CN114561015A - Dual-functional group T containing tetraene hexaphenyl10Cage-like silsesquioxane and preparation method thereof - Google Patents
Dual-functional group T containing tetraene hexaphenyl10Cage-like silsesquioxane and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000005672 tetraenes Chemical class 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 19
- FWARSGQTQWAOHZ-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetrahydroxy-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O[Si]1(O[Si](O[Si](O[Si](O1)(C=C)O)(C=C)O)(C=C)O)C=C FWARSGQTQWAOHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 10
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 7
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 7
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 7
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract 1
- 229960001545 hydrotalcite Drugs 0.000 abstract 1
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 22
- 238000001035 drying Methods 0.000 description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000002274 desiccant Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VEPTXBCIDSFGBF-UHFFFAOYSA-M tetrabutylazanium;fluoride;trihydrate Chemical compound O.O.O.[F-].CCCC[N+](CCCC)(CCCC)CCCC VEPTXBCIDSFGBF-UHFFFAOYSA-M 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- -1 vinyl phenyl Chemical group 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
Abstract
The invention belongs to the technical field of organic-inorganic nano hybrid materials, and discloses a bifunctional T containing tetraethylene hexaphenyl10Disclosed are a cage-like silsesquioxane and a preparation method thereof. Dissolving vinyl triethoxysilane in isopropanol, and adding into mixed solution containing potassium methoxide and water to obtain tetrahydroxy tetravinylcyclotetrasiloxane; dissolving the above-mentioned raw material in 1, 4-dioxane, adding phenylsilane, catalyst and inert gas protection to make them produce reaction so as to obtain the invented product containing tetraene hexaphenyl bifunctional group T10A cage silsesquioxane. The invention has simple reaction process, definite product structure and excellent solubility in common solvents, and can be applied to inorganic materials such as intercalation modified montmorillonite, hydrotalcite and the like to increase the interlayer spacing and the like.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic nano hybrid materials, and particularly relates to a dual-functional group T containing tetraene hexaphenyl10Disclosed are a cage-like silsesquioxane and a preparation method thereof.
Background
Cage-like silsequioxanes (CSQ, also called polyhedral oligomeric silsesquioxane) are nano-sized organic-inorganic hybrid closed siloxane molecular clusters formed by inorganic frameworks (cores) formed by two-dimensional Si-O-Si short chains and organic substituents bonded on the Cage-like frameworks, and the general formula of the Cage-like silsesquioxane is [ RSiO1.5]n(n is 4, 6, 8, 10, 12, etc.). Where n determines its cage topology, according to which n isMay be also referred to as T for short6、T8、T10Etc.; the R group can be an inert group or an active group, and the groups are combined with silicon atoms at the vertex angle by a chemical reaction covalent bond to ensure good compatibility of CSQ molecules and organic macromolecules, simultaneously have the performance characteristics of inorganic materials, and are commonly used for constructing inorganic/organic nano composite materials. Currently, CSQ is widely used in various fields such as biomedicine, paint, optical material, porous material, low dielectric material, liquid crystal material, and the like. However, most of the currently used CSQ are monofunctional groups, and cannot meet the requirements of various applications at the same time, so how to controllably synthesize bifunctional or polyfunctional CSQ with an exact structure, and further construct multifunctional materials is of great significance and has led researchers to make extensive research.
In the CSQ structure, the R substituents are not simultaneously referred to as bifunctional or polyfunctional polyhedral silsesquioxanes HFSQ (Hetero-functional silsquioxanes). For the synthesis research report of HFSQ, the main synthesis methods include a silane mixed hydrolysis condensation method, a functional group partial conversion derivation method, a 'vertex angle-capping' method, a co-condensation method of different semi-cage structures and the like. However, the synthesis methods cannot control the determined positions and the accurate numbers of different R groups on the cage-shaped molecules, and most of the obtained products are mixed homologues, so that the yield is low, and the separation and purification are difficult, so that an experimental scheme needs to be improved to obtain the heterofunctional group cage-shaped silsesquioxane with a specific structure.
At present, cyclotetrasiliconate is adopted as a reaction platform, trichlorosilane is continuously utilized to grow on the reaction platform, and the bifunctional cage-like silsesquioxane can be obtained through condensation reaction.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a tetravinyl hexaphenyl bifunctional T10Disclosed are a cage-like silsesquioxane and a preparation method thereof.
