CN104672273B - Asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane and its synthetic method and application - Google Patents
Asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane and its synthetic method and application Download PDFInfo
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Abstract
The present invention relates to oligomeric silsesquioxane synthesis technical field, synthesis to solve existing asymmetric polyhedral oligomeric silsesquioxane focuses mostly on to be carried on the cage type polyhedral oligomeric silsesquioxane of different functional groups in polyhedral oligomeric silsesquioxane of the left and right with two kinds of different functional groups with upper and lower surfaces, the problem of product functional group random distribution being there is in terms of synthesis, the present invention proposes asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane and its synthetic method and application, described asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane, while with parallel hydroxyl, while with other groups, its structural formula such as (I), (II) shown in：
Description
Technical field
The present invention relates to oligomeric silsesquioxane synthesis technical field, more particularly to new asymmetric hydroxyl double-deck
Shape and trapezoidal oligomeric silsesquioxane and its high-efficiency synthesis method and application.
Background technology
Asymmetric hydroxyl double-deck shape has important use with trapezoidal oligomeric silsesquioxane, is such as used to develop a beading
The new polysiloxanes such as type, ladder-cage type, trapezoidal, hyperbranched and big ring；Develop novel coupling agent；Develop novel catalyst carrier
Deng.So far, seeing the asymmetric oligomeric silsesquioxane of report has two types.The first asymmetric oligomeric silsesquioxane
Alkane is polyhedral oligomeric silsesquioxane of the left and right with two kinds of different functional groups, and such as Y.Kawakami et al. is published in
Advanced Polymer Science paper (Advanced Polymer Science, 2011,235,185-228), is situated between
Continued the polyhedral oligomeric silsesquioxane for being respectively provided with dimethylsilyl bis and cyclobutyl silicon substrate, and this asymmetric polyhedron is low
Polysilsesquioxane is only used for synthesizing linear polymer, is of limited application, and is not provided in paper this asymmetric
The characterize data of polyhedral oligomeric silsesquioxane.Another asymmetric oligomeric silsesquioxane is upper and lower surfaces with difference
The cage type polyhedral oligomeric silsesquioxane of functional group, this kind of asymmetric polyhedral oligomeric silsesquioxane is mostly carried by two kinds
The silanol of cyclotetrasiloxane four of different functional groups is what raw material cocondensation was obtained, but function is often generated in building-up process
The polyhedral oligomeric silsesquioxane that group randomly arranges.As S.Tateyama et al. is published in Journal of
Organometallic Chemistry paper (Journal of Organometallic Chemistry, 2010,695,
898-902), with 1,3,5,7- tetraphenyls -1,3,5,7- tetrahydroxy cyclotetrasiloxanes and 1,3,5,7- tetra- deuterated phenyl -1,3,5,
7- tetrahydroxys cyclotetrasiloxane is the cage type polyhedron that raw material obtains Liao Liangzhong functional groups random distribution under the catalysis of quaternary ammonium base
Oligomeric silsesquioxane.
In a word, the synthesis of existing asymmetric polyhedral oligomeric silsesquioxane focuses mostly in left and right with two kinds of different functions
The polyhedral oligomeric silsesquioxane of group carries the cage type polyhedral oligomeric silsesquioxane of different functional groups with upper and lower surfaces
On, the problem of there is product functional group random distribution in terms of synthesis, application aspect is only applicable to develop linear polymeric.
The content of the invention
Synthesis to solve existing asymmetric polyhedral oligomeric silsesquioxane focuses mostly in left and right with two kinds of different officials
The polyhedral oligomeric silsesquioxane that can be rolled into a ball carries the cage type polyhedral oligomeric silsesquioxane of different functional groups with upper and lower surfaces
On alkane, the problem of there is product functional group random distribution in terms of synthesis, the present invention proposes asymmetric hydroxyl double-deck shape
With trapezoidal oligomeric silsesquioxane and its synthetic method and application, asymmetric hydroxyl double-deck shape of the invention with it is trapezoidal oligomeric
Silsesquioxane application is wider, and synthetic method has that reaction condition is gentle, energy consumption is low, combined coefficient is high, product is purified
The advantages of journey is simple and easy to apply.
The present invention is to be achieved through the following technical solutions：Asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane
Alkane, while with parallel hydroxyl, while with other groups, its structural formula is such as shown in (I), (II)：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic radical, epoxy radicals, ester
It is a kind of in base, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl.
