CN101220052A - A kind of preparation method of silsesquioxane with acid anhydride group in the top angle - Google Patents

Abstract

The invention discloses a preparation method of silsesquioxane with an acid anhydride group at the top angle, relating to a preparation method of a compound. Provided is a method for preparing silsesquioxane with anhydride groups at the top angle by adopting "top angle-capping" and multi-step functional group conversion method. Dissolve trihydroxyheptaR-based heptapolysiloxane 1 and triethylamine in tetrahydrofuran, add tetrachlorosilane, remove triethylamine hydrochloride, and remove the solvent to obtain the product monochloroheptaR-based octapolysilsesquioxane 2. Then add THF/H ₂ O to reflux to remove the solvent to obtain the product hydroxyhepta-R-based octasilsesquioxane 3, and react with dimethyl monochlorosilane and Et ₃ N to remove Et ₃ N·HCl, The solid obtained after the filtrate was desolvated was dissolved in THF, and the THF phase was filtered to remove the solvent to obtain dimethylsiloxyhepta-R-based octasilsesquioxane 4, which was dissolved in toluene with an acid anhydride for catalysis, and the solvent was removed to obtain a precipitate and Soluble in acetic acid and toluene, reflux, remove the solvent from the filtrate, and dry to obtain the product.

Description

A kind of preparation method of silsesquioxane with acid anhydride group in the top angle

technical field

The invention relates to a method for preparing a compound, in particular to a method for preparing a silsesquioxane with an acid anhydride group at the vertex.

Background technique

Silsesquioxane has the general molecular structure formula: (RSiO _1.5 )n, and exists in different structural forms such as random, ladder, bridge, and cage. Among them, silsesquioxanes with trapezoidal structure and cage structure have attracted extensive attention, especially oligomeric cage silsesquioxane (POSS) with hexahedral structure has become a research hotspot in recent years.

POSS contains a polyhedral silicon-oxygen nanostructure framework whose molecular structure is shown below:

According to the size of the R group, the size of POSS is about 1.5-3 nm, the molecular weight is about 1000, and it has a cage structure. It has two notable features: (1) The ratio of the number of silicon-oxygen atoms in the POSS molecule is 1.5, which is a type of hybrid between silicon dioxide SiO ₂ and silicone resin R ₂ SiO; (2) POSS molecular size and The polymer segments or coils are of comparable size.

POSS is an organic-inorganic hybrid material, which not only has the superior properties of the organic and inorganic components, but also has the characteristics of the synergistic effect of the two. When the organic group (R) on POSS is non-reactive, it can be used as a reinforcing material for the resin system, and POSS can achieve molecular level dispersion in the hybrid system; when POSS has reactive functional groups, copolymerization can occur Or self-polymerization to generate organic-inorganic hybrid homopolymers or copolymers.

At present, the synthesis of monofunctional POSS compounds mainly has the following two routes:

(1) The "top angle-capping" method refers to the reaction of chlorosilane containing the desired functional group with incompletely hydrolyzed POSS trisilanol to obtain completely hydrolyzed POSS. The "angle-capping" method can be used to synthesize a variety of functionalized POSS, and the reaction yield is high and the cycle is short. It is an important functionalization method. Song Xiaoyan et al. (Song Xiaoyan, Li Qifang, Synthesis and Characterization of Magnetic Polyhedral Oligomeric Silsesquioxane (POSS) and its Polystyrene/POSS Nanocomposite, Doctoral Dissertation, Beijing University of Chemical Technology, 2006) used cyclopentyltrichlorosilane As a raw material, trihydroxyheptacyclopentyl heptapolysiloxane (T ₇ ) was prepared by hydrolysis and condensation. T ₇ and 4-chlorobenzyltrichlorosilane obtained 4-chlorobenzylcyclopentyl POSS through the "top angle-capping" reaction, then reacted with triphenylphosphine, and then reacted with ferrocene formaldehyde to synthesize a compound containing Magnetic polyhedral oligomeric silsesquioxane 4-(2-ferrocenylvinyl)-phenylcyclopentyl compounds of metals and double bonds.