The purpose of the scheme is realized by the following scheme:
bifunctional group containing tetraene hexaphenylT10The preparation method of the cage-like silsesquioxane comprises the following steps:
(3) tetrahydroxy tetravinylcyclotetrasiloxane (Vi-T)4) The synthesis of (2): mixing vinyl triethoxy siloxane (VTES) with an organic solvent, potassium methoxide and water, reacting at room temperature, adding hydrochloric acid for continuous reaction after the reaction is finished, and filtering and rotary-steaming to remove the solvent after the reaction is finished to obtain tetrahydroxy tetravinylcyclotetrasiloxane;
(4) tetravinyl hexaphenyl-containing bifunctional group T10Synthesis of cage-type silsesquioxane: mixing a phenyl silane monomer with an organic solvent, the tetrahydroxy tetravinylcyclotetrasiloxane obtained in the step (1), potassium methoxide and water, adding a fluorine ion catalyst, carrying out heating reaction under the protection of inert gas, and separating and purifying after the reaction is finished to obtain the T-shaped polymer containing the tetraene hexaphenyl bifunctional group10A cage silsesquioxane.
Preferably, the organic solvent in step (1) is at least one of isopropyl alcohol, acetone, N-dimethylformamide and the like. The molar volume ratio of the vinyl triethoxy siloxane to the organic solvent is 80-120 mmol: 20ml, preferably 100 mmol: 20 ml.
Preferably, the molar ratio of the vinyltriethoxysilane to the potassium methoxide to the water in the step (1) is 1: 1-3, preferably 1:1: 1.
Preferably, the reaction time in step (1) is 24-48 h.
After the hydrochloric acid is added in the step (1), the pH value of the solution is 1-4, and the solution is preferably 3.
And (2) adding hydrochloric acid to continue the reaction for 15-30 h.
Preferably, the phenyl silane monomer in step (2) is at least one of Phenyl Trimethoxysilane (PTMS), Phenyl Triethoxysilane (PTES) and Phenyl Trichlorosilane (PTCS).
Preferably, the organic solvent in step (2) is 1, 4-dioxane. The molar volume ratio of the tetrahydroxy tetravinylcyclotetrasiloxane to the organic solvent is 1 mmol: 5-15 ml, preferably 1 mmol: 10 ml.
Preferably, the molar mass ratio of the phenyl silane monomer, the tetrahydroxy tetravinylcyclotetrasiloxane, the potassium methoxide and the water in the step (2) is 62 mmol: 8-12 mmol: 2-3 g: 1-3 g, preferably 62 mmol: 10 mmol: 2.3 g: 2g of the total weight.
Preferably, the fluoride ion catalyst in step (2) is at least one of tetramethylammonium fluoride, tetraethylammonium fluoride and benzyltrimethylammonium fluoride.
Preferably, the amount of the catalyst used in step (2) is 0.1 to 3.0% of the sum of the molar amounts of the tetrahydroxytetravinylcyclotetrasiloxane and the phenylsilane monomer.
Preferably, the heating reaction in the step (2) is carried out under the condition of 30-60 ℃ for 24-48 h.
Preferably, the method for separating and purifying in step (2) is: and after the reaction is finished, adding anhydrous calcium chloride into the reaction liquid to remove the fluoride ion catalyst in the reaction liquid, filtering to remove calcium fluoride precipitate and excessive anhydrous calcium chloride, and performing rotary evaporation to remove the solvent to obtain the product.
Dual-functional group T containing tetraene hexaphenyl10Cage-like silsesquioxane, prepared by the above method.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the method has simple reaction process, can react at room temperature and near room temperature, takes (3) tetrahydroxy tetravinylcyclotetrasiloxane as a reaction platform, utilizes a special space two-dimensional platform structure unique to the (3) tetrahydroxy tetravinylcyclotetrasiloxane, guides a second monomer to grow on a template of the (3) tetrahydroxy tetravinylcyclotetrasiloxane in a condensation reaction mode, realizes controllable synthesis of vinyl phenyl difunctional group CSQ, has higher safety and simple post-treatment, and has the yield of the obtained product of more than 40 percent.
(2) The synthesized tetravinyl hexaphenyl-containing bifunctional group T10The cage-shaped silsesquioxane has an exact cage-shaped structure, the position and the number of functional groups on the cage are determined, and the cage-shaped silsesquioxane has excellent solubility in common solvents such as dichloromethane, ethyl acetate, acetone, tetrahydrofuran, toluene, acetonitrile, chloroform and the like.
Drawings
FIG. 1 shows the preparation route of the synthetic method of the present invention.
FIG. 2 is an IR spectrum of the product obtained in example 2 of the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the product obtained in example 2 of the present invention.
FIG. 4 is a nuclear magnetic carbon spectrum of the product obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The room temperature and the unspecified temperature are both 20-35 ℃.