Described asymmetric hydroxyl double-deck shape and the synthetic method of trapezoidal oligomeric silsesquioxane are following steps：With
Ring four silica of double-deck shape oligomeric silsesquioxane four silanol or structural formula of the structural formula as shown in (III) as shown in (IV)
The silanol of alkane four is raw material with the disiloxane containing two reactive functionalities, and in the presence of catalyst, in organic solvent
Reacted, then by last handling process, respectively obtain asymmetric hydroxyl double-deck shape of the structural formula as shown in (I), (II)
With trapezoidal oligomeric silsesquioxane, course of reaction is as follows：
In reaction equation, R1、R2、R3、R4、R5Separately it is selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic radical, epoxy
A kind of in base, ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl, X is separately selected
It is a kind of from hydrogen, fluorine, chlorine, bromine, iodine, alkoxy.
Preferably, cyclotetrasiloxane four silanol of the structural formula as shown in (IV) is selected from complete same-silanol of cyclotetrasiloxane four
Or suitable, anti-, the cis- silanol of cyclotetrasiloxane four.
Described organic solvent is one or more of in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone, preferably,
Organic solvent is selected from hexane, hexamethylene, toluene, chlorobenzene, 1,3,5- trimethylbenzenes, ether, butyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxy
It is one or more of in six rings, acetone, butanone, cyclohexanone, methyl iso-butyl ketone (MIBK).Amount used in organic solvent is to make what solute dissolved
Amount.
Described catalyst is selected from inorganic ammonia, organic amine, quaternary ammonium base, metal simple-substance, metal oxide, metal salt, complexing
It is a kind of in thing, preferably, catalyst is selected from ammonia, ammoniacal liquor, dimethylamine, diethylamine, trimethylamine, triethylamine, pyridine, tetramethyl
Ammonium hydroxide, tetraethyl ammonium hydroxide, tetra-tert ammonium hydroxide and iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, osmium, iridium, gold, silver,
A kind of simple substance of metal or corresponding compound in copper, tin, zinc, titanium, pick, chromium, manganese, lanthanide series metal.
Double-deck shape oligomeric silsesquioxane four silanol or structural formula of the structural formula as shown in (III) are as shown in (IV)
The mass ratio of the silanol of cyclotetrasiloxane four and catalyst is 1: 0.001~1, with the matter containing two reactive functionality disiloxane
Amount is than being 1: 0.001~1.
Preferably, reaction temperature is -20~140 DEG C, the reaction time is 30 minutes~24 hours.
Preferably, last handling process is recrystallization, precipitation, column chromatography or vacuum drying.
The silanol of double-deck shape oligomeric silsesquioxane four or structural formula of the invention with structural formula as shown in (III) is such as
(IV) silanol of cyclotetrasiloxane four shown in being raw material containing two reactive functionality disiloxane, inorganic ammonia, organic amine,
In the presence of quaternary ammonium base or metallic catalyst, occur condensation reaction or dehydrogenation/dealcoholysis coupling reaction, realize asymmetric containing hydroxyl
Base double-deck shape is efficiently synthesized with trapezoidal oligomeric silsesquioxane, and yield can reach 60~95%.Product structure passes through red
External spectrum and proton nmr spectra etc. are characterized.Infrared spectrum containing functional group with matching in theory, hydrogen nuclear magnetic resonance
Spectrum matches with theoretical proton number with chemical shift.
The present invention asymmetric oligomeric silsesquioxane molecule in contain a variety of functional groups, available for exploitation bead type, ladder-
The new polysiloxanes such as cage type, trapezoidal, hyperbranched and big ring；Develop novel coupling agent；Develop novel catalyst carrier etc..
Compared with prior art, the beneficial effects of the invention are as follows：
(1) synthetic method has reaction condition is gentle, energy consumption is low, combined coefficient is high, product purification process is simple and easy to apply etc.
Advantage；
(2) asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane application of the invention are wider.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane in embodiment 1；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane in embodiment 1；
Fig. 3 is the infrared spectrogram of the asymmetric trapezoidal oligomeric silsesquioxane of hydroxyl in embodiment 2.
Embodiment
Embodiment 1：The preparation of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing methyl, phenyl and hydrogen
, will 10 milliliters of Isosorbide-5-Nitrae-dioxies six containing 3 grams of 1,3- dimethyl -1,3- dichloro disiloxane at a temperature of -20 DEG C
Ring solution is slowly dropped to equipped with the silanol of double-deck shape oligomeric silsesquioxane four, the 3 grams of diethylamine and 10 that 3 grams of side bases are phenyl
In 50 milliliters of three-necked flasks of milliliter Isosorbide-5-Nitrae-dioxane, then stirring reaction 30 minutes, are washed with water organic layer to neutrality, add
After anhydrous sodium sulfate drying, vacuum drying removes solvent, obtains white solid, yield 78%.
