CN104672273A - Asymmetric double-deck and trapezoid polysilsesquioxane containing hydroxyl and synthesis method and application of asymmetric double-deck and trapezoid polysilsesquioxane - Google Patents

Abstract

The invention relates to the technical field of synthesis of oligomeric silsesquioxanes. In order to solve the problem that the synthesis of existing asymmetric polyhedral oligomeric silsesquioxanes mostly focuses on polyhedral oligomeric silsesquioxanes with two different functional groups on the left and right On the clathrate polyhedral oligomeric silsesquioxane with different functional groups on the upper and lower sides, there is a problem of random distribution of product functional groups in the synthesis. The present invention proposes an asymmetric hydroxyl-containing double deck and trapezoidal oligomeric Siloxane and its synthesis method and application, the asymmetric hydroxyl-containing double-decked and trapezoidal oligomeric silsesquioxanes have parallel hydroxyl groups on one side and other groups on the other side, and its structural formula is as (I), As shown in (II): The asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxane of the present invention has a wider application range, and the synthesis method has the advantages of mild reaction conditions, low energy consumption, high synthesis efficiency, simple and easy product purification process, and the like.

Description

Asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxanes and their synthesis methods and applications

technical field

The invention relates to the technical field of synthesis of oligomeric silsesquioxanes, in particular to novel asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxanes and their high-efficiency synthesis methods and applications.

Background technique

Asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxanes have important uses, such as the development of new polysiloxanes such as beaded, ladder-cage, trapezoidal, hyperbranched and macrocyclic; the development of new coupling agents; development of new catalyst supports, etc. There are two types of asymmetric oligomeric silsesquioxanes reported so far. The first asymmetric oligomeric silsesquioxane is a polyhedral oligomeric silsesquioxane with two different functional groups on the left and right, such as the paper published by Y.Kawakami et al. in Advanced Polymer Science (Advanced Polymer Science, 2011, 235, 185-228), introduced polyhedral oligomeric silsesquioxane with dimethylsiloxy group and cyclobutylsilyl group respectively, this asymmetric polyhedral oligomeric silsesquioxane can only be used for Synthesis of linear polymers has a limited range of applications, and the paper does not give characterization data for this asymmetric polyhedral oligosilsesquioxane. Another asymmetric oligomeric silsesquioxane is a cage polyhedral oligomeric silsesquioxane with different functional groups on the upper and lower sides. This type of asymmetric polyhedral oligomeric silsesquioxane is mostly composed of two Cyclotetrasiloxane tetrasilanols with different functional groups are obtained by co-condensation of raw materials, but polyhedral oligomeric silsesquioxanes with random functional groups are often produced during the synthesis process. For example, in the paper published by S. Tateyama et al. in Journal of Organometallic Chemistry (Journal of Organometallic Chemistry, 2010, 695, 898-902), 1,3,5,7-tetraphenyl-1,3,5,7- Tetrahydroxycyclotetrasiloxane and 1,3,5,7-tetradeuterophenyl-1,3,5,7-tetrahydroxycyclotetrasiloxane obtained two kinds of raw materials under the catalysis of quaternary ammonium base A clathrate polyhedral oligomeric silsesquioxane with random distribution of functional groups.

In short, the existing synthesis of asymmetric polyhedral oligomeric silsesquioxanes mostly focuses on polyhedral oligomeric silsesquioxanes with two different functional groups on the left and right sides and cage polyhedral oligomeric silsesquioxanes with different functional groups on the upper and lower sides. For silsesquioxane, there is a problem of random distribution of product functional groups in synthesis, and in application, it is only suitable for the development of linear polymers.

Contents of the invention

In order to solve the existing asymmetric polyhedral oligomeric silsesquioxane synthesis, most of them focus on polyhedral oligomeric silsesquioxane with two different functional groups on the left and right sides and cage polyhedral oligomeric polyhedral oligomeric silsesquioxane with different functional groups on the upper and lower sides. On the silsesquioxane, there is a problem of random distribution of product functional groups in the synthesis aspect. The present invention proposes an asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxane and its synthesis method and application. The present invention is not Symmetrical hydroxyl-containing double-decked and trapezoidal oligomeric silsesquioxanes have a wider range of applications, and the synthesis method has the advantages of mild reaction conditions, low energy consumption, high synthesis efficiency, and simple and easy product purification process.

