structure centre are covered by organic substituent, therefore POSS and its derivative set are organic and inorganic is permitted
More features.Each POSS particles contain one or more organic active functional groups, and these functional groups can be polymerize, be connect
Branch, surface bond or other reactions, form POSS- polymeric materials.
It is mainly that " Star Network " and " suspended pattern " structure POSS base gathers to study more POSS base polymeric materials at present
Compound.Due to being not introduced into main polymer chain, POSS effect weakens significantly.Therefore, synthesis carries double activated function
The POSS of base seems particularly critical.Due to by reaction condition is unmanageable, target product is uncontrollable and product is difficult to purify
Limited etc. factor, double activated functional group POSS synthesis is still to perplex a great problem of researcher.
The content of the invention
In order to solve the shortcomings that prior art and weak point, primary and foremost purpose of the invention is to provide a kind of nitrobenzene-containing
The preparation method of base and phenyl difunctionality base cage-type silsesquioxane.This method is by the polysilsesquioxane sodium salt of half cage modle of phenyl four
Set out, first nitration reaction obtains the polysilsesquioxane sodium salt of half cage modle of phenyl four, and then is occurred using phenyl trichlorosilane and its
Reaction progress is bonded, is condensed to yield double activated functional group's cage-type silsesquioxane of complete cage modle in acid condition.
A further object of the present invention is to provide nitrobenzene-containing base and phenyl difunctionality base cage that above-mentioned preparation method obtains
Type silsesquioxane.
Another object of the present invention is to provide above-mentioned nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane to exist
Prepare the application in the precursor raw material of beading POSS base polymeric materials.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane, including following operation step
Suddenly：
(1) 9.9g phenyltrimethoxysila,es, 50mL isopropanols and 2.0g sodium hydroxides are mixed to form reaction system, then
By 0.9mL H2O is added dropwise in reaction system, reacts at room temperature 24h, and white solid separates out, and reaction is filtrated to get solid after terminating,
50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of phenyl four；
(2) the polysilsesquioxane sodium salt of half cage modle of 5.0g phenyl four is added in 30mL fuming nitric aicds by several times, ice-water bath is anti-
30min is answered, room temperature is then moved to and continues to react 12h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, separate out faint yellow solid, in fume hood overnight, after filtering, washing, alcohol are washed vacuum drying it is poly- to obtain the cage modle four of nitrobenzophenone half
Silsesquioxane sodium salt；
(3) under nitrogen protective condition, the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four is scattered in methanol, obtained
To methanol dispersion, then phenyl trichlorosilane is dissolved in after n-hexane and is added dropwise in methanol dispersion, hybrid reaction body
Stirring reaction at room temperature is tied up to, insoluble salt NaCl separates out the progress for indicating growth response, and reaction is filtered off after terminating except not
Dissolubility NaCl, methanol organic phase is separated, dried, rotary evaporation removal solvent obtains the ethylbenzene dimethoxy of tetranitro phenyl four and spread out
Biology；
(4) under nitrogen protective condition, the ethylbenzene dimethoxy derivatives of tetranitro phenyl four are dissolved in methanol, are added dropwise
Enter hydrochloric acid solution, reaction system is reacted at ambient temperature, and white insoluble product is separated out, and nitrobenzene-containing is dried to obtain after filtering
Base and phenyl difunctionality base cage-type silsesquioxane.
The time that reaction is stirred at room temperature in step (3) the hybrid reaction system is 24~72h；The nitrobenzophenone half
The polysilsesquioxane sodium salt of cage modle four is 1 with phenyl trichlorosilane monomeric charge mol ratio：(2~8)；The drying is to use nothing
Water magnesium sulfate is dried.
It is further preferred that the time that reaction is stirred at room temperature in step (3) the hybrid reaction system is 48h；The nitre
The polysilsesquioxane sodium salt of half cage modle of base phenyl four is 1 with phenyl trichlorosilane monomeric charge mol ratio：4.
Step (4) described hydrochloric acid solution be by volume ratio be 10：The water and concentrated hydrochloric acid of (1~6) mix；Four nitre
The mass volume ratio of concentrated hydrochloric acid is 1g in the ethylbenzene dimethoxy derivatives of base phenyl four and hydrochloric acid solution：(1.5~6) mL；Institute
It is 24~72h to state the time that reaction system is reacted at ambient temperature.
It is further preferred that step (4) described hydrochloric acid solution be by volume ratio be 10：3 water and concentrated hydrochloric acid mixes；Institute
The mass volume ratio for stating concentrated hydrochloric acid in the ethylbenzene dimethoxy derivatives of tetranitro phenyl four and hydrochloric acid solution is 1g：3mL；It is described
The time that reaction system is reacted at ambient temperature is 48h.
