CN101838394B

CN101838394B - Method for preparing highly-ordered ladder-like poly-phenyl silsesquioxane

Info

Publication number: CN101838394B
Application number: CN201010190169XA
Authority: CN
Inventors: 杨荣杰; 蒋云芸; 李向梅
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2010-06-03
Filing date: 2010-06-03
Publication date: 2011-11-09
Anticipated expiration: 2030-06-03
Also published as: CN101838394A

Abstract

The invention relates to a method for preparing highly-ordered ladder-like poly-phenyl silsesquioxane (PPSQ), belonging to the technical field of nanometer materials. The PPSQ synthesized by the method is particularly an organic/inorganic hybrid material with a ladder-like structure, which is widely applicable in the fields of polymer modification, heat-insulating materials, low-k dielectric materials, coatings, gas-separation membranes and the like. The method comprises the following steps: mixing phenyl trichlorosilane, solvent and deionized water to hydrolyze the phenyl trichlorosilane; then, adding the supernatant to a metal chloride solution, increasing the temperature, adding catalysts, and refluxing at 80 to 120 DEG C to obtain a solid-liquid mixture; and filtering, adding precipitator to the filtrate, carrying out suction filtration, washing, and drying in a vacuum to obtain the product, particularly white spherical grains with the diameter thereof being 0.5mum to 1mum and the weight-average molecular weight thereof being 3,000 to 8,000. The invention has the advantages of wild and controllable reaction conditions and economic and simple method; the obtained ladder-like PPSQ is structurally hydroxyl-free and has the advantages of highly-ordered molecular chains and good thermal stability.

Description

A kind of preparation method of high-tacticity trapezoidal polyphenyl silicious sesquioxane

Technical field

The present invention relates to a kind of preparation method of high-tacticity trapezoidal polyphenyl silicious sesquioxane, belong to technical field of nano material, by this method synthetic poly-phenyl silsesquioxane is the hybrid inorganic-organic materials of ladder structure, can be widely used in fields such as polymer modification, thermal insulation material, dielectric materials, coated coating, gas separation membrane.

Background technology

Poly-phenyl silsesquioxane (PPSQ) is by two Si-O main chains and the middle ladder polymer that connects by oxo bridge, is hybrid inorganic-organic materials in the molecule, and its structural formula is (C ₆H ₅SiO _1.5) _nPPSQ has excellent thermotolerance, weathering resistance, chemical resistant properties, heatproof oxidation performance, electrical insulating property, optical transparence, water-repellancy and flame retardant resistance etc., therefore can be widely used in fields such as polymer modification, thermal insulation material, dielectric materials, coated coating, gas separation membrane.

The preparation of poly-silicious sesquioxane and derivative thereof receives scientific workers' very big concern so far from the beginning of the sixties in last century, and they are constantly seeking the synthetic method of science.Wherein more famous method is " a balance method of condensing " and " progressively coupling polymerization reaction ".Nineteen sixty, Brown as catalyzer, at first synthesizes ladderlike polymer PPSQ with stereoregularity by thermal equilibrium polycondensation method with KOH, but reacting the later stage need use high boiling solvent (biphenyl, phenyl ether), and the product structure regularity that obtains is relatively poor.The nineties in last century, domestic investigator is doing a large amount of systematic research work aspect the preparation of trapezoidal poly-silicious sesquioxane and the sign, proposition is referred to as the method for " progressively coupling polymerization reaction ", this method can obtain compound with regular structure trapezoidal polyalkyl silsesquioxane oxygen alkane preferably, but complex synthetic route.

In the prior art, the good or high performance PPSQ synthesis temperature of regularity substantially all is controlled at 180 ℃-250 ℃, long reaction time, and synthetic route is complicated, the expense costliness.

Summary of the invention

The objective of the invention is to propose a kind of preparation method of high-tacticity trapezoidal polyphenyl silicious sesquioxane in order to solve the problem of the synthetic good or high performance PPSQ long reaction time of regularity, complex synthetic route, expense costliness in the prior art.

The objective of the invention is to be achieved through the following technical solutions.

