CN109970976A - The polysilsesquioxane and its preparation method and application of tetraphenylethylene base bridging - Google Patents
The polysilsesquioxane and its preparation method and application of tetraphenylethylene base bridging Download PDFInfo
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Abstract
The present invention relates to Intelligent luminous Material Field more particularly to a kind of polysilsesquioxanes and its preparation method and application of tetraphenylethylene base bridging.The present invention will contain the organic sesqui siloxane of aggregation-induced emission (AIE) group as presoma, using chiral cation surfactant as template, the polysilsesquioxane of tetraphenylethylene base bridging is prepared by sol-gel method, present invention process route is simple, consumption of raw materials amount is few, the reaction time is short, easy to operate.
Description
Technical field
The present invention relates to Intelligent luminous Material Field more particularly to a kind of polysilsesquioxanes of tetraphenylethylene base bridging
And its preparation method and application.
Background technique
Organic bridged polysilsesquioxane is covalently keyed by Si-C by inorganic component and organic component and is formed, so
Have the performance of the two concurrently.The thermal stability that organic bridged polysilsesquioxane has inorganic material excellent, while wherein containing
Functional organic group also assign its excellent performance, catalysis, controlled drug transport, fluorescence and sensing, pollutant prison
The fields such as survey have a wide range of applications.Organic bridged polysilsesquioxane is to pass through hydrolysis contracting by organic sesqui siloxane presoma
It closes and is made.Therefore, the exploitation of silsesquioxane is answered with design for developing the organic bridged polysilsesquioxane of diversification, expanding it
It is had great significance with field.
Many functionality organic groups can be introduced into organic bridged polysilsesquioxane, such as chipal compounds, liquid
Brilliant primitive and luminophore etc..But the luminescent organic molecule of planar structure usually shines very by force in the solution, and is assembling
Luminescent decay or quenching under state or solid conditions limit its application in luminous organic bridged polysilsesquioxane.Closely
Nian Lai, one kind have the light emitting molecule of propeller-like structures, such as tetraphenylethylene, thiophene are coughed up, and do not shine and are gathering in the solution
Strong light is strong under collection state or solid conditions, shows aggregation-induced emission (AIE) effect, obtains in High Efficiency Solid-State field of light emitting materials
To being widely applied.For example, Tang Benzhong et al. is with the silsesquioxane and ethyl orthosilicate (TEOS) of the group containing tetraphenylethylene
Mixture is the precursor preparation good fluorescent nano particles of luminescent properties, and is applied to cell imaging
(Chem.Eur.J.,2010,16,4266–4272；small.,2011,7,1448–1455).
The organosiloxane with AIE group is to prepare fluorescence nano as dopant or coating material mostly at present
Material, and poly- times using the silsesquioxane of AIE group bridging as single precursor preparation and with excellent luminance performance
Half silicone compositions have not been reported.Application No. is the Chinese patents of 20l410318789.5 to disclose in a kind of skeleton containing Asia
The preparation method of the chiral bridged polysilsesquioxane nanofiber of aryl, application No. is 201410278614.6 Chinese patents
A kind of preparation method of spiral mesoporous phenolic resin nanofiber is disclosed, which is prepared by cationic template
It arrives.But these nano materials do not fluoresce, and do not have circular polarised luminescence performance.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of poly- silsesquioxanes of tetraphenylethylene base bridging
Alkane and its preparation method and application, the present invention will contain the organic sesqui siloxane of AIE group as presoma, with chiral sun from
Sub- surfactant is template, prepares polysilsesquioxane by sol-gel method, present invention process route is simple, raw material disappears
Consumption is few, the reaction time is short, easy to operate.
The first purpose of the invention is to provide a kind of preparation method of the polysilsesquioxane of tetraphenylethylene base bridging,
The following steps are included:
Chiral cation surfactant shown in formula (1) is dissolved in normal propyl alcohol and ammonium hydroxide, 0 DEG C~20 DEG C (preferably 0 DEG C
~5 DEG C) plastic, then tetraphenylethylene base bridging silsesquioxane shown in formula (2) or formula (3) is added thereto and is mixed
The mixture is stirred up to bleaching strongly, then stands 0~10 day at -5~25 DEG C (preferably -5 DEG C~5 DEG C) by object, and 60
~85 DEG C (preferably 80~85 DEG C) stand 0~10 day, obtain the polysilsesquioxane of the tetraphenylethylene base bridging:
Wherein, R ' be selected from Valine, D-Val, l-Alanine, D-alanine, L-phenylalanine, D-phenylalanine,
L-Isoleucine, D-Ile, L-lysine, D-Lys, L-Leu or D-Leu；
X is selected from Br, Cl or I；
A is selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, methoxyl group or aryl；
R is selected from methyl or ethyl；
N is any one integer in 1~17；M is any one integer in 1~10.