Example 1
(1) Adding 7g of CH3OK (100mmol) was placed in a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H were added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; filtering after the reaction is finished, adding anhydrous magnesium sulfate, drying overnight, filtering, evaporating in a rotary manner, and drying in vacuum to obtain viscous yellow transparent liquid, namely vinyl T4(as shown in formula I):
(2) the T obtained in the step (1) is43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced2And then 12.3g (62mmol) of Phenyltrimethoxysilane (PTMS) added into the constant-pressure funnel is slowly added into the flask, 0.14g (0.146mmol) of tetramethylammonium fluoride as a catalyst is simultaneously added, the mixture reacts for 24 hours at the temperature of 40 ℃ after the dropwise addition is finished, and after the reaction is finished, the anhydrous calcium chloride fluoride ion removal catalyst is added at the room temperature, and the reaction is continued for 12 hours. Filtering to remove the generated calcium fluoride precipitate and excessive anhydrous calcium chloride, collecting filtrate, adding anhydrous magnesium sulfate, drying overnight, and filtering to removeDrying with a drying agent, evaporating and drying at 80 ℃ in vacuum to obtain a light yellow solid. Dissolving the obtained solid with a very small amount of dichloromethane, recrystallizing and separating the product by using normal hexane, collecting the recrystallized product, drying to obtain white solid powder, wherein the yield of the product is about 40 percent, and the white solid powder is the tetravinyl hexaphenyl bifunctional T10Cage silsesquioxane (as shown in formula II):
example 2
(1) Adding 7g of CH3OK (100mmol) was placed in a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H were added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; filtering after the reaction is finished, adding anhydrous magnesium sulfate, drying overnight, filtering, rotatably steaming, and vacuum drying to obtain viscous yellow transparent liquid, namely vinyl T4；
(2) The T obtained in the step (1) is43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced2And then 14.9g (62mmol) of Phenyltriethoxysilane (PTES) added into the constant-pressure funnel is slowly added into the flask, 0.063g (0.2mmol) of tetrabutylammonium fluoride trihydrate serving as a catalyst is added at the same time, the mixture reacts for 24 hours at 40 ℃ after the dropwise addition is finished, and after the reaction is finished, anhydrous calcium chloride fluoride ion removal catalyst is added at room temperature, and the reaction is continued for 12 hours. The resulting calcium fluoride precipitate and excess anhydrous calcium chloride were removed by filtration, the filtrate was collected and dried over night with anhydrous magnesium sulfate, filtered to remove the desiccant and dried under rotary evaporation vacuum at 80 ℃ to give a pale yellow solid. Dissolving the obtained solid with a small amount of dichloromethane, recrystallizing and separating the product by using normal hexane, collecting the recrystallized product, drying to obtain white solid powder, wherein the yield of the product is about 51 percent, namely the product containing the tetraene hexaphenyl bifunctional T10A cage silsesquioxane.
Example 3
(1) Adding 7g of CH3OK (100mmol) was placed in a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H were added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; filtering after the reaction is finished, adding anhydrous magnesium sulfate, drying overnight, filtering, rotatably steaming, and vacuum drying to obtain viscous yellow transparent liquid, namely vinyl T4；
(2) The T obtained in the step (1)43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced2And then 15.6g (65mmol) of Phenyltriethoxysilane (PTES) which is added into the constant-pressure funnel is slowly added into the flask, 0.25g (1.5mmol) of benzyltrimethylammonium fluoride which is a catalyst is added at the same time, the mixture reacts for 24 hours at the temperature of 60 ℃ after the dropwise addition is finished, and after the reaction is finished, the anhydrous calcium chloride fluoride ion removal catalyst is added at the room temperature, and the reaction is continued for 12 hours. The resulting calcium fluoride precipitate and excess anhydrous calcium chloride were removed by filtration, the filtrate was collected and dried over night with anhydrous magnesium sulfate, filtered to remove the desiccant and dried under rotary evaporation vacuum at 80 ℃ to give a pale yellow solid. Dissolving the obtained solid with a small amount of dichloromethane, recrystallizing and separating the product by using normal hexane, collecting the recrystallized product, drying to obtain white solid powder, wherein the yield of the product is about 41 percent, namely the product containing the tetraene hexaphenyl bifunctional T10A cage silsesquioxane.
