CN103214510A

CN103214510A - Octohydroxy cage-like silsesquioxane monomer and preparation method thereof

Info

Publication number: CN103214510A
Application number: CN2013101231615A
Authority: CN
Inventors: 牟建新; 张卫海; 王岩; 许玖多; 姜振华
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2013-04-10
Filing date: 2013-04-10
Publication date: 2013-07-24
Anticipated expiration: 2033-04-10
Also published as: CN103214510B

Abstract

The invention discloses an octohydroxy cage-like silsesquioxane monomer and a preparation method thereof, which belong to the technical field of silsesquioxane. The preparation method comprises the steps of: adding dimethylsilyl cage-like polysilsesquioxane (8Si-H) monomers and eugenol monomers with a feeding mole ratio of 1:(8-48); adding toluene as a solvent; dropwise adding a Castors reagent as a catalyst, wherein the Castors reagent contains 0.3% of Pt by weight and takes account for 0.1% capacity of toluene; increasing the temperature to 65-110 DEG C and reacting for 6-36 hours at constant temperature; cooling a reaction system to room temperature, decompressing for distilling a reaction mixture liquid at the temperature of 80-110 DEG C and removing the unreacted eugenol; and cooling to the room temperature again, thus obtaining a light yellow solid 8Si-OH. The 8Si-OH structure monomer has eight symmetrical reactivity points and can serve as a hyperbranched center, and the synthetic method is simple and efficient.

Description

A kind of eight hydroxyl cagelike silsesquioxane monomers and preparation method thereof

Technical field

The invention belongs to the silsesquioxane technical field, be specifically related to a kind of silsesquioxane monomer and preparation method thereof with eight hydroxyl cagelike structures.

Background technology

Organosilicon material is a kind of novel synthetic material of excellent performance, have the double attribute of inorganic materials and organic materials concurrently, can be made into products such as the various intermediate of quantity, oily matter, elastomerics and resin, is the outstanding person in the synthetic materials, and the title of industrial VITAMIN is arranged.

Polysilsesquioxane (POSS) is a kind of interesting structure, and it is to be arranged in together a kind of material of organic-inorganic nano structure with complete square shape of formation by what inorganic Si-O key gauge was restrained.Can connect different R(organic groups on the summit of square), with going up different active groups, can carry out block, reactions such as grafting.

Journal of Scientific﹠Industrial Research(D Gnanasekaran, K Madhavan and B S R Reddy, Vol.68, June2009, pp.437-464) reported and utilized the synthetic cage-type silsesquioxane monomer of silicon hydrogen addition two-step approach with eight hydroxyl structures, make its complex process, complex operation, aftertreatment is loaded down with trivial details.

Summary of the invention

The purpose of this invention is to provide a kind of silsesquioxane (8Si-OH) and preparation method thereof,, make technology simply efficient, low-carbon environment-friendly, environmentally safe to overcome prior art complex operation, the low defective of security with eight hydroxyl cagelike structures.

The present invention is according to the method one-step synthesis 8Si-OH of silicon hydrogen addition, and reaction formula is as follows:

Wherein:

Concrete synthetic 8Si-OH process can be as described below: add dimethylsilyl cage type polysilsesquioxane (8Si-H) monomer and Eugenol monomer in the container of nitrogen protection, 8Si-H and Eugenol molar ratio are 1: 8～48, add toluene do solvent (in the reaction system quality of toluene be 8Si-H and Eugenol quality and 3.3～10 times), drip Pt quality percentage composition and be 0.3% the Karst reagent that accounts for solvent volume mark 0.1% as catalyzer, be warming up to 65～110 ℃ of isothermal reaction 6～36h; After reaction system is reduced to room temperature, reaction mixture 80～110 ℃ of underpressure distillation, is removed unreacted Eugenol; Obtain faint yellow solid 8Si-OH after reducing to room temperature once more.By infrared, means such as nuclear-magnetism silicon spectrum and nucleus magnetic hydrogen spectrum characterize it, to confirm its structure.

Description of drawings:

The infrared spectrum of the monomer 8Si-H (a) among Fig. 1: the embodiment 1,8Si-OH (b), Eugenol (c).

The monomer 8Si-OH nucleus magnetic hydrogen spectrum figure of Fig. 2: embodiment 1 preparation.

The monomer 8Si-OH nuclear-magnetism silicon spectrogram of Fig. 3: embodiment 1 preparation.

Embodiment

Embodiment 1:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (5.36g; 0.032mol); in system, add toluene (38mL) and make solvent; be warming up to 65 ℃; dropping Pt massfraction content is 0.3% Karst reagent 0.38ml; be cooled to room temperature behind 65 ° of C isothermal reaction 6h; reaction mixture is added in the vacuum distillation apparatus; in 80 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain faint yellow solid 8Si-OH5.6g after reducing to room temperature again, productive rate is 48.9%.

With the infrared spectra of Nicolet Impact410 Fourier transformation infrared spectrometer mensuration 8Si-OH and Eugenol, sweep limit 4000～400cm ^-1, resolving power 4cm ^-1, the KBr compressing tablet the results are shown in Figure 1.As seen from Figure 1, C=C key absorption peak in the Eugenol and the Si-H key absorption peak among the 8Si-H disappear in 8Si-OH, and occur among the reacted 8Si-OH Si-O key characteristic peak and-OH key absorption peak, illustrate to successfully synthesize 8Si-OH.