Infrared spectrum such as Fig. 1 of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing methyl, phenyl and hydrogen
Shown, the hydrogen nuclear magnetic resonance spectrogram of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing methyl, phenyl and hydrogen is such as
Shown in Fig. 2.
Embodiment 2：The preparation of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing methyl, phenyl and hydrogen
, will 20 milliliters of tetrahydrofuran solutions containing 2 grams of 1,3- dimethyl -1,3- dichloro disiloxane at a temperature of 60 DEG C
It is slowly dropped to equipped with all-cis-silanol of cyclotetrasiloxane four, 2 grams of triethylamines and the 300 milliliters of tetrahydrochysene furans that 200 grams of side bases are phenyl
In the 500 milliliters of three-necked flasks muttered, then stirring reaction 8 hours, question response solution is down to after room temperature, add 300 milliliters just oneself
Alkane, is washed with water organic layer to neutrality, adds after anhydrous sodium sulfate drying, vacuum drying removes solvent, obtains white solid, yield
85%.
The infrared spectrum of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing methyl, phenyl and hydrogen is as shown in Figure 3.
Embodiment 3：The asymmetric oligomeric sesquialter of hydroxyl double-deck shape containing vinyl, ethyl acrylate base and pi-allyl
The preparation of siloxanes
At a temperature of 90 DEG C, 16 grams of silica of 1,3- divinyl -1,3- ethyl diacrylate bases -1,3- dichloro two will be contained
20 milliliters of methyl isobutyl ketone solutions of alkane are slowly dropped to equipped with the oligomeric sesquialter silicon of double-deck shape that 100 grams of side bases are pi-allyl
In 500 milliliters of three-necked flasks of the silanol of oxygen alkane four, 0.1 gram of TMAH and 200 milliliters of methyl iso-butyl ketone (MIBK)s, then stir
Reaction 16 hours is mixed, is down to after room temperature, organic layer is washed with water to neutrality, adds after anhydrous sodium sulfate drying, vacuum drying is removed
Solvent, obtains white solid, yield 78%.
Embodiment 4：Asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing p- chloromethyl phenyls, ethyl and hydrogen
Preparation
At a temperature of 120 DEG C, by 20 milliliters containing 5 grams of 1,3- bis- (p- chloromethyl phenyls) -1,3- dichloro disiloxane
It is the silanol of double-deck shape oligomeric silsesquioxane four of ethyl that chlorobenzene solution, which is slowly dropped to equipped with 50 grams of side bases, 2 grams of pyridines with
In 500 milliliters of three-necked flasks of 100 milliliters of chlorobenzenes, then stirring reaction 16 hours, question response solution is down to after room temperature, is washed with water
Organic layer is added after anhydrous sodium sulfate drying to neutrality, and vacuum drying removes solvent, obtains white solid, yield 95%.
Embodiment 5：The preparation of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing vinyl, itrile group and pi-allyl
, will 10 millis containing 3 grams of 1,3- divinyl -1,3- dinitrile -1,3- dichloro disiloxane at a temperature of 30 DEG C
Acetone soln is risen to be slowly dropped to equipped with suitable, anti-, the cis- silanol of cyclotetrasiloxane four, the 0.3 gram of ammoniacal liquor that 30 grams of side bases are pi-allyl
With in 500 milliliters of three-necked flasks of 100 milliliters of acetone, then stirring reaction 20 hours add 300 milliliters of n-hexanes, are washed with water
Organic layer adds after anhydrous sodium sulfate drying to neutrality, solution is poured into methanol, there is white solid precipitation, is filtrated to get white
Color solid, vacuum drying obtains target product, yield 65%.
Embodiment 6：The system of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing 3- chloropropyls, naphthyl and hydrogen
It is standby
, will 50 milliliters of rings containing 0.2 gram of 1,3- bis- (3- chloropropyls) -1,3- dichloro disiloxane at a temperature of 140 DEG C
Hexanone solution is slowly dropped to equipped with the silanol of double-deck shape oligomeric silsesquioxane four, 20 gram of four uncle that 200 grams of side bases are naphthyl
In 1000 milliliters of three-necked flasks of butyl ammonium hydroxide and 300 milliliters of cyclohexanone, then stirring reaction 24 hours, question response solution
It is down to after room temperature, organic layer is washed with water to neutrality, adds after anhydrous sodium sulfate drying, solution is poured into ethanol, there is white solid
Separate out, be filtrated to get white solid and vacuum drying, obtain target product, yield 90%.