A kind of nitrobenzene-containing base obtained according to above-mentioned preparation method and phenyl difunctionality base cage-type silsesquioxane.
Above-mentioned nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane is preparing beading POSS based polyalcohols
Application in the precursor raw material of material.
The polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded
Obtain nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane process schematic is as shown in Figure 3.
The present invention compared with prior art, has the following advantages that：
(1) present invention is based on the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer reaction key
Connect, be condensed under further acidic catalysis conditions and prepare nitrobenzene-containing base and phenyl difunctionality base POSS, have structure clear and definite, receive
The advantages of rate is higher；
(2) it can be to prepare specific " string that the present invention, which prepares nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane,
Pearl type " structure POSS base polymeric material provides precursor raw material；
(3) present invention catalysis used and reaction reagent are easily implemented with condition, and preparation technology is simpler, easy to operate, fits
In industrialized production.
Brief description of the drawings
Fig. 1 is the fourier infrared spectrum of nitrobenzene-containing base prepared by embodiment 4 and benzene difunctionality base cage-type silsesquioxane
Figure；
Fig. 2 is the hydrogen spectrum nuclear-magnetism spectrum of nitrobenzene-containing base prepared by embodiment 4 and phenyl difunctionality base cage-type silsesquioxane
Figure；
Fig. 3 is that the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded
Generate the procedure chart of nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) 9.9g phenyltrimethoxysila,es, 50mL isopropanols are added in flask for molten, 2.0g sodium hydroxides, 0.9mL
H2O is added dropwise to reaction system, reacts at room temperature 24h.A large amount of white solids separate out, and reaction terminates rear filtered on buchner funnel and consolidated
Body, 50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of 8.9g white solid product phenyl four.
(2) the polysilsesquioxane nitration reaction of half cage modle of phenyl four prepares the polysilsesquioxane sodium of half cage modle of nitrobenzophenone four
Salt.The polysilsesquioxane sodium salt of half cage modle of 5.0g phenyl four is slowly added in 30mL fuming nitric aicds (ice-water bath reaction in batches
30min), then move to room temperature to continue to react 12h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, faint yellow solid is separated out, is stayed overnight in fume hood, filtering, washing, alcohol are dried in vacuo after washing and obtain 5.8g faint yellow solids；
(3) the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded,
Generate tetranitro phenyl tetraphenyl dimethoxy derivatives.Experimental procedure is：Under nitrogen protection, in 250mL round-bottomed flasks, 3.3g
The polysilsesquioxane sodium salt (4.0mmol) of half cage modle of nitrobenzophenone four is scattered in 100mL methanol solvates.1.7g phenyl trichlorosilane
(8.0mmol) is dissolved in 100mL n-hexanes, is slowly added dropwise into methanol dispersion.Reaction is stirred at room temperature in hybrid reaction system
24h, insoluble salt NaCl separate out the progress for indicating growth response, and reaction is filtered off after terminating except insoluble NaCl, separates first
Alcohol organic phase, add anhydrous magnesium sulfate and dry, rotary evaporation removes solvent and obtains 2.1g faint yellow solid products.
(4) condensation reaction obtains nitrobenzophenone under the ethylbenzene dimethoxy derivatives acidic catalysis conditions of tetranitro phenyl four
And benzene key difunctionality base cage-type silsesquioxane.Under nitrogen protection, in 50mL round-bottomed flasks, 1.0g tetranitro phenyl tetravinyls
Dimethoxy derivatives are dissolved in 25mL methanol, are added dropwise to 10mL H2O, 1.17g (1mL) dense HCl solution, reaction system room temperature
React 24h.White insoluble product separates out, and is dried after filtering, obtains 0.35g products.
Embodiment 2
(1) 9.9g phenyltrimethoxysila,es, 50mL isopropanols are added in flask for molten, 2.0g sodium hydroxides, 0.9mL
H2O is added dropwise to reaction system, reacts at room temperature 24h.A large amount of white solids separate out, and reaction terminates rear filtered on buchner funnel and consolidated
Body, 50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of 8.9g white solid product phenyl four.