Further, aryl is
Preferably, R ' is selected from Valine or D-Val.
Preferably, X is selected from Br or I.
Preferably, A is selected from hydrogen or methyl, propyl, isopropyl, tert-butyl or methoxyl group.
Preferably, n=15~17；M is 7~10.It is highly preferred that n=17；M is 7 or 10.
Further, in mixture, chiral cation surfactant, tetraphenylethylene base bridging silsesquioxane, just
The ratio of propyl alcohol and ammonium hydroxide is 1~50mg:1~100mg:1~20mL:1~20mL.
Further, the concentration of ammonium hydroxide is 2~25wt%.
Tetraphenylethylene base is AIE group, further, the preparation method packet of tetraphenylethylene base bridging silsesquioxane
Include following steps:
(1) under inert atmosphere protection, the benzophenone derivates that halogen is replaced under the action of zinc and titanium tetrachloride,
The reaction 8~for 24 hours at 60~90 DEG C in organic solvent, it is derivative to obtain shown in formula (4) or formula (5) double halogenated tetraphenylethylenes
Object:
Wherein, X is selected from Br, Cl or I；
A is selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, methoxyl group or aryl；
(2) under inert atmosphere protection, by double halogenated tetraphenylethylene derivatives and trialkoxy silane HSi
(OR)3It is anti-at 60~90 DEG C in organic solvent in the presence of (1,5- cyclo-octadiene) chlorine rhodium (I) dimer and triethylamine
Answer 4~for 24 hours, obtain the tetraphenylethylene base bridging silsesquioxane；Wherein, R is selected from methyl or ethyl.
Further, in step (1), the ratio of benzophenone derivates, zinc and titanium tetrachloride that the halogen replaces
For 10~15g:10~15g:8~12mL.
Further, in step (1), the benzophenone derivates that the halogen replaces are 4- bromine benzophenone, 4- is bromo-
4 '-methyl benzophenones, 4- iodine benzophenone, the iodo- 4 '-methyl benzophenone of 4-, 4- chlorobenzophenone or the chloro- 4 '-methyl of 4-
Benzophenone.
Further, in step (2), double halogenated tetraphenylethylene derivative, trialkoxy silane, (1, the 5- rings
Octadiene) ratio of chlorine rhodium (I) dimer and triethylamine is 1~6g:2~10mL:10~50mg:5~20mL.
Further, in step (1), organic solvent is preferably tetrahydrofuran (THF)；In step (2), organic solvent
Preferably N,N-dimethylformamide (DMF).
It further, further include using concentration for 5~20wt% wet chemical after fully reacting in step (1)
Quenching reaction is added hydrochloric acid except dezincify and potassium carbonate and then product, drying is extracted with dichloromethane out and uses chromatography post separation
The step of product out.
Further, chiral cation surfactant preparation method the following steps are included:
(S1) by the amino acid of benzyloxy protection and alkylamine in triethylamine and benzotriazole-N-N-N '-N '-tetramethyl
In the presence of urea hexafluorophosphoric acid sylvite (HBTU), 1~10h is reacted in organic solvent, then reaction solution is added to the water, precipitated
Object, taking precipitate are dissolved in alcohol, react 5~24 hours at Pd/C and hydrogen effect, obtain intermediate product A；
(S2) intermediate product A is dissolved in CH2Cl2In, it is mixed with triethylamine, halogen acyl chloride, 1~10h of reaction obtains compound
B；Then will compound B be added pyridine in, at 50~150 DEG C react 6~for 24 hours, obtain chiral cation surfactant.
Further, in step (S1), the amino acid in the amino acid of benzyloxy protection is Valine, D- figured silk fabrics ammonia
Acid, l-Alanine, D-alanine, L-phenylalanine, D-phenylalanine, l-Isoleucine, D-Ile, L-lysine, D-
Lysine, L-Leu or D-Leu.
Further, in step (S1), alkylamine is the primary amine of 2~18 carbon atoms.
Further, in step (S2), halogen acyl chloride is the halogen acyl chloride of 1~10 carbon atom.In the present invention, inertia
Atmosphere is preferably nitrogen atmosphere.