(2) Functional group conversion method refers to the method of converting POSS containing functional groups into required functional groups through organic chemical methods. This method adopts different synthetic methods due to the difference of required functional groups, and the yields are also different. Because some POSS containing common functional groups have been commercialized, this method has become the main method of POSS functionalization. Zhang Lipei (Zhang Lipei, Li Qifang, Synthesis and Characterization of Functionalized Caged Silsesquioxane (POSS) and Its Properties of Epoxy Resin Composite Materials, Master Thesis, Beijing University of Chemical Technology, 2004) synthesized 1-phenyl-3, 5,7,9,11,13,15-heptacyclopentyl pentacyclo-[9.5.1.13.9.15,15.17.13]octapolysilsesquioxane, and then nitrated with fuming nitric acid to obtain 1-(2( 4) Nitrophenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.13.9.15, 15.17.13]octasilsesquioxane.

However, the above two methods generally can only synthesize POSS with basic or neutral groups in the vertex.

Contents of the invention

The purpose of the present invention is to provide a method for preparing silsesquioxane with anhydride groups in the apex using the "top angle-capping" and multi-step functional group conversion method.

The synthetic route of the present invention is as follows:

Concrete steps of the present invention are as follows:

1) Under a dry nitrogen atmosphere, dissolve trihydroxyheptapylheptapolysiloxane 1 and triethylamine (Et ₃ N) in tetrahydrofuran (THF), add tetrachlorosilane (SiCl ₄ ), and remove triethylamine Amine hydrochloride (Et ₃ N HCl), vacuumize to remove the solvent, collect the white precipitate after drying, and obtain the product monochloroheptaR-based octapolysilsesquioxane (POSS-Cl) 2; in molar ratio, trihydroxy Seven R group heptapolysiloxane: tetrachlorosilane: triethylamine is 1: (1~2): (3~3.5);

2) Add chloroheptaR-based octapolysilsesquioxane (POSS-Cl)2 into THF/H ₂ O to reflux and stir, and remove the solvent in a vacuum to obtain the product hydroxyl hepta-R-based octapolysilsesquioxane (POSS-Cl) -OH) 3; By volume ratio, the volume ratio of THF and deionized water is 2: 1;

3) Under the protection of vacuum or nitrogen, mix and react hydroxyl hepta-R-based octasilsesquioxane (POSS-OH)3, dimethyl monochlorosilane (ClSi(CH ₃ ) ₂ H) and Et ₃ N, and filter Et ₃ N HCl was removed, the filtrate was vacuumized to remove the solvent, and the solid obtained was dissolved in THF, and then washed with deionized water, HCl, and NaCl solution respectively. After liquid separation, the THF phase was dried with MgSO ₄ , filtered, and the filtrate was vacuumized to remove solvent to obtain the product dimethylsiloxyl seven R base octasilsesquioxane 4; in molar ratio, hydroxyl seven R base octasilsesquioxane: dimethyl monochlorosilane: triethylamine is 1 :(1～2):(1～2);

4) Under the protection of argon, dissolve dimethylsiloxyheptyl octasilsesquioxane 4 in toluene together with acid anhydride, add 0.2mol% Karstedt's reagent for catalytic reaction, and remove the solvent by vacuuming , to remove unreacted acid anhydride, after washing with acetone, a solid precipitate was obtained, the precipitate was dissolved in anhydrous acetic acid and toluene, added activated carbon to reflux, filtered, the filtrate was evacuated to remove the solvent, and dried to obtain the final product with an anhydride group. Silsesquioxane 5 with hepta-R base and octa-silsesquioxane 5; in molar ratio, the ratio of dimethylsiloxy-7-R-base and octa-silsesquioxane::acid anhydride is 1:(1～1.5).

In step 1), the R group in the trihydroxyheptaR group heptapolysiloxane can be methyl, ethyl, propyl, isobutyl, phenyl, cyclohexyl, cyclopentyl or vinyl, etc.; It is best to stir for 10-16 hours after adding tetrachlorosilane (SiCl ₄ ).