The present invention is realized through the following technical solutions: asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxane, with parallel hydroxyl groups on one side and other groups on the other side, its structural formula is as shown in (I), (II) Show:

Wherein, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are independently selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic, epoxy, ester, sulfonic acid, carboxyl, One of nitrile, haloalkyl, haloalkenyl, haloalkynyl and hydroxyl.

The synthesis method of the described asymmetric hydroxyl-containing double-decked and trapezoidal oligomeric silsesquioxane comprises the following steps: the double-decked oligomeric silsesquioxane tetrasilanol or the structural formula shown in (III) As shown in (IV), cyclotetrasiloxane tetrasilanol and disiloxane containing two reactive functional groups are used as raw materials, and under the action of a catalyst, react in an organic solvent, and then undergo post-treatment process, respectively Obtain structural formula as shown in (I), (II) the asymmetry hydroxyl-containing double deck shape and trapezoidal oligomeric silsesquioxane, reaction process is as follows:

In the reaction formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are independently selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic, epoxy, ester, sulfonic acid, One of carboxyl, nitrile, haloalkyl, haloalkenyl, haloalkynyl, and hydroxyl, and X is independently selected from one of hydrogen, fluorine, chlorine, bromine, iodine, and alkoxy.

Preferably, the cyclotetrasiloxane tetrasilanol with the structural formula (IV) is selected from iso-cyclotetrasiloxane tetrasilanol or cis, trans, cis-cyclotetrasiloxane tetrasilanol.

The organic solvent is selected from one or more of alkanes, aromatic hydrocarbons, ethers, cyclic ethers, and ketones. Preferably, the organic solvent is selected from hexane, cyclohexane, toluene, chlorobenzene, 1,3, One or more of 5-trimethylbenzene, diethyl ether, butyl ether, tetrahydrofuran, 1,4-dioxane, acetone, butanone, cyclohexanone, and methyl isobutyl ketone. The amount of organic solvent used is that which dissolves the solute.

The catalyst is selected from one of inorganic ammonia, organic amine, quaternary ammonium base, metal element, metal oxide, metal salt, complex compound, as preferably, the catalyst is selected from ammonia, ammonia water, dimethylamine, diethylamine Amine, Trimethylamine, Triethylamine, Pyridine, Tetramethylammonium Hydroxide, Tetraethylammonium Hydroxide, Tetra-tert-Butylammonium Hydroxide and Iron, Cobalt, Nickel, Ruthenium, Rhodium, Platinum, Palladium, Osmium, Iridium, Gold , silver, copper, tin, zinc, titanium, pickaxe, chromium, manganese, and lanthanide metals as a single substance or a corresponding compound.

The mass ratio of the double-decked oligomeric silsesquioxane tetrasilanol with the structural formula as shown in (III) or the cyclotetrasiloxane tetrasilanol with the structural formula as shown in (IV) is 1: 0.001～1, The mass ratio to the disiloxane containing two reactive functional groups is 1:0.001-1.

Preferably, the reaction temperature is -20-140°C, and the reaction time is 30 minutes-24 hours.

Preferably, the post-treatment process is recrystallization, precipitation, column chromatography or vacuum drying.

In the present invention, a double-plate-shaped oligomeric silsesquioxane tetrasilanol with a structural formula such as (III) or a cyclotetrasiloxane tetrasilanol with a structural formula such as (IV) and a disiloxane containing two reactive functional groups Alkanes as raw materials, in the presence of inorganic ammonia, organic amines, quaternary ammonium bases or metal catalysts, condensation reactions or dehydrogenation/dealcoholization coupling reactions occur to achieve asymmetric hydroxyl-containing double deck and trapezoidal oligomeric silsesquioxane Efficient synthesis of alkanes, the yield can reach 60-95%. The structure of the product was characterized by infrared spectroscopy and hydrogen nuclear magnetic resonance spectroscopy. The infrared spectrum is consistent with the theoretically containing functional groups, and the hydrogen nuclear magnetic resonance spectrum is consistent with the theoretical proton number and chemical shift.