(2) the polysilsesquioxane nitration reaction of half cage modle of phenyl four prepares the polysilsesquioxane sodium of half cage modle of nitrobenzophenone four
Salt.The polysilsesquioxane sodium salt of half cage modle of 5.0g phenyl four is slowly added in 30mL fuming nitric aicds (ice-water bath reaction in batches
30min), then move to room temperature to continue to react 12h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, faint yellow solid is separated out, is stayed overnight in fume hood, filtering, washing, alcohol are dried in vacuo after washing and obtain 5.8g faint yellow solids；
(3) the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded,
Generate tetranitro phenyl tetraphenyl dimethoxy derivatives.Experimental procedure is：Under nitrogen protection, in 250mL round-bottomed flasks, 3.3g
The polysilsesquioxane sodium salt (4.0mmol) of half cage modle of nitrobenzophenone four is scattered in 100mL methanol solvates.3.4g phenyl trichlorosilane
(16.0mmol) is dissolved in 100mL n-hexanes, is slowly added dropwise into methanol dispersion.Reaction is stirred at room temperature in hybrid reaction system
24h, insoluble salt NaCl separate out the progress for indicating growth response, and reaction is filtered off after terminating except insoluble NaCl, separates first
Alcohol organic phase, add anhydrous magnesium sulfate and dry, rotary evaporation removes solvent and obtains 2.5g faint yellow solid products.
(4) condensation reaction obtains nitrobenzophenone under the ethylbenzene dimethoxy derivatives acidic catalysis conditions of tetranitro phenyl four
And benzene key difunctionality base cage-type silsesquioxane.Under nitrogen protection, in 50mL round-bottomed flasks, 1.0g tetranitro phenyl tetravinyls
Dimethoxy derivatives are dissolved in 25mL methanol, are added dropwise to 10mL H2O, 3.54g (3mL) dense HCl solution, reaction system room temperature
React 24h.White insoluble product separates out, and is dried after filtering, obtains 0.38g products.
Embodiment 3
(1) 9.9g phenyltrimethoxysila,es, 50mL isopropanols are added in flask for molten, 2.0g sodium hydroxides, 0.9mL
H2O is added dropwise to reaction system, reacts at room temperature 24h.A large amount of white solids separate out, and reaction terminates rear filtered on buchner funnel and consolidated
Body, 50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of 8.9g white solid product phenyl four.
(2) the polysilsesquioxane nitration reaction of half cage modle of phenyl four prepares the polysilsesquioxane sodium of half cage modle of nitrobenzophenone four
Salt.The polysilsesquioxane sodium salt of half cage modle of 5.0g phenyl four is slowly added in 30mL fuming nitric aicds (ice-water bath reaction in batches
30min), then move to room temperature to continue to react 12h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, faint yellow solid is separated out, is stayed overnight in fume hood, filtering, washing, alcohol are dried in vacuo after washing and obtain 5.8g faint yellow solids；
(3) the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded,
Generate tetranitro phenyl tetraphenyl dimethoxy derivatives.Experimental procedure is：Under nitrogen protection, in 250mL round-bottomed flasks, 3.3g
The polysilsesquioxane sodium salt (4.0mmol) of half cage modle of nitrobenzophenone four is scattered in 100mL methanol solvates.6.8g phenyl trichlorosilane
(32.0mmol) is dissolved in 100mL n-hexanes, is slowly added dropwise into methanol dispersion.Reaction is stirred at room temperature in hybrid reaction system
24h, insoluble salt NaCl separate out the progress for indicating growth response, and reaction is filtered off after terminating except insoluble NaCl, separates first
Alcohol organic phase, add anhydrous magnesium sulfate and dry, rotary evaporation removes solvent and obtains 2.4g faint yellow solid products.
(4) condensation reaction obtains nitrobenzophenone under the ethylbenzene dimethoxy derivatives acidic catalysis conditions of tetranitro phenyl four
And benzene key difunctionality base cage-type silsesquioxane.Under nitrogen protection, in 50mL round-bottomed flasks, 1.0g tetranitro phenyl tetravinyls
Dimethoxy derivatives are dissolved in 25mL methanol, are added dropwise to 10mL H2O, 7.08g (6mL) dense HCl solution, reaction system room temperature
React 24h.White insoluble product separates out, and is dried after filtering, obtains 0.36g products.
Embodiment 4
(1) 9.9g phenyltrimethoxysila,es, 50mL isopropanols are added in flask for molten, 2.0g sodium hydroxides, 0.9mL
H2O is added dropwise to reaction system, reacts at room temperature 24h.A large amount of white solids separate out, and reaction terminates rear filtered on buchner funnel and consolidated
Body, 50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of 8.9g white solid product phenyl four.