In step 3), the temperature for mixing and reacting hydroxyhepta-R-based octasilsesquioxane (POSS-OH)3, dimethylmonochlorosilane (ClSi(CH ₃ ) ₂ H) and Et ₃ N is the best The temperature is 60°C, and the reaction time is preferably 16-20 hours; the concentration of HCl is preferably 1mol/L, and the NaCl solution is preferably a saturated NaCl solution.

In step 4), the acid anhydride can be tetrahydrophthalic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride or chlorendic anhydride, etc.; the temperature of the catalytic reaction is the best The best time for catalytic reaction is 20-26 hours; after vacuuming to remove the solvent, it is best to heat up to 200 °C, and then remove unreacted anhydride; the best time for adding activated carbon to reflux is 2-3 hours.

The present invention adopts "vertex-capping" and multi-step functional group conversion method, and uses Karstedt's reagent as a catalyst to carry out the addition reaction of silicon hydrogen, which is carried out step by step and purified multiple times. The synthesized POSS-acid anhydride with acid anhydride group at the top angle can be used as a curing agent for epoxy resin system, which can cure, nano-toughen and increase the thermal decomposition temperature of epoxy resin.

Detailed ways

Below by embodiment the present invention will be further described.

Example 1

Step 1. Put 0.930 g of trihydroxyheptaphenylheptapolysiloxane into a two-necked bottle, seal it, and repeatedly vacuumize and blow nitrogen to replace it 3 times. 0.303g of Et ₃ N was dissolved in 20ml of THF and injected into a two-neck bottle, and 0.170g of SiCl ₄ was slowly added at room temperature. After stirring for 12 hours at room temperature, remove triethylamine hydrochloride (Et ₃ N·HCl) by filtration, vacuumize the filtrate to remove the solvent, collect the white precipitate after drying, and obtain the product monochloroheptaphenyl octasilsesquioxane .

Step 2. Add the above product monochloroheptaphenyl octasilsesquioxane into 30ml THF/H ₂ O, stir under reflux for 18 hours, and remove the solvent in vacuo to obtain the product hydroxyheptaphenyl octasilsesquioxane. Wherein the volume ratio of THF to deionized water is 2:1.

Step 3. Take another two-neck bottle, put the above-mentioned product hydroxyheptaphenyloctasilsesquioxane in it, seal it, vacuumize it, blow nitrogen, and replace it repeatedly 3 times. 0.095g of ClSi(CH ₃ ) ₂ H, 0.101g of Et ₃ N and 20ml of THF were mixed, and slowly injected into a two-neck bottle. React at 60°C for 18 hours, remove Et ₃ N·HCl by filtration, vacuumize the filtrate to remove the solvent, dissolve the solid in THF, wash with deionized water, 1mol/L HCl, and saturated NaCl solution respectively, and separate the liquid, The THF phase was dried over MgSO ₄ to remove water, filtered, and the solvent was removed in vacuo to give the product dimethylsiloxyheptaphenyloctasilsesquioxane.

Step 4. Put the reaction product dimethylsiloxyheptaphenyloctasilsesquioxane in another two-neck bottle, seal it, vacuumize it, and blow it with argon gas, and replace it three times. 0.152g of tetrahydrophthalic anhydride was dissolved in 20ml of toluene and slowly injected into a two-neck bottle, and 0.2mol% Karstedt's catalyst was added with a micro injector. After reacting at 75°C for 24 hours, vacuumize to remove the solvent, raise the temperature to 200°C to remove unreacted anhydrides, wash with acetone to obtain a solid precipitate, dissolve the precipitate in anhydrous acetic acid and toluene, add activated carbon to reflux for 2 hours, filter, and vacuumize the filtrate The solvent is removed and dried to obtain the final product of dimethylsiloxyheptaphenyloctasilsesquioxane with acid anhydride groups.