Embodiment 7：The preparation of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing phenyl, butyl and epoxy radicals
At a temperature of 20 DEG C, the 60 of 6 grams of 1,3- diphenyl -1,3- dibutyl -1,3- dimethoxy disiloxane will be contained
Milliliter Isosorbide-5-Nitrae-dioxane solution be slowly dropped to equipped with 30 grams of side bases for epoxy radicals all-cis-silanol of cyclotetrasiloxane four, 3 grams
In 500 milliliters of three-necked flasks of palladium bichloride and 60 milliliters of Isosorbide-5-Nitrae-dioxane, then stirring reaction 3 hours, question response liquid is down to
After room temperature, palladium bichloride is removed with column chromatography, vacuum drying removes solvent, obtains white solid, yield 81%.
Embodiment 8：The asymmetric oligomeric sesquialter of hydroxyl double-deck shape containing epoxy radicals, pi-allyl and ethyl acrylate base
The preparation of siloxanes
At a temperature of 30 DEG C, 30 grams of 1,3- bicyclic oxygen -1,3- diallyl -1,3- diethoxy disiloxane will be contained
60 milliliters of butanone solutions be slowly dropped to equipped with 50 grams of side bases be ethyl acrylate base double-deck shape oligomeric silsesquioxane
In 250 milliliters of three-necked flasks of four silanols, 3 grams of palladium/carbon and 60 milliliters of butanone, then stirring reaction 15 hours, are removed with column chromatography
Palladium/carbon is removed, after being recrystallized with ethanol as solvent, clear crystal, yield 78% is obtained.
Embodiment 9：The asymmetric oligomeric sesquialter of hydroxyl double-deck shape containing p- chloromethyl phenyls, n-octyl and normal-butyl
The preparation of siloxanes
At a temperature of 10 DEG C, 5 grams of 1,3- bis- (p- chloromethyl phenyls) -1,3- di-n-octyl -1,3- dimethoxys will be contained
20 milliliter 1 of disiloxane, 3,5- trimethylbenzene solutions are slowly dropped to low for the double-deck shape of normal-butyl equipped with 20 grams of side bases
In the silanol of polysilsesquioxane four, 2 grams of chloroplatinic acids and 50 milliliter 1,250 milliliters of three-necked flasks of 3,5- trimethylbenzenes, then stir
Reaction 16 hours is mixed, after question response solution is warmed to room temperature, chloroplatinic acid is removed with column chromatography, vacuum drying removes solvent, obtains white
Color solid, yield 75%.
Claims (6)
1. a kind of synthetic method of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane, it is characterised in that described synthesis
Method be with double-deck shape oligomeric silsesquioxane four silanol of the structural formula as shown in (III) with containing two reactive functionalities
Disiloxane is raw material, and in the presence of catalyst, is reacted in organic solvent, and reaction temperature is -20~140 DEG C,
Reaction time is 30 minutes~24 hours, then by last handling process, obtains asymmetric hydroxyl of the structural formula as shown in (I) double
Deck shape oligomeric silsesquioxane, course of reaction is as follows：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic radical, epoxy radicals, ester group, sulphur
A kind of in acidic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl, X is separately selected from hydrogen, alkoxy
Middle one kind；
Organic solvent is one or more of in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone；
Described catalyst is a kind of in metal simple-substance, metal oxide, metal salt, complex compound.
2. the synthetic method of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane according to claim 1, its feature
Be, organic solvent be selected from hexane, hexamethylene, toluene, chlorobenzene, 1,3,5- trimethylbenzenes, ether, butyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-
It is one or more of in dioxane, acetone, butanone, cyclohexanone, methyl iso-butyl ketone (MIBK).
3. the synthetic method of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane according to claim 1, its feature
It is, double-deck shape oligomeric silsesquioxane four silanol of the structural formula as shown in (III) is with containing two silicon of reactive functionality two
The mass ratio of oxygen alkane is 1: 0.001~1.
4. the synthetic method of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane according to claim 1, its feature exists
In, double-deck shape oligomeric silsesquioxane four silanol and catalyst of the structural formula as shown in (III) mass ratio for 1: 0.001~
1。
5. the synthetic method of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane according to claim 1, its feature
It is, last handling process is recrystallization, precipitation, column chromatography or vacuum drying.
6. a kind of synthetic method of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane as claimed in claim 1 is obtained not
Symmetrical hydroxyl double-deck shape oligomeric silsesquioxane is in new poly- silica such as exploitation bead type, ladder-cage type, hyperbranched and big rings
Alkane, the application developed on novel coupling agent, exploitation novel catalyst carrier.
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| Nonacyclic Ladder Silsesquioxanes and Spectral Features of Ladder Polysilsesquioxanes;Masafumi Unno et al.;《International Journal of Polymer Science》;20121231;第2012卷;摘要，图1-3,第1页2.1节 * |
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