With DMSO is solvent, is interior mark with tetramethylsilane (TMS), measures 8Si-OH proton magnetic spectrum figure with Bruker Advance510 type nuclear magnetic resonance analyser (300MHz), the results are shown in Figure 2.As seen from Figure 2, the chemical shift ownership between 0ppm～0.1ppm is the H on the Si-CH3, and the chemical shift ownership between the 0.5ppm-2.5ppm is CH ₂On H, chemical shift ownership is CH between 3.5ppm～4ppm ₃H on the-O is the H the on-OH in the chemical shift between 8.5ppm～8.7ppm ownership, and the chemical shift ownership between 6.0ppm～7.0ppm is the H on the phenyl ring.The chemical displacement value of each H all has good ownership, proves the 8Si-OH monomer that successfully synthesizes expected structure.

With CDCl ₃Being solvent, is interior mark with tetramethylsilane (TMS), measures 8Si-OH silicon nuclear magnetic spectrogram with Bruker AVANCEIII500 type nuclear magnetic resonance analyser (500MHz), the results are shown in Figure 3.As seen from Figure 3, chemical shift between 10ppm～15ppm ownership is the Si on the Si-CH3 ,-105ppm～-chemical shift ownership between the 110ppm is the Si on the cage type POSS drift angle.The chemical displacement value of each Si all has good ownership, proves the 8Si-OH monomer that successfully synthesizes expected structure.

Embodiment 2:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (6.45g 0.039mol), adds toluene (38mL) and makes solvent in system; be warming up to 65 ℃; dropping Pt massfraction content is 0.3% Karst reagent 0.38ml, is cooled to room temperature behind the isothermal reaction 12h, and reaction mixture is added in the vacuum distillation apparatus; in 90 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 5.8g faint yellow solid 8Si-OH after the cooling, productive rate is 50.6%.

Embodiment 3:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (6.56g 0.04mol), adds toluene (38mL) and makes solvent in system; be warming up to 70 ℃; dropping Pt massfraction content is 0.3% Karst reagent 0.38ml, is cooled to room temperature behind the isothermal reaction 12h, and reaction mixture is added in the vacuum distillation apparatus; in 90 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 6.0g faint yellow solid 8Si-OH after the cooling, productive rate is 52.4%.

Embodiment 4:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (8.32g 0.05mol), adds toluene (38mL) and makes solvent in system; be warming up to 90 ℃; dropping Pt massfraction content is 0.3% Karst reagent 0.38ml, is cooled to room temperature behind the isothermal reaction 12h, and reaction mixture is added in the vacuum distillation apparatus; in 90 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 8.2g faint yellow solid 8Si-OH after the cooling, productive rate is 71.6%.

Embodiment 5:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (8.32g 0.05mol), adds toluene (50mL) and makes solvent in system; be warming up to 110 ℃; dropping Pt massfraction content is 0.3% Karst reagent 0.5ml, is cooled to room temperature behind the isothermal reaction 36h, and reaction mixture is added in the vacuum distillation apparatus; in 90 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 10.4g faint yellow solid 8Si-OH after the cooling, productive rate is 88.5%.

Embodiment 6:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (6.56g 0.04mol), adds toluene (38mL) and makes solvent in system; be warming up to 110 ℃; dropping Pt massfraction content is 0.3% Karst reagent 0.38ml, is cooled to room temperature behind the isothermal reaction 36h, and reaction mixture is added in the vacuum distillation apparatus; in 90 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 9.5g faint yellow solid 8Si-OH after the cooling, productive rate is 83.0%.

Embodiment 7:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (6.56g; 0.04mol); in system, add toluene (330mL) and make solvent; be warming up to 100 ℃; dropping Pt massfraction content is 0.3% reagent 3.3ml Karst, Karst reagent solution; be cooled to room temperature behind the isothermal reaction 12h; reaction mixture is added in the vacuum distillation apparatus; in 90 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 9.3g faint yellow solid 8Si-OH after the cooling, productive rate is 81.2%.

Embodiment 8:

In the container of nitrogen protection, add 8Si-H(5.0g; 0.004mol) and Eugenol (31.52g; 0.192mol); in system, add toluene (330mL) and make solvent; be warming up to 110 ℃; dropping Pt massfraction content is 0.3% Karst reagent 3.3ml; be cooled to room temperature behind the isothermal reaction 24h; reaction mixture is added in the vacuum distillation apparatus; in 110 ℃ of underpressure distillation; remove unreacted Eugenol and solvent toluene, obtain 9.6g faint yellow solid 8Si-OH after the cooling, productive rate is 83.8%.

8Si-OH structure monomer has symmetric eight reactive behavior points, can be used as hyperbranched center and exist, and this synthetic method is simple, and is efficient.

Claims

1. hydroxyl cagelike silsesquioxane monomer, its structural formula is as follows:

2. the monomeric preparation method of the described eight hydroxyl cagelike silsesquioxanes of claim 1, its step is as follows:

A) in the container of nitrogen protection, add structural formula dimethylsilyl cage type polysilsesquioxane monomer and Eugenol monomer as follows, dimethylsilyl cage type polysilsesquioxane monomer and Eugenol molar ratio are 1: 8～48, add toluene and make solvent, in the reaction system quality of toluene be dimethylsilyl cage type polysilsesquioxane monomer and Eugenol quality and 3.3～10 times, drip Pt quality percentage composition and be 0.3% and the Karst reagent that accounts for solvent volume mark 0.1% as catalyzer, be warming up to 65～110 ℃ of isothermal reaction 6～36h;

B) after reaction system is reduced to room temperature, reaction mixture 80～110 ℃ of underpressure distillation, is removed unreacted Eugenol;

C) obtain faint yellow solid after reducing to room temperature once more, i.e. eight hydroxyl cage type polysilsesquioxane monomers;