Example 2: Similar to Example 1, the difference is that the reactant in step 1 is replaced by trihydroxyheptaethylheptapolysiloxane, the addition amount is 0.594g, and the rest of the conditions remain unchanged.

Example 3

Step 1. Put 0.790 g of trihydroxyheptaisobutylheptapolysiloxane into a two-necked bottle, seal it, and repeatedly vacuumize and blow nitrogen to replace it 3 times. 0.354g of Et ₃ N was dissolved in 20ml of THF and injected into a two-neck bottle, and 0.204g of SiCl ₄ was slowly added at room temperature. After stirring for 10 h at room temperature, Et ₃ N·HCl was removed by filtration, the filtrate was vacuumed to remove the solvent, and the white precipitate was collected after drying to obtain the product monochloroheptaisobutyloctasilsesquioxane.

Step 2. Add the above product monochloroheptaisobutyl octasilsesquioxane into 30ml THF/H ₂ O, stir under reflux for 10 hours, and remove the solvent in vacuo to obtain the product hydroxyheptaisobutyl octasilsesquioxane. Wherein the volume ratio of THF to deionized water is 2:1.

Step 3. Take another two-neck bottle, put the above-mentioned product hydroxyheptaisobutyloctasilsesquioxane in it, seal it, vacuumize it, blow nitrogen, and replace it repeatedly 3 times. 0.095g of ClSi(CH ₃ ) ₂ H, 0.101g of Et ₃ N and 20ml of THF were mixed, and slowly injected into a two-neck bottle. React at 60°C for 16 hours, remove Et ₃ N·HCl by filtration, vacuumize the filtrate to remove the solvent, dissolve the solid in THF, wash with deionized water, 1mol/L HCl, and saturated NaCl solution, and separate the liquids, The THF phase was dried over MgSO ₄ to remove water, filtered, and the solvent was removed in vacuo to give the product dimethylsiloxyheptaisobutyloctasilsesquioxane.

Step 4. Put the reaction product dimethylsiloxyheptaisobutyloctapolysilsesquioxane in another two-neck bottle, seal it, vacuumize it, blow it with argon, and replace it three times. 0.164g of methyl nadic acid anhydride was dissolved in 20ml of toluene and slowly injected into the two-necked flask, and 0.2mol% Karstedt's catalyst was added with a micro injector. After reacting at 75°C for 20 hours, vacuumize to remove the solvent, raise the temperature to 200°C to remove unreacted anhydride, wash with acetone to obtain a solid precipitate, dissolve the precipitate in anhydrous acetic acid and toluene, add activated carbon to reflux for 2h, filter, and vacuumize the filtrate The solvent is removed, and the final product is dried to obtain dimethylsiloxyheptaisobutyloctapolysilsesquioxane with acid anhydride groups.

Example 4: Similar to Example 3, the difference is that the reactant in step 1 is replaced by trihydroxyheptamethylheptapolysiloxane, the addition amount is 0.496g, and the other conditions remain unchanged.

Example 5

Step 1. Put 0.972 g of trihydroxyheptacyclohexyl heptapolysiloxane into a two-necked bottle, seal it, and repeatedly vacuumize and blow nitrogen to replace it 3 times. 0.303g of Et ₃ N was dissolved in 20ml of THF and injected into a two-neck bottle, and 0.170g of SiCl ₄ was slowly added at room temperature. After stirring for 16 h at room temperature, Et ₃ N·HCl was removed by filtration, the filtrate was vacuumed to remove the solvent, and the white precipitate was collected after drying to obtain the product monochloroheptacyclohexyl octasilsesquioxane.

Step 2. Add the above-mentioned monochloroheptacyclohexyl octasilsesquioxane into 30ml THF/H ₂ O, stir under reflux for 20 hours, and remove the solvent in vacuo to obtain the product hydroxycyclohexyl silsesquioxane. Wherein the volume ratio of THF to deionized water is 2:1.