Further, further include being separated by filtration after washing product after standing 0~10 day at 60~85 DEG C, then remove mould
Plate and the step of drying.
Further, using water, ethyl alcohol and acetone successively washed product.It is extracted repeatedly using hydrochloric acid and methanol mixed solution
To remove template.
A second object of the present invention is to provide a kind of using tetraphenylethylene base bridging prepared by above-mentioned preparation method
Polysilsesquioxane.
Third object of the present invention is that the polysilsesquioxane of above-mentioned tetraphenylethylene base bridging is claimed to prepare
Application in luminescent device.
Further, the polysilsesquioxane of tetraphenylethylene base bridging of the invention is used as fluorescent nano material,
It can be used for preparing such as optical probe, sensor, circularly polarized laser luminescent device.
According to the above aspect of the present invention, the present invention has at least the following advantages:
1, the present invention selects the silsesquioxane of tetraphenylethylene base bridging separately as presoma for the first time, is prepared for shining
The polysilsesquioxane haveing excellent performance.
2, the polysilsesquioxane for the tetraphenylethylene base bridging that the present invention is prepared is a kind of organic inorganic hybridization material
Material, the material have circular polarised luminescence performance, have a wide range of applications in light emitting device field.
3, preparation method of the invention is simple, easy to operate, and consumption of raw materials is few, the polysilsesquioxane nanometer being prepared
Material property is stablized, and good biocompatibility is pollution-free.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of tetraphenylethylene base bridged polysilsesquioxane S1 prepared by the embodiment of the present invention 1；
Fig. 2 is that the fluorescence microscope of tetraphenylethylene base bridged polysilsesquioxane S1 prepared by the embodiment of the present invention 1 shines
Piece；
Fig. 3 is the circular dichroism spectrogram of tetraphenylethylene base bridged polysilsesquioxane S1 prepared by the embodiment of the present invention 1；
Fig. 4 is the stereoscan photograph of tetraphenylethylene base bridged polysilsesquioxane S2 prepared by the embodiment of the present invention 2；
Fig. 5 is that the fluorescence microscope of tetraphenylethylene base bridged polysilsesquioxane S2 prepared by the embodiment of the present invention 2 shines
Piece；
Fig. 6 is the circular dichroism spectrogram of tetraphenylethylene base bridged polysilsesquioxane S2 prepared by the embodiment of the present invention 2.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
In the present invention, the preparation of tetraphenylethylene base bridged polysilsesquioxane is implemented with the following technical solutions:
One, the preparation of the silsesquioxane of tetraphenylethylene base bridging:
(1) under nitrogen protection, benzophenone derivates and 10~15g zinc powder that 10~15g halogen replaces are dissolved in 50
In~200mLTHF, 8~12mL titanium tetrachloride (TiCl is then slowly added dropwise under ice-water bath4)；Then reflux is anti-at room temperature
Answer 8~for 24 hours.After reaction, the wet chemical of 5~20wt% is added dropwise to quench the reaction into solution；Add hydrochloric acid
Zinc powder and potassium carbonate are removed, product is finally extracted with dichloromethane out and is dried with anhydrous magnesium sulfate；After being filtered to remove magnesium sulfate
It collects filtrate and carries out chromatography post separation with petroleum ether (PE) after being evaporated under reduced pressure, the double halogenated tetraphenyl ethylenes for obtaining white are derivative
Object.
(2) to the bis- halogenated tetraphenyl ethylene derivatives of 1~6g and 10~50mg (1,5- cyclo-octadiene) chlorine rhodium (I) dimer
([Rh(cod)Cl]2) in 5~30mLDMF, 5~20mL be added steam triethylamine (Et again3) and 2~10mL trialkoxy silane N
(HSi(OR)3), under nitrogen protection react 4~for 24 hours.Solvent is removed after reaction, is added suitable n-hexane and ultrasound, is used
Orange solution is obtained by filtration in diatomite.Column chromatography for separation purifies to obtain flaxen tetraphenylethylene base bridging after vacuum distillation
Silsesquioxane.Its reaction route is as follows:
Two, the preparation of chiral cation surfactant:
(1) by 10~50mmol benzyloxy protect amino acid be dissolved in 50~200mLDMF, then be added 10.5~
The triethylamine that 10~50mmol steams again is added after stirring and dissolving by 52.5mmolHBTU.After stirring half an hour, it is slowly added to thereto
The DMF solution of 10~50mmol alkylamine is stirred to react 1~10 hour.Reaction solution is added in deionized water and obtains flocculent deposit,
With obtaining white solid after ethyl alcohol recrystallization.It is dissolved in the ethyl alcohol of 100~1000mL and is added the Pd/C of 1~10g, is passed through
Hydrogen flows back 5~24 hours.It filters and removes Pd/C, filtrate rotary evaporation removes solvent, obtains centre after being recrystallized with petroleum ether
Product A.