(2) the polysilsesquioxane nitration reaction of half cage modle of phenyl four prepares the polysilsesquioxane sodium of half cage modle of nitrobenzophenone four
Salt.The polysilsesquioxane sodium salt of half cage modle of 5.0g phenyl four is slowly added in 30mL fuming nitric aicds (ice-water bath reaction in batches
30min), then move to room temperature to continue to react 12h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, faint yellow solid is separated out, is stayed overnight in fume hood, filtering, washing, alcohol are dried in vacuo after washing and obtain 5.8g faint yellow solids；
(3) the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded,
Generate tetranitro phenyl tetraphenyl dimethoxy derivatives.Experimental procedure is：Under nitrogen protection, in 250mL round-bottomed flasks, 3.3g
The polysilsesquioxane sodium salt (4.0mmol) of half cage modle of nitrobenzophenone four is scattered in 100mL methanol solvates.3.4g phenyl trichlorosilane
(16.0mmol) is dissolved in 100mL n-hexanes, is slowly added dropwise into methanol dispersion.Reaction is stirred at room temperature in hybrid reaction system
48h, insoluble salt NaCl separate out the progress for indicating growth response, and reaction is filtered off after terminating except insoluble NaCl, separates first
Alcohol organic phase, add anhydrous magnesium sulfate and dry, rotary evaporation removes solvent and obtains 3.2g faint yellow solid products.
(4) condensation reaction obtains nitrobenzophenone under the ethylbenzene dimethoxy derivatives acidic catalysis conditions of tetranitro phenyl four
And benzene key difunctionality base cage-type silsesquioxane.Under nitrogen protection, in 50mL round-bottomed flasks, 1.0g tetranitro phenyl tetravinyls
Dimethoxy derivatives are dissolved in 25mL methanol, are added dropwise to 10mL H2O, 3.54g (3mL) dense HCl solution, reaction system room temperature
React 48h.White insoluble product separates out, and is dried after filtering, obtains 0.41g products.Such as accompanying drawing 1, sample fourier infrared spectrum
Shown in figure：1099、1134cm-1For Si-O-Si characteristic absorption peaks, 1465,1612cm-1For phenyl ring framework characteristic peak, 1352,
1531cm-1For nitro is symmetrical and antisymmetric stretching vibration peak.Accompanying drawing 2, shown in sample hydrogen spectrum nuclear magnetic spectrogram：Chemical shift 7-8 it
Between be phenyl ring proton hydrogen characteristic peak.As a result show successfully to prepare nitrobenzene-containing base and phenyl difunctionality base cage model sesquialter silica
Alkane.
Embodiment 5
(1) 9.9g phenyltrimethoxysila,es, 50mL isopropanols are added in flask for molten, 2.0g sodium hydroxides, 0.9mL
H2O is added dropwise to reaction system, reacts at room temperature 24h.A large amount of white solids separate out, and reaction terminates rear filtered on buchner funnel and consolidated
Body, 50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of 8.9g white solid product phenyl four.
(2) the polysilsesquioxane nitration reaction of half cage modle of phenyl four prepares the polysilsesquioxane sodium of half cage modle of nitrobenzophenone four
Salt.The polysilsesquioxane sodium salt of half cage modle of 5.0g phenyl four is slowly added in 30mL fuming nitric aicds (ice-water bath reaction in batches
30min), then move to room temperature to continue to react 12h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, faint yellow solid is separated out, is stayed overnight in fume hood, filtering, washing, alcohol are dried in vacuo after washing and obtain 5.8g faint yellow solids；
(3) the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane monomer heterogeneous reaction are bonded,
Generate tetranitro phenyl tetraphenyl dimethoxy derivatives.Experimental procedure is：Under nitrogen protection, in 250mL round-bottomed flasks, 3.3g
The polysilsesquioxane sodium salt (4.0mmol) of half cage modle of nitrobenzophenone four is scattered in 100mL methanol solvates.3.4g phenyl trichlorosilane
(16.0mmol) is dissolved in 100mL n-hexanes, is slowly added dropwise into methanol dispersion.Reaction is stirred at room temperature in hybrid reaction system
72h, insoluble salt NaCl separate out the progress for indicating growth response, and reaction is filtered off after terminating except insoluble NaCl, separates first
Alcohol organic phase, add anhydrous magnesium sulfate and dry, rotary evaporation removes solvent and obtains 3.0g faint yellow solid products.