Step 3. Take another two-neck bottle, put the above-mentioned product hydroxyheptacyclohexyl octasilsesquioxane in it, seal it, vacuumize it, and blow it with nitrogen gas, and replace it 3 times repeatedly. 0.189g of ClSi(CH ₃ ) ₂ H, 0.101g of Et ₃ N and 20ml of THF were mixed, and slowly injected into a two-neck bottle. React at 60°C for 20 hours, remove Et ₃ N·HCl by filtration, vacuumize the filtrate to remove the solvent, dissolve the solid in THF, wash with deionized water, 1mol/L HCl, and saturated NaCl solution, and separate the liquids. The THF phase was dried over MgSO ₄ to remove water, filtered, and the solvent was removed in vacuo to give the product dimethylsiloxyheptacyclohexyloctasilsesquioxane.

Step 4. Put the reaction product dimethylsiloxyheptacyclohexyloctasilsesquioxane in another two-neck bottle, seal it, vacuumize it, blow it with argon, and replace it three times. 0.660g maleic anhydride was dissolved in 20ml toluene and slowly injected into a two-necked bottle, and 0.2mol% Karstedt's catalyst was added with a micro injector. After reacting at 75°C for 26 hours, vacuumize to remove the solvent, raise the temperature to 200°C to remove unreacted anhydride, wash with acetone to obtain a solid precipitate, dissolve the precipitate in anhydrous acetic acid and toluene, add activated carbon, reflux for 2h, filter, and pump the filtrate The solvent was removed in vacuo and dried to obtain the final product dimethylsiloxyheptacyclohexyl octasilsesquioxane with acid anhydride groups.

Example 6: Similar to Example 5, the difference is that the reactant in step 1 is replaced by trihydroxyheptacyclopentyl heptapolysiloxane, the addition amount is 0.874g, and other conditions remain unchanged.

Example 7

Step 1. Put 0.580 g of trihydroxyheptavinylheptapolysiloxane into a two-necked bottle, seal it, and repeatedly vacuumize and blow nitrogen to replace it 3 times. 0.303g of Et ₃ N was dissolved in 20ml of THF and injected into a two-neck bottle, and 0.170g of SiCl ₄ was slowly added at room temperature. After stirring for 14 h at room temperature, Et ₃ N·HCl was removed by filtration, the filtrate was vacuumed to remove the solvent, and the white precipitate was collected after drying to obtain the product monochloroheptavinyl octasilsesquioxane.

Step 2. Add the above product monochloroheptavinyl octasilsesquioxane into 30ml THF/H ₂ O, stir under reflux for 18 hours, and remove the solvent in vacuo to obtain the product hydroxyheptavinyl silsesquioxane. Wherein the volume ratio of THF to deionized water is 2:1.

Step 3. Take another two-necked bottle, put the above-mentioned product hydroxyheptavinyl octasilsesquioxane in it, seal it, vacuumize it, blow nitrogen, and replace it repeatedly 3 times. 0.095g of ClSi(CH ₃ ) ₂ H, 0.101g of Et ₃ N and 20ml of THF were mixed, and slowly injected into a two-neck bottle. React at 60°C for 18 hours, remove Et ₃ N·HCl by filtration, vacuumize the filtrate to remove the solvent, dissolve the solid in THF, wash with deionized water, 1mol/L HCl, and saturated NaCl solution respectively, and separate the liquid, The THF phase was dried over MgSO ₄ to remove water, filtered, and the solvent was removed in vacuo to give the product dimethylsiloxyheptavinyloctasilsesquioxane.

Step 4. Put the reaction product dimethylsiloxyheptavinyloctasilsesquioxane in another two-neck bottle, seal it, vacuumize it, blow it with argon, and replace it three times. 0.361g of chlorendic anhydride was dissolved in 20ml of toluene and slowly injected into the two-necked bottle, and 0.2mol% Karstedt's catalyst was added with a micro injector. After reacting at 75°C for 24 hours, vacuumize to remove the solvent, raise the temperature to 200°C to remove unreacted anhydride, wash with acetone to obtain a solid precipitate, dissolve the precipitate in anhydrous acetic acid and toluene, add activated carbon, reflux for 3h, filter, and pump the filtrate The solvent was removed in vacuo and dried to obtain the final product of dimethylsiloxyheptavinyl octasilsesquioxane with acid anhydride groups.