(2) 10~50mmol intermediate product A is taken to be dissolved in the CH that 100~1000mL steams again2Cl2In, it is added under ice-water bath
The triethylamine and 15~75mmol halogen acyl chloride that 15~75mmol steams again react 1~10 hour.Rotary evaporation removes molten after reaction
Agent obtains intermediate product B after being recrystallized with dehydrated alcohol.
(3) 10~50mmol intermediate product B is added to 10~100mL to steam in pyridine again, is heated to 50 under nitrogen protection
It~150 DEG C, reacts 6~24 hours.Be spin-dried for after reaction mixture is cooled to room temperature, with obtained after Diethyl ether recrystallization chiral sun from
Sub- surfactant.
Three, the preparation of tetraphenylethylene base bridged polysilsesquioxane:
1~50mg chiral cation surfactant is dissolved in 1~20mL normal propyl alcohol and 1~20mL, 2~25wt% ammonia
Water.1~100mg tetraphenylethylene base bridging silsesquioxane is added at 0 DEG C, and stirring strongly is until reactant bleaches.0℃
Lower standing stands 0~10 day at 0~10 day, 80 DEG C.Then it is separated by filtration with deionized water, ethyl alcohol and acetone washing, is finally used
The mixed solution of hydrochloric acid and methanol extracts repeatedly removes template, dries to obtain the poly- silsesquioxane of tetraphenylethylene base bridging in air
Alkane.
The present invention is further elaborated combined with specific embodiments below.
Embodiment one
The present embodiment is prepared for living with the tetraphenylethylene base bridging silsesquioxane 1 of flowering structure and cationic surface respectively
Property agent L-18Val11PyBr, and further prepare tetraphenylethylene base bridged polysilsesquioxane S1:
The structural formula of tetraphenylethylene base bridging silsesquioxane 1 is as follows:
The structural formula of cationic surfactant L-18Val11PyBr is as follows:
The first step, the preparation of tetraphenylethylene base bridging silsesquioxane 1:
(1) synthesis of double halogenated tetraphenyl ethylene derivatives:
Weigh 4- bromine benzophenone (13.056g, 50mmol), zinc powder (13.076g, 200mmol) is put in two mouthfuls of flasks,
It vacuumizes repeatedly and uses nitrogen protection.The tetrahydrofuran (THF) that 150mL steams again, which is added, dissolves 4- bromine benzophenone, then exists
Titanium tetrachloride (10.96mL, 100mmol) is slowly added dropwise under ice-water bath.Restore to room temperature, back flow reaction 8h in dislocation oil bath.
The wet chemical 100mL of configuration 10% after reaction, is slowly dropped into quench the reaction while stirring.Then it is added
Appropriate hydrochloric acid removes zinc powder and potassium carbonate, and product is finally extracted with dichloromethane out and is dried overnight with anhydrous magnesium sulfate.Filtering
Collection filtrate carries out chromatography post separation with petroleum ether (PE) after being evaporated under reduced pressure after removing magnesium sulfate, obtains white product.Yield
87%.