Example 4
(1) 7g of CH3OK (100mmol) was placed in a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H were added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; after the reaction is finishedFiltering, adding anhydrous magnesium sulfate, drying overnight, filtering, rotary steaming, and vacuum drying to obtain viscous yellow transparent liquid, i.e. vinyl T4；
(2) The T obtained in the step (1) is43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced213.8g (65mmol) of Phenyltrichlorosilane (PTCS) added into the constant-pressure funnel is slowly added into the flask, 0.25g (1.5mmol) of benzyltrimethylammonium fluoride serving as a catalyst is simultaneously added, the mixture reacts for 24 hours at 40 ℃ after the dropwise addition is finished, and after the reaction is finished, an anhydrous calcium chloride fluoride ion removal catalyst is added at room temperature, and the reaction is continued for 12 hours. The resulting calcium fluoride precipitate and excess anhydrous calcium chloride were removed by filtration, the filtrate was collected and dried over night with anhydrous magnesium sulfate, filtered to remove the desiccant and dried under rotary evaporation vacuum at 80 ℃ to give a pale yellow solid. Dissolving the obtained solid with a small amount of dichloromethane, recrystallizing and separating the product by using normal hexane, collecting the recrystallized product, drying to obtain white solid powder, wherein the yield of the product is about 43 percent, namely the product containing the tetraene hexaphenyl bifunctional T10A cage silsesquioxane.
Example 5
(1) Adding 7g of CH3OK (100mmol) was placed in a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H were added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; filtering after the reaction is finished, adding anhydrous magnesium sulfate, drying overnight, filtering, rotatably steaming, and vacuum drying to obtain viscous yellow transparent liquid, namely vinyl T4；
(2) The T obtained in the step (1) is43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced215.6g (65mmol) of Phenyltrichlorosilane (PTCS) charged in a constant pressure funnel was slowly charged into the flask while 0.32g (1.0 m) of tetrabutylammonium fluoride trihydrate as a catalyst was addedmol), reacting for 24 hours at 40 ℃ after the dropwise addition is finished, adding an anhydrous calcium chloride fluoride ion removal catalyst at room temperature after the reaction is finished, and continuing the reaction for 12 hours. The resulting calcium fluoride precipitate and excess anhydrous calcium chloride were removed by filtration, the filtrate was collected and dried over night with anhydrous magnesium sulfate, filtered to remove the desiccant and dried under rotary evaporation vacuum at 80 ℃ to give a pale yellow solid. Dissolving the obtained solid with a small amount of dichloromethane, recrystallizing and separating the product by using normal hexane, collecting the recrystallized product, drying to obtain white solid powder, wherein the yield of the product is about 42 percent, namely the product containing the tetraene hexaphenyl bifunctional T10A cage silsesquioxane.
Example 6
(1) Adding 7g of CH3OK (100mmol) was placed in a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H were added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; filtering after the reaction is finished, adding anhydrous magnesium sulfate, drying overnight, filtering, rotatably steaming, and vacuum drying to obtain viscous yellow transparent liquid, namely vinyl T4；
(2) The T obtained in the step (1) is43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced2And then 14.9g (62mmol) of Phenyltriethoxysilane (PTES) added into the constant-pressure funnel is slowly added into the flask, 0.32g (1.0mmol) of tetrabutylammonium fluoride trihydrate catalyst is added at the same time, the mixture reacts for 24 hours at 50 ℃ after the dropwise addition is finished, and after the reaction is finished, anhydrous calcium chloride fluoride ion removal catalyst is added at room temperature, and the reaction is continued for 12 hours. The resulting calcium fluoride precipitate and excess anhydrous calcium chloride were removed by filtration, the filtrate was collected and dried over night with anhydrous magnesium sulfate, filtered to remove the desiccant and dried under rotary evaporation vacuum at 80 ℃ to give a pale yellow solid. Dissolving the obtained solid with a small amount of dichloromethane, recrystallizing and separating the product with n-hexane, collecting the recrystallized product, drying to obtain white solid powder with high product yieldAbout 41 percent, namely the tetravinyl hexaphenyl-containing bifunctional group T10A cage silsesquioxane.