The asymmetric oligosilsesquioxane molecule of the present invention contains a variety of functional groups, which can be used to develop new polysiloxanes such as beaded, ladder-cage, trapezoidal, hyperbranched and macrocyclic; develop new coupling agents; Development of new catalyst supports, etc.

Compared with prior art, the beneficial effect of the present invention is:

(1) The synthesis method has the advantages of mild reaction conditions, low energy consumption, high synthesis efficiency, and simple and easy product purification process;

(2) The application scope of the asymmetric hydroxyl-containing double-decked and trapezoidal oligomeric silsesquioxanes of the present invention is wider.

Description of drawings

Fig. 1 is the infrared spectrogram of asymmetric hydroxyl-containing double deck type oligomeric silsesquioxane in embodiment 1;

Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the asymmetric hydroxyl-containing double-plate-shaped oligomeric silsesquioxane in embodiment 1;

FIG. 3 is an infrared spectrogram of the asymmetric hydroxyl-containing ladder-shaped oligomeric silsesquioxane in Example 2. FIG.

Detailed ways

Example 1: Preparation of asymmetric hydroxyl-containing double deck-shaped oligomeric silsesquioxane containing methyl, phenyl and hydrogen

At -20°C, 10 ml of 1,4-dioxane solution containing 3 g of 1,3-dimethyl-1,3-dichlorodisiloxane was slowly added dropwise to the side containing 3 g In a 50-milliliter three-neck flask containing two deck-shaped oligomeric silsesquioxane tetrasilanols whose base is phenyl, 3 grams of diethylamine and 10 milliliters of 1,4-dioxane, then stirred and reacted for 30 minutes, washed with water The organic layer was neutralized, dried by adding anhydrous sodium sulfate, and dried in vacuum to remove the solvent to obtain a white solid with a yield of 78%.

The infrared spectrum of the asymmetric hydroxyl-containing bidecyl oligomeric silsesquioxane containing methyl, phenyl and hydrogen is shown in Figure 1, and the asymmetric hydroxyl-containing bidecyl oligomeric silsesquioxane The H NMR spectrum of silsesquioxane is shown in Figure 2.

Example 2: Preparation of asymmetric hydroxyl-containing ladder-shaped oligosilsesquioxane containing methyl, phenyl and hydrogen

At a temperature of 60°C, 20 ml of tetrahydrofuran solution containing 2 g of 1,3-dimethyl-1,3-dichlorodisiloxane was slowly added dropwise to a trans-cyclone containing 200 g of pendant phenyl groups. Tetrasiloxane tetrasilanol, 2 g of triethylamine and 300 ml of tetrahydrofuran were placed in a 500 ml three-neck flask, then stirred and reacted for 8 hours, and after the reaction solution was lowered to room temperature, 300 ml of n-hexane was added, and the organic layer was washed with water to medium After drying by adding anhydrous sodium sulfate, the solvent was removed by vacuum drying to obtain a white solid with a yield of 85%.

The infrared spectrum of the asymmetric hydroxyl-containing ladder-shaped oligosilsesquioxane containing methyl, phenyl and hydrogen is shown in Figure 3.

Example 3: Preparation of asymmetric hydroxyl-containing double deck-shaped oligomeric silsesquioxane containing vinyl, ethyl acrylate and allyl groups

At a temperature of 90°C, a solution of 20 ml of methyl isobutyl ketone containing 16 g of 1,3-divinyl-1,3-diacrylate ethyl-1,3-dichlorodisiloxane was slowly dropped Add to a 500 ml three-neck flask containing 100 g of double-decked oligomeric silsesquioxane tetrasilanol, 0.1 g of tetramethylammonium hydroxide, and 200 ml of methyl isobutyl ketone , then stirred and reacted for 16 hours, and after cooling down to room temperature, the organic layer was washed with water until neutral, dried by adding anhydrous sodium sulfate, and dried in vacuum to remove the solvent to obtain a white solid with a yield of 78%.