(2) synthesis of tetraphenylethylene base bridging silsesquioxane:
Weigh double halogenated tetraphenyl ethylene derivatives (2.45g, 5mmol), (1,5- cyclo-octadiene) chlorine rhodium (I) dimer
(37mg, 0.075mmol) is put in two mouth flask, is vacuumized and is used nitrogen protection.Measure the N that 10mL steams again, N- dimethyl methyl
Amide (DMF), 4.17mL steam triethylamine (30mmol) again and 7.4mL triethoxysilane (40mmol) is added in sample bottle,
12h is reacted under nitrogen protection.Solvent is removed after reaction, is added suitable n-hexane and ultrasound, is obtained by filtration with diatomite
Orange solution.Column chromatography for separation purifies to obtain faint yellow viscous samples, as tetraphenylethylene base bridging times after vacuum distillation
Half siloxanes 1.Yield 35%.Test result is as follows for its nucleus magnetic hydrogen spectrum:
1H NMR(400MHz,CDCl3)δ7.43-7.36(m,4H),7.03-7.00(m,14H),3.99-3.76(m,
12H), 1.21 (t, J=6.8Hz, 18H) .MS m/z (rel.int.): 656 (M+,100),679(M++Na,16.11)。
Second step, the preparation of cationic surfactant L-18Val11PyBr:
The Valine Z-L-Val (12.564g, 50mmol) for taking benzyloxy to protect is dissolved by heating in the N of 200mL, N- bis-
19.9g (52.5mmol) benzotriazole-N-N-N '-N '-tetramethylurea hexafluorophosphoric acid is then added in methylformamide (DMF)
The triethylamine (50mmol) that 5.06g steams again is added after stirring and dissolving for sylvite (HBTU).After stirring half an hour, octadecylamine is taken
(13.476g, 50mmol) is slowly added in reaction vessel after being dissolved by heating with 400mL DMF, and mechanical stirring 10 hours.It will reaction
Flocculent deposit is added in deionized water to obtain in liquid, with obtaining white solid after ethyl alcohol recrystallization.8g is weighed to be dissolved in the ethyl alcohol of 500mL
And the Pd/C of 0.4g is added, it is passed through hydrogen and flows back 12 hours.It filters and removes Pd/C, filtrate rotary evaporation removes solvent, uses petroleum
Intermediate product L-Val-NH-C is obtained after ether recrystallization18H37。
Take 6.06g (16.4mmol) intermediate product L-Val-NH-C18H37It is dissolved in the CH that 400mL steams again2Cl2In, in ice
The triethylamine and 5.7mL (24.6mmol) Br (CH that 3.4mL (24.6mmol) steams again are slowly added under water-bath2)10COCl, reaction 6
Hour.Evaporation of solvent is rotated after reaction, and intermediate product L-18Val11Br is obtained after being recrystallized with dehydrated alcohol.
7.5g (12mmol) intermediate product L-18Val11Br is added to 50mL to steam in pyridine again, is heated under nitrogen protection
To 100 DEG C, react 12 hours.It is spin-dried for after reaction mixture is cooled to room temperature, with obtaining cationic surface after Diethyl ether recrystallization
Activating agent L-18Val11PyBr.
Third step, the preparation of tetraphenylethylene base bridged polysilsesquioxane S1:
It weighs 12mgL-18Val11PyBr to be placed in test tube, 1.05mL normal propyl alcohol and 0.45mL 10wt% ammonium hydroxide, which is added, to be made
Dissolution.The tetraphenylethylene base bridging silsesquioxane 1 of the above-mentioned preparation of 20mg and stirring strongly are added at 0 DEG C until reaction
Object bleaches.4 days are stood at standing 1 day, 80 DEG C at 0 DEG C.Then it is separated by filtration with deionized water, ethyl alcohol and acetone washing, finally
It is extracted repeatedly with the mixed solution of 5mL36.0wt% hydrochloric acid and 100mL methanol and removes template, dry to obtain final product in air
S1。
As shown in Figure 1, product S1 is left hand helix nanotube bundle, and single nanotube diameter is about 80~200nm, and length is about
It is more than ten micron.It can be seen that polysilsesquioxane issues bright green fluorescence from fluorescent microscopy images (Fig. 2).
The tetraphenylethylene base bridged polysilsesquioxane being prepared as shown in Figure 3 has CD letter in ultraviolet visible light region
Number, show that S1 has optical activity.
Embodiment two
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 1 and cationic surfactant D-
18Val11PyBr prepares tetraphenylethylene base bridged polysilsesquioxane S2, wherein tetraphenylethylene base bridging silsesquioxane
1 structure and preparation method is the same as embodiment one.
(1) structural formula of cationic surfactant D-18Val11PyBr and preparation method difference are as follows:
Benzyloxy protection D-Val Z-D-Val (12.564g, 50mmol) is taken to dissolve by heating in the N of 200mL, N- diformazan
19.9g (52.5mmol) benzotriazole-N-N-N '-N '-tetramethylurea Potassium Hexafluorophosphate is then added in base formamide (DMF)
The triethylamine (50mmol) that 5.06g steams again is added after stirring and dissolving for salt (HBTU).After stirring half an hour, octadecylamine is taken
(13.476g, 50mmol) is slowly added in reaction vessel after being dissolved by heating with 400mL DMF, and mechanical stirring 10 hours.It will reaction
Flocculent deposit is added in deionized water to obtain in liquid, with obtaining white solid after ethyl alcohol recrystallization.8g is weighed to be dissolved in the ethyl alcohol of 500mL
And the Pd/C of 0.4g is added, it is passed through hydrogen and flows back 12 hours.It filters and removes Pd/C, filtrate rotary evaporation removes solvent, uses petroleum
Intermediate product D-Val-NH-C is obtained after ether recrystallization18H37。
Take 6.06g (16.4mmol) product D-Val-NH-C18H37It is dissolved in the CH that 400mL steams again2Cl2In, in ice-water bath
Under be slowly added to the triethylamine and 5.7mL (24.6mmol) Br (CH that 3.4mL (24.6mmol) steams again2)10COCl reacts 6 hours.