(4) condensation reaction obtains nitrobenzophenone under the ethylbenzene dimethoxy derivatives acidic catalysis conditions of tetranitro phenyl four
And benzene key difunctionality base cage-type silsesquioxane.Under nitrogen protection, in 50mL round-bottomed flasks, 1.0g tetranitro phenyl tetravinyls
Dimethoxy derivatives are dissolved in 25mL methanol, are added dropwise to 10mL H2O, 3.54g (3mL) dense HCl solution, reaction system room temperature
React 72h.White insoluble product separates out, and is dried after filtering, obtains 0.40g products.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (5)
1. the preparation method of a kind of nitrobenzene-containing base and phenyl difunctionality base cage-type silsesquioxane, it is characterised in that including following
Operating procedure：
（1）9.9 g phenyltrimethoxysila,es, 50 mL isopropanols and 2.0 g sodium hydroxides are mixed to form reaction system, then
By 0.9 mL H2O is added dropwise in reaction system, reacts at room temperature 24 h, and white solid separates out, and reaction is filtrated to get solid after terminating
Body, 50 DEG C of vacuum drying obtain the polysilsesquioxane sodium salt of half cage modle of phenyl four；
（2）The polysilsesquioxane sodium salt of 5.0 g phenyl, half cage modle four is added in 30 mL fuming nitric aicds by several times, ice-water bath reaction
30 min, then move to room temperature and continue to react 12 h, reaction is filtered after terminating using glass funnel removes insoluble matter, is added dropwise to trash ice
In, separate out faint yellow solid, in fume hood overnight, after filtering, washing, alcohol are washed vacuum drying it is poly- to obtain the cage modle four of nitrobenzophenone half
Silsesquioxane sodium salt；
（3）Under nitrogen protective condition, the polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four is scattered in methanol, obtains first
Alcohol dispersion, then phenyl trichlorosilane is dissolved in after n-hexane and is added dropwise in methanol dispersion, hybrid reaction system exists
Stirring reaction at room temperature, insoluble salt NaCl separate out the progress for indicating growth response, and reaction is filtered off except insoluble after terminating
NaCl, methanol organic phase is separated, dried, rotary evaporation removes solvent and obtains tetranitro phenyl tetraphenyl dimethoxy derivatives；
（4）Under nitrogen protective condition, tetranitro phenyl tetraphenyl dimethoxy derivatives are dissolved in methanol, are added dropwise to hydrochloric acid
Solution, reaction system are reacted at ambient temperature, and white insoluble product is separated out, and nitrobenzene-containing base and benzene are dried to obtain after filtering
Base difunctionality base cage-type silsesquioxane.
2. preparation method according to claim 1, it is characterised in that：Step（3）The hybrid reaction system is at room temperature
The time of stirring reaction is 24~72 h；The polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four and phenyl trichlorosilane list
Body molar ratio is 1：（2~8）；The drying is dried using anhydrous magnesium sulfate.
3. preparation method according to claim 1, it is characterised in that：Step（3）The hybrid reaction system is at room temperature
The time of stirring reaction is 48h；The polysilsesquioxane sodium salt of half cage modle of nitrobenzophenone four is thrown with phenyl trichlorosilane monomer
It is 1 to expect mol ratio：4.
4. preparation method according to claim 1, it is characterised in that：Step（4）The hydrochloric acid solution is to be by volume ratio
10：（1~6）Water and concentrated hydrochloric acid mix；In the tetranitro phenyl tetraphenyl dimethoxy derivatives and hydrochloric acid solution
The mass volume ratio of concentrated hydrochloric acid is 1 g：（1.5~6）mL；The time that the reaction system is reacted at ambient temperature is 24~72
h。
5. preparation method according to claim 1, it is characterised in that：Step（4）The hydrochloric acid solution is to be by volume ratio
10：3 water and concentrated hydrochloric acid mixes；Concentrated hydrochloric acid in the tetranitro phenyl tetraphenyl dimethoxy derivatives and hydrochloric acid solution
Mass volume ratio be 1 g：3 mL；The time that the reaction system is reacted at ambient temperature is 48 h.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172972A (en) * | 1996-04-01 | 1998-02-11 | 陶氏康宁亚洲株式会社 | Ultraviolet-curable composition and method for forming cured-product patterns therefrom |
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| US7868198B2 (en) * | 2007-06-15 | 2011-01-11 | Laine Richard M | Multi-functional silsesquioxanes for novel coating applications |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172972A (en) * | 1996-04-01 | 1998-02-11 | 陶氏康宁亚洲株式会社 | Ultraviolet-curable composition and method for forming cured-product patterns therefrom |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of functional ladder-like polysilsesquioxane and their hybrid films with polyimide;Qiushuang Gao等;《Thin Solid Films》;ELSEVIER;20110510;第519卷;第6499-6507页 * |
| 硝基笨基倍半硅氧烷用作气相色谱固定相的研究;黄慕斌等;《山东大学学报（自然科学版）》;CNKI;19871231;第22卷(第4期);第94-99页 * |
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