Example 4: Preparation of asymmetric hydroxyl-containing double deck-shaped oligosilsesquioxane containing p-chloromethylphenyl, ethyl and hydrogen

At a temperature of 120°C, 20 ml of chlorobenzene solution containing 5 g of 1,3-bis(p-chloromethylphenyl)-1,3-dichlorodisiloxane was slowly added dropwise to a 50 g side Base is in the 500 milliliter three-neck flask of the double deck shape oligomeric silsesquioxane tetrasilanol of ethyl, 2 grams of pyridines and 100 milliliters of chlorobenzene, then stirred and reacted for 16 hours, after the reaction solution was down to room temperature, washed with water The organic layer was neutralized, dried by adding anhydrous sodium sulfate, and dried in vacuum to remove the solvent to obtain a white solid with a yield of 95%.

Example 5: Preparation of asymmetric hydroxyl-containing ladder-shaped oligomeric silsesquioxane containing vinyl, nitrile and allyl groups

At a temperature of 30°C, 10 ml of acetone solution containing 3 g of 1,3-divinyl-1,3-dicyano-1,3-dichlorodisiloxane was slowly added dropwise to a side with 30 g of cis, trans, cis-cyclotetrasiloxane tetrasilanol, 0.3 gram of ammonia water and 100 milliliters of acetone in a 500 milliliter three-necked flask whose base is allyl, then stirred and reacted for 20 hours, added 300 milliliters of n-hexane, and washed the organic layer to neutral, add anhydrous sodium sulfate to dry, pour the solution into methanol, a white solid precipitates, filter to obtain a white solid, and vacuum dry to obtain the target product with a yield of 65%.

Example 6: Preparation of asymmetric hydroxyl-containing bisdecyl oligosilsesquioxane containing 3-chloropropyl, naphthyl and hydrogen

At a temperature of 140°C, 50 ml of cyclohexanone solution containing 0.2 g of 1,3-bis(3-chloropropyl)-1,3-dichlorodisiloxane was slowly added dropwise to a solution containing 200 g of side groups. Be in the 1000 milliliter three-neck flask of the two-decked oligomeric silsesquioxane tetrasilanol of naphthyl, 20 gram tetra-tert-butylammonium hydroxides and 300 milliliters of cyclohexanone, then stirred and reacted for 24 hours, and the reaction solution was down to room temperature Finally, the organic layer was washed with water until neutral, dried by adding anhydrous sodium sulfate, the solution was poured into ethanol, a white solid was precipitated, the white solid was obtained by filtration and vacuum-dried to obtain the target product with a yield of 90%.

Example 7: Preparation of asymmetric hydroxyl-containing ladder-shaped oligomeric silsesquioxane containing phenyl, butyl and epoxy groups

At a temperature of 20°C, a solution of 60 ml of 1,4-dioxane containing 6 g of 1,3-diphenyl-1,3-dibutyl-1,3-dimethoxydisiloxane Slowly added dropwise to the 500 ml three-necked flask equipped with 30 g of pendant all-cis-cyclotetrasiloxane tetrasilanol, 3 g of palladium chloride and 60 ml of 1,4-dioxane, and then The reaction was stirred for 3 hours. After the reaction solution was cooled to room temperature, palladium chloride was removed by column chromatography, and the solvent was removed by vacuum drying to obtain a white solid with a yield of 81%.