Evaporation of solvent is rotated after reaction, and intermediate product D-18Val11Br is obtained after being recrystallized with dehydrated alcohol.
7.5g (12mmol) product D-18Val11Br is added to 50mL to steam in pyridine again, is heated to 100 under nitrogen protection
DEG C, it reacts 12 hours.It is spin-dried for after reaction mixture is cooled to room temperature, with obtaining cationic surfactant after Diethyl ether recrystallization
D-18Val11PyBr。
(2) preparation of tetraphenylethylene base bridged polysilsesquioxane S2:
12mg chiral cation template D-18Val11PyBr is weighed to be placed in test tube, be added 1.05mL normal propyl alcohol and
0.45mL10wt% ammonium hydroxide is allowed to dissolve.Tetraphenylethylene base bridging sesquialter silicon prepared by 20mg embodiment one is added at 0 DEG C
Oxygen alkane 1 and strongly stirring are until reactant bleaches.4 days are stood at standing 1 day, 80 DEG C at 0 DEG C.Then deionized water, ethyl alcohol are used
It is separated by filtration with acetone washing, is finally extracted repeatedly with the mixed solution of 5mL36.0wt% hydrochloric acid and 100mL methanol and remove mould
Plate dries to obtain final product S2 in air.
As shown in Figure 4, product S2 is right-handed helix nanotube bundle, and single nanotube diameter is about 100~250nm, length
About more than ten micron.(Fig. 5) is it can be seen that polysilsesquioxane issues bright green fluorescence from fluorescent microscopy images.
The tetraphenylethylene base bridged polysilsesquioxane being prepared as shown in Figure 6 has CD letter in ultraviolet visible light region
Number, show that S2 has optical activity.
Embodiment three
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 1 and cationic surfactant L-18Val8PyBr
Prepare tetraphenylethylene base bridged polysilsesquioxane S3, wherein the structure and system of tetraphenylethylene base bridging silsesquioxane 1
Preparation Method is the same as embodiment one.
(1) structural formula of cationic surfactant L-18Val8PyBr is as follows:
L-18Val8PyBr is prepared according to the method for embodiment one, the difference is that, by the Br (CH in second step2)10COCl replaces with equimolar Br (CH2)7COCl (5.93g, 24.6mmol).
(2) preparation of tetraphenylethylene base bridged polysilsesquioxane S3:
12mg chiral cation template L-18Val8PyBr is weighed to be placed in test tube, be added 1.05mL normal propyl alcohol and
0.45mL10wt% ammonium hydroxide is allowed to dissolve.Tetraphenylethylene base bridging sesquialter silicon prepared by 20mg embodiment one is added at 0 DEG C
Oxygen alkane 1 and strongly stirring are until reactant bleaches.4 days are stood at standing 1 day, 80 DEG C at 0 DEG C.Then deionized water, ethyl alcohol are used
It is separated by filtration with acetone washing, is finally extracted repeatedly with the mixed solution of 5mL36.0wt% hydrochloric acid and 100mL methanol and remove mould
Plate dries to obtain final product S3 in air.
Example IV
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 1 and cationic surfactant D-18Val8PyBr
Prepare tetraphenylethylene base bridged polysilsesquioxane S4, wherein the structure and system of tetraphenylethylene base bridging silsesquioxane 1
Preparation Method is the same as embodiment one.
(1) structural formula of cationic surfactant D-18Val8PyBr is as follows:
D-18Val8PyBr is prepared according to the method for embodiment two, the difference is that, by the Br (CH in second step2)10COCl replaces with equimolar Br (CH2)7COCl (5.93g, 24.6mmol).