Example 7
(1) Adding 7g of CH3OK (100mmol) was charged into a 250ml single-neck flask, and 90ml of isopropyl alcohol, 1.8ml of H, was added2O (100mmol), the reaction system is white turbid; adding 19g (100mmol) of vinyltriethoxysilane and 20ml of isopropanol which are added into a constant pressure funnel slowly dropwise into the flask, reacting for 24h at room temperature for about 10 min; continuously dropwise adding concentrated hydrochloric acid into the reaction bottle until the pH value is about 3, and reacting for 24 hours; filtering after the reaction is finished, adding anhydrous magnesium sulfate, drying overnight, filtering, rotatably steaming, and vacuum drying to obtain viscous yellow transparent liquid, namely vinyl T4；
(2) The T obtained in the step (1) is43.5g (10mmol) and 100ml 1, 4-dioxane were placed in a 500ml three-neck flask, 2.3g potassium methoxide and 2g water were added, and dissolved by stirring, and N was introduced2And then 12.9g (65mmol) of Phenyltrimethoxysilane (PTMS) added into a constant pressure funnel is slowly added into the flask, 0.25g (1.5mmol) of benzyltrimethylammonium fluoride as a catalyst is added at the same time, the mixture reacts at 40 ℃ for 24 hours after the dropwise addition is finished, an anhydrous calcium chloride fluoride ion removal catalyst is added at room temperature after the reaction is finished, the reaction is continued for 12 hours, the generated calcium fluoride precipitate and excessive anhydrous calcium chloride are removed by filtration, the filtrate is collected and added with anhydrous magnesium sulfate for drying overnight, a drying agent is removed by filtration, and the mixture is dried at 80 ℃ in rotary evaporation vacuum to obtain a light yellow solid. Dissolving the obtained solid with a small amount of dichloromethane, recrystallizing and separating the product by using normal hexane, collecting the recrystallized product, drying to obtain white solid powder, wherein the yield of the product is about 40 percent, namely the product containing the tetraene hexaphenyl bifunctional T10A cage silsesquioxane.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications, etc., which are made without departing from the spirit and principle of the present invention, are all equivalent substitutions and are included in the protection scope of the present invention.
Claims (10)
1. Dual-functional group T containing tetraene hexaphenyl10The preparation method of the cage-like silsesquioxane is characterized by comprising the following steps:
(1) synthesis of tetrahydroxy tetravinylcyclotetrasiloxane: mixing vinyl triethoxy siloxane with an organic solvent, potassium methoxide and water, reacting at room temperature, adding hydrochloric acid for continuous reaction after the reaction is finished, and filtering and rotary-steaming to remove the solvent after the reaction is finished to obtain tetrahydroxy tetravinylcyclotetrasiloxane;
(2) tetravinyl hexaphenyl-containing bifunctional group T10Synthesis of cage-type silsesquioxane: mixing a phenyl silane monomer with an organic solvent, the tetrahydroxy tetravinylcyclotetrasiloxane obtained in the step (1), potassium methoxide and water, adding a fluorine ion catalyst, carrying out heating reaction under the protection of inert gas, and separating and purifying after the reaction is finished to obtain the T-shaped polymer containing the tetraene hexaphenyl bifunctional group10A cage silsesquioxane.
2. The method of claim 1, wherein: the molar volume ratio of the vinyl triethoxy siloxane to the organic solvent is 80-120 mmol: 20ml of the solution;
the molar ratio of the vinyl triethoxy siloxane to the potassium methoxide to the water in the step (1) is 1: 1-3.
3. The method of claim 1, wherein:
the reaction time in the step (1) is 24-48 h; after the hydrochloric acid is added in the step (1), the pH value of the solution is 1-4; and (2) adding hydrochloric acid in the step (1) and continuously reacting for 15-30 h.
4. The method of claim 1, wherein: in the step (2), the phenyl silane monomer is at least one of phenyl trimethoxy silane, phenyl triethoxy silane and phenyl trichlorosilane.
5. The method of claim 1, wherein: the molar volume ratio of the tetrahydroxy tetravinylcyclotetrasiloxane to the organic solvent is 1 mmol: 5-15 ml.
6. The method of claim 1, wherein: in the step (2), the molar mass ratio of the phenyl silane monomer, the tetrahydroxy tetravinylcyclotetrasiloxane, the potassium methoxide and the water is 62 mmol: 8-12 mmol: 2-3 g: 1-3 g.
7. The method of claim 1, wherein: in the step (2), the fluoride ion catalyst is at least one of tetramethylammonium fluoride, tetraethylammonium fluoride and benzyltrimethylammonium fluoride; the dosage of the catalyst in the step (2) is 0.1 to 3.0 percent of the sum of the molar weight of the tetrahydroxy tetravinylcyclotetrasiloxane and the molar weight of the phenyl silane monomer.
8. The method of claim 1, wherein: the heating reaction condition in the step (2) is that the reaction time is 24-48h at the temperature of 30-60 ℃.
9. The method of claim 1, wherein: the organic solvent in the step (1) is at least one of isopropanol, acetone and N, N-dimethylformamide; in the step (2), the organic solvent is 1, 4-dioxane.
10. Dual-functional group T containing tetraene hexaphenyl10A cage silsesquioxane prepared by the method of any one of claims 1 to 9.
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