Example 8: Preparation of asymmetric hydroxyl-containing double deck-shaped oligomeric silsesquioxanes containing epoxy groups, allyl groups and ethyl acrylate groups

At a temperature of 30°C, 60 ml of butanone solution containing 30 g of 1,3-diepoxy-1,3-diallyl-1,3-diethoxydisiloxane was slowly added dropwise to 50 grams of side groups are installed in the 250 milliliters three-necked flask of double-decked oligomeric silsesquioxane tetrasilanol, 3 grams of palladium/carbon and 60 milliliters of methyl ethyl ketone, then stirring and reacting for 15 hours, using Palladium/carbon was removed by column chromatography, and colorless crystals were obtained after recrystallization using ethanol as a solvent with a yield of 78%.

Example 9: Preparation of asymmetric hydroxyl-containing bisdecyl oligomeric silsesquioxane containing p-chloromethylphenyl, n-octyl and n-butyl

At a temperature of 10°C, 20 ml of 1 , 3,5-Trimethylbenzene solution was slowly added dropwise to 20 grams of n-butyl double deck-shaped oligomeric silsesquioxane tetrasilanol, 2 grams of chloroplatinic acid and 50 milliliters of 1,3 , in 250 milliliters of three-necked flasks of 5-trimethylbenzene, then stirred and reacted for 16 hours, after the reaction solution rose to room temperature, chloroplatinic acid was removed by column chromatography, and the solvent was dried in vacuum to obtain a white solid with a yield of 75%. .

Claims (10)

1. asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane, it is characterized in that, described double-deck shape is with trapezoidal oligomeric silsesquioxane while with parallel hydroxyl, and with other groups, its structural formula is as shown in (I), (II):

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of.

2. the synthetic method of an asymmetric hydroxyl double-deck shape as claimed in claim 1 and trapezoidal oligomeric silsesquioxane, it is characterized in that, described synthetic method be with double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or cyclotetrasiloxane four silanol of structural formula as shown in (IV) with the sily oxide containing two reactive functionality for raw material, and under the effect of catalyzer, react in organic solvent, again through last handling process, obtain structural formula respectively as (I), (II) the asymmetric hydroxyl double-deck shape shown in and trapezoidal oligomeric silsesquioxane, reaction process is as follows:

Wherein, R ₁, R ₂, R ₃, R ₄, R ₅separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of, X is separately selected from hydrogen, fluorine, chlorine, bromine, iodine, alkoxyl group a kind of.

3. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, it is characterized in that, cyclotetrasiloxane four silanol of structural formula as shown in (IV) is selected from complete in. cyclotetrasiloxane four silanol or suitable, anti-, suitable. cyclotetrasiloxane four silanol.

4. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, is characterized in that, organic solvent is selected from one or more in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone.

5. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 4 and trapezoidal oligomeric silsesquioxane, it is characterized in that, organic solvent is selected from hexane, hexanaphthene, toluene, chlorobenzene, 1,3,5. Three methyl Benzene, ether, butyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae. in dioxane, acetone, butanone, pimelinketone, methyl iso-butyl ketone (MIBK) one or more.

6. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, it is characterized in that, double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or cyclotetrasiloxane four silanol of structural formula as shown in (IV) are 1: 0.001 ~ 1 with the mass ratio containing two reactive functionality sily oxide.

7. the synthetic method of asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane according to claim 2, it is characterized in that, described catalyzer to be selected from inorganic ammonia, organic amine, quaternary ammonium hydroxide, metal simple-substance, metal oxide, metal-salt, complex compound a kind of, and the mass ratio of cyclotetrasiloxane four silanol as shown in (IV) of double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or structural formula and catalyzer is 1: 0.001 ~ 1.

8. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, is characterized in that, temperature of reaction is .20 ~ 140 DEG C, and the reaction times is 30 minutes ~ 24 hours.

9. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, is characterized in that, last handling process is recrystallization, precipitation, column chromatography or vacuum drying.

10. an asymmetric hydroxyl double-deck shape as claimed in claim 1 and trapezoidal oligomeric silsesquioxane are developing bead type, ladder. and cage type, trapezoidal, hyperbranched with new polysiloxanes such as large rings, development of new coupling agent, the application in development of new support of the catalyst.