(2) preparation of tetraphenylethylene base bridged polysilsesquioxane S4:
12mg chiral cation template D-18Val8PyBr is weighed to be placed in test tube, be added 1.05mL normal propyl alcohol and
0.45mL 10wt% ammonium hydroxide is allowed to dissolve.Tetraphenylethylene base bridging sesquialter silicon prepared by 20mg embodiment one is added at 0 DEG C
Oxygen alkane 1 and strongly stirring are until reactant bleaches.4 days are stood at standing 1 day, 80 DEG C at 0 DEG C.Then deionized water, ethyl alcohol are used
It is separated by filtration with acetone washing, is finally extracted repeatedly with the mixed solution of 5mL36.0wt% hydrochloric acid and 100mL methanol and remove mould
Plate dries to obtain final product S4 in air.
Embodiment five
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 2 and cationic surfactant L-
18Val11PyBr prepares tetraphenylethylene base bridged polysilsesquioxane S5, wherein cationic surfactant L-
The structure and preparation method of 18Val11PyBr is the same as embodiment one.
(1) structural formula of the preparation of tetraphenylethylene base bridging silsesquioxane 2 is as follows:
Preparation method as in the first embodiment, the difference is that: the 4- bromine benzophenone in step (1) is replaced with etc. and is rubbed
Your bromo- 4 '-methyl benzophenone (13.757g, 50mmol) of 4-.
(2) preparation of tetraphenylethylene base bridged polysilsesquioxane S5:
It weighs 12mgL-18Val11PyBr to be placed in test tube, 1.05mL normal propyl alcohol and 0.45mL 10wt% ammonium hydroxide, which is added, to be made
Dissolution.The tetraphenylethylene base bridging silsesquioxane 2 of 20mg preparation and stirring strongly are added at 0 DEG C until reactant becomes
It is white.4 days are stood at standing 1 day, 80 DEG C at 0 DEG C.Then it is separated by filtration with deionized water, ethyl alcohol and acetone washing, finally uses 5mL
The mixed solution of 36.0wt% hydrochloric acid and 100mL methanol extracts repeatedly removes template, dries to obtain final product S5 in air.
Embodiment six
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 2 and cationic surfactant D-
18Val11PyBr prepares tetraphenylethylene base bridged polysilsesquioxane S6, wherein tetraphenylethylene base bridging silsesquioxane
2 structure and preparation method is with embodiment five, and the structure and preparation method of cationic surfactant D-18Val11PyBr is the same as real
Apply example two.
Preparing for tetraphenylethylene base bridged polysilsesquioxane S6 is as follows:
It weighs 12mgD-18Val11PyBr to be placed in test tube, 1.05mL normal propyl alcohol and 0.45mL 10wt% ammonium hydroxide, which is added, to be made
Dissolution.20mg tetraphenylethylene base bridging silsesquioxane 2 and stirring strongly are added at 0 DEG C until reactant bleaches.0℃
Lower standing stands 4 days at 1 day, 80 DEG C.Then it is separated by filtration with deionized water, ethyl alcohol and acetone washing, finally uses 5mL
The mixed solution of 36.0wt% hydrochloric acid and 100mL methanol extracts repeatedly removes template, dries to obtain final product S6 in air.
Embodiment seven
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 3 and cationic surfactant L-
18Val11PyBr prepares tetraphenylethylene base bridged polysilsesquioxane S7, wherein cationic surfactant L-
The structure and preparation method of 18Val11PyBr is the same as embodiment one.
(1) structural formula of the preparation of tetraphenylethylene base bridging silsesquioxane 3 is as follows:
Preparation method as in the first embodiment, the difference is that: the triethoxysilane in step (2) is replaced with etc. and is rubbed
Your trimethoxy silane (40mmol).
(2) preparation of tetraphenylethylene base bridged polysilsesquioxane S7:
It weighs 12mgL-18Val11PyBr to be placed in test tube, 1.05mL normal propyl alcohol and 0.45mL 10wt% ammonium hydroxide, which is added, to be made
Dissolution.20mg tetraphenylethylene base bridging silsesquioxane 3 and stirring strongly are added at 0 DEG C until reactant bleaches.0℃
Lower standing stands 4 days at 1 day, 80 DEG C.Then it is separated by filtration with deionized water, ethyl alcohol and acetone washing, finally uses 5mL
The mixed solution of 36.0wt% hydrochloric acid and 100mL methanol extracts repeatedly removes template, dries to obtain final product S7 in air.
Embodiment eight
The present embodiment is using tetraphenylethylene base bridging silsesquioxane 3 and cationic surfactant D-
18Val11PyBr prepares tetraphenylethylene base bridged polysilsesquioxane S8, wherein tetraphenylethylene base bridging silsesquioxane
3 structure and preparation method is with embodiment seven, and the structure and preparation method of cationic surfactant D-18Val11PyBr is the same as real
Apply example two.