Example 8: Similar to Example 7, the difference is that the reactant in step 1 is replaced by trihydroxyheptapropylheptapolysiloxane, and the addition amount is 0.692g, and the acid anhydride in step 4 is replaced by methyltetrahydro-ortho Phthalic anhydride, the addition is 0.166g, all the other conditions are constant.

Claims (9)

1. a drift angle has the preparation method of the silsesquioxane of anhydride group, it is characterized in that its synthetic route is as follows:

Its concrete steps are as follows:

1) under the exsiccant nitrogen atmosphere, trihydroxy-seven R base seven polysiloxane 1 and triethylamine are dissolved in the tetrahydrofuran (THF), add tetrachloro silicane, remove triethylamine hydrochloride, vacuumize and desolventize, white precipitate is collected in dry back, obtains product one chlorine seven R base eight polysilsesquioxanes 2; In molar ratio, trihydroxy-seven R base seven polysiloxane: tetrachloro silicane: triethylamine is 1: 1～2: 3～3.5;

2) chlorine seven R base eight polysilsesquioxanes 2 are added THF/H ₂Reflux among the O and stir, solvent removed in vacuo obtains product hydroxyl seven R base eight polysilsesquioxanes 3; By volume, the volume ratio of THF and deionized water is 2: 1;

3) under vacuum or the nitrogen protection, with hydroxyl seven R base eight polysilsesquioxanes 3, chlorodimethyl silane and Et ₃The N hybrid reaction removes by filter Et ₃NHCl, the solid that obtains after filtrate vacuumizing desolventizes is dissolved in THF, uses deionized water, HCl, NaCl solution washing more respectively, and behind the separatory, THF uses MgSO mutually ₄Drying is filtered, and filtrate vacuumizes to remove and desolvates, and obtains product dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 4; In molar ratio, hydroxyl seven R base eight polysilsesquioxanes: chlorodimethyl silane: triethylamine is 1: 1～2: 1～2;

4) under argon shield, dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 4 are dissolved together with acid anhydrides in toluene, after adding 0.2mol%Karstedt ' s reagent carries out catalyzed reaction, vacuumize and remove solvent, remove unreacted acid anhydrides, behind the washing with acetone, obtain solid precipitation, throw out is dissolved in anhydrous acetic acid and toluene, adding gac refluxes, filter, filtrate vacuumizing desolventizes, and drying obtains dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes 5 that final product has anhydride group; In molar ratio, dimethyl-silicon alcoxyl base seven R base eight polysilsesquioxanes:: acid anhydrides is 1: 1～1.5.

2. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 1) the R group in trihydroxy-seven R base seven polysiloxane is selected from methyl, ethyl, propyl group, isobutyl-, phenyl, cyclohexyl, cyclopentyl or vinyl.

3. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 1), stirs 10～16h behind the adding tetrachloro silicane.

4. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 3), with the temperature of hydroxyl seven R base eight polysilsesquioxanes 3, chlorodimethyl silane and triethylamine hybrid reaction is 60 ℃, and the time of reaction is 16～20h.

5. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 3), and the concentration of HCl is 1mol/L, and NaCl solution is saturated NaCl solution.

6. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4) acid anhydrides is selected from Tetra Hydro Phthalic Anhydride, MALEIC ANHYDRIDE, methyl tetrahydrophthalic anhydride, methyl carbic anhydride or chlorendic anhydride.

7. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4), and the temperature of catalyzed reaction is 75 ℃, and the time of catalyzed reaction is 20～26h.

8. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4), vacuumizes to be warming up to 200 ℃ after removing solvent, removes unreacted acid anhydrides again.

9. a kind of drift angle as claimed in claim 1 has the preparation method of the silsesquioxane of anhydride group, it is characterized in that in step 4), and the time that adds the gac backflow is 2～3h.