Preparing for tetraphenylethylene base bridged polysilsesquioxane S8 is as follows:
It weighs 12mgD-18Val11PyBr to be placed in test tube, 1.05mL normal propyl alcohol and 0.45mL 10wt% ammonium hydroxide, which is added, to be made
Dissolution.20mg tetraphenylethylene base bridging silsesquioxane 3 and stirring strongly are added at 0 DEG C until reactant bleaches.0℃
Lower standing stands 4 days at 1 day, 80 DEG C.Then it is separated by filtration with deionized water, ethyl alcohol and acetone washing, finally uses 5mL
The mixed solution of 36.0wt% hydrochloric acid and 100mL methanol extracts repeatedly removes template, dries to obtain final product S8 in air.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the polysilsesquioxane of tetraphenylethylene base bridging, which comprises the following steps:
Chiral cation surfactant shown in formula (1) is dissolved in normal propyl alcohol and ammonium hydroxide, 0 DEG C~20 DEG C plastics, then by formula
(2) or tetraphenylethylene base bridging silsesquioxane shown in formula (3) is added thereto to obtain mixture, and the mixture is stirred
Until bleaching, 0~10 day then is stood at -5~25 DEG C, 60~85 DEG C stand 0~10 day, obtain the tetraphenylethylene Ji Qiao
The polysilsesquioxane of connection:
Wherein, it is different to be selected from Valine, D-Val, l-Alanine, D-alanine, L-phenylalanine, D-phenylalanine, L- by R '
Leucine, D-Ile, L-lysine, D-Lys, L-Leu or D-Leu；
X is selected from Br, Cl or I；
A is selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, methoxyl group or aryl；
R is selected from methyl or ethyl；
N is any one integer in 1~17；M is any one integer in 1~10.
2. preparation method according to claim 1, it is characterised in that: chiral cation surfactant, normal propyl alcohol and ammonia
The ratio of water is 1~50mg:1~20mL:1~20mL.
3. preparation method according to claim 1, it is characterised in that: in the mixture, chiral cation surface-active
The mass ratio of agent and tetraphenylethylene base bridging silsesquioxane is 1~50:1~100.
4. preparation method according to claim 1, which is characterized in that the tetraphenylethylene base bridging silsesquioxane
Preparation method the following steps are included:
(1) under inert atmosphere protection, the benzophenone derivates that halogen is replaced are having under the action of zinc and titanium tetrachloride
The reaction 8~for 24 hours at 60~90 DEG C in solvent, obtains shown in formula (4) or formula (5) double halogenated tetraphenylethylene derivatives:
Wherein, X is selected from Br, Cl or I；
A is selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl, methoxyl group or aryl；
(2) under inert atmosphere protection, by double halogenated tetraphenylethylene derivatives and trialkoxy silane HSi (OR)3?
In the presence of (1,5- cyclo-octadiene) chlorine rhodium (I) dimer and triethylamine, in organic solvent at 60~90 DEG C reaction 4~
For 24 hours, the tetraphenylethylene base bridging silsesquioxane is obtained；Wherein, R is selected from methyl or ethyl.
5. the preparation method according to claim 4, it is characterised in that: in step (1), the hexichol first of the halogen substitution
The ratio of ketone derivatives, zinc and titanium tetrachloride is 10~15g:10~15g:8~12mL.
6. the preparation method according to claim 4, it is characterised in that: in step (1), the hexichol first of the halogen substitution
Ketone derivatives are 4- bromine benzophenone, the bromo- 4 '-methyl benzophenone of 4-, 4- iodine benzophenone, the iodo- 4 '-methyldiphenyl first of 4-
Ketone, 4- chlorobenzophenone or the chloro- 4 '-methyl benzophenone of 4-.
7. the preparation method according to claim 4, it is characterised in that: in step (2), double halogenated tetraphenylethylenes
Derivative, trialkoxy silane, (1,5- cyclo-octadiene) chlorine rhodium (I) dimer and triethylamine ratio be 1~6g:2~10mL:
10~50mg:5~20mL.
8. preparation method according to claim 1, it is characterised in that: further include after standing 0~10 day at 60~85 DEG C by
It is separated by filtration after product washing, then removes the step of template and drying.
9. a kind of poly- sesquialter silicon of tetraphenylethylene base bridging prepared by preparation method of any of claims 1-8
Oxygen alkane.
10. the polysilsesquioxane of tetraphenylethylene base bridging as claimed in claim 9 is preparing the application in luminescent device.
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