The preparation method of a kind of high-tacticity trapezoidal polyphenyl silicious sesquioxane of the present invention, its concrete steps are:

1) phenyl-trichloro-silicane and solvent are joined in the reactor, stir, add deionized water then, continue to stir and make the phenyl-trichloro-silicane hydrolysis, layering after hydrolysis is finished, it is stand-by to get upper organic phase;

2) in the organic phase that step 1) obtains, add the metal chloride aqueous solution, stirring at normal temperature; Be warming up to 80～120 ℃ then, add catalyzer, stirring and refluxing 12～36h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, adding precipitation agent in filtrate precipitates, leave standstill 3～12h, suction filtration, normal hexane washing, vacuum-drying obtain poly-phenyl silsesquioxane then, the poly-phenyl silsesquioxane that obtains is white spheroidal particle, particle diameter is at 0.5～1 μ m, and weight-average molecular weight is 3000～8000;

Above-mentioned steps 1) hydrolysis time is 2～8h in, and hydrolysis temperature is-5～5 ℃; Solvent is a kind of in benzene, toluene or the dimethylbenzene, is preferably benzene; Phenyl-trichloro-silicane is 18～42g: 100ml with the ratio of solvent; Phenyl-trichloro-silicane is 5～20g: 100ml with the ratio of deionized water;

Above-mentioned steps 2) metal chloride is AlCl in ₃, MgCl ₂, CaCl ₂, NaCl, KCl or FeCl ₃In a kind of, be preferably AlCl ₃Or MgCl ₂The mol ratio of phenyl-trichloro-silicane and metal chloride is 3～10; The content of water dissolves the solid metal muriate for being enough in the metal chloride aqueous solution; Catalyzer is the methanol solution of alkaline matter, and alkaline matter is a kind of or its mixture in sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide, the ammoniacal liquor, is preferably Tetramethylammonium hydroxide; The mass concentration of alkaline matter methanol solution is 5%～50%; The mass ratio of catalyzer and phenyl-trichloro-silicane is 0.03～0.3: 1;

Above-mentioned steps 3) precipitation agent is a kind of or its mixture in ethanol, methyl alcohol, normal hexane, sherwood oil, deionized water, the hexanaphthene in, is preferably ethanol.

The poly-phenyl silsesquioxane that aforesaid method obtains is tested, and its testing method and condition are as follows:

Nicolet 6700 type infrared spectrometers (FTIR), total reflection, scanning times 32, resolving power is 4cm ^-1RFS100 fourier Raman spectrometer (Raman), scanning times 100, resolving power is 4cm ^-1F209 type thermogravimetric analyzer, German NETZSCH company, temperature range is 40 ℃～850 ℃, nitrogen and air atmosphere, temperature rise rate are 10 ℃/min; X ' Pert PRO MPD type pressed powder X-ray diffractometer (XRD) adopts Cu K α 1 ray, and pipe is pressed 40kV, pipe stream 40mA, and scanning step footpath 0.033 (2 θ), the step is 20s/step frequently; ²⁹Si nuclear magnetic resonance method BRUKER AV600 liquid NMR spectrometer with superconducting magnet, solvent C ₆D ₆, circulation delay time 5.0sec, pulse width 5.00 μ sec, experimental temperature 293.7K; HITACHI S650 type scanning electronic microscope is carried out metal spraying to sample and is handled, and observes main accessories under the high vacuum condition: X-ray energy spectrometer (EDAX9100).

Beneficial effect

Reaction conditions gentleness of the present invention does not need protection of inert gas, is easy to control, and is economical simple; There is not hydroxyl by adding in the ladder-like poly-phenyl silsesquioxane structure that an amount of metal chloride aqueous solution and catalyzer obtain, molecular chain regularity height, Heat stability is good, microscopic appearance are spheroidal particle.

Description of drawings

The structural representation of the poly-phenyl silsesquioxane that Fig. 1 obtains for embodiment 1;

The infrared spectrum of the poly-phenyl silsesquioxane that Fig. 2 obtains for embodiment 1;

The Raman spectrogram of the poly-phenyl silsesquioxane that Fig. 3 obtains for embodiment 1;

The XRD spectra of the poly-phenyl silsesquioxane that Fig. 4 obtains for embodiment 1;

The poly-phenyl silsesquioxane that Fig. 5 obtains for embodiment 1 ²⁹The SiNMR spectrogram;

The hot analysis of spectra of the poly-phenyl silsesquioxane that Fig. 6 obtains for embodiment 1;

The SEM photo of the poly-phenyl silsesquioxane that Fig. 7 obtains for embodiment 1.

Embodiment

The present invention will be further described below in conjunction with embodiment.

Embodiment 1

A kind of preparation method of high-tacticity trapezoidal polyphenyl silicious sesquioxane, its concrete steps are:

1) under 0 ℃, 21.2g phenyl-trichloro-silicane and 100ml benzene are joined in the there-necked flask, stir, add the 200ml deionized water then, continue to stir and make phenyl-trichloro-silicane hydrolysis 3h, layering after hydrolysis is finished, it is stand-by to get upper organic phase;

2) in the organic phase that step 1) obtains, add 10ml and contain 2.23g AlCl ₃The aqueous solution, stirring at normal temperature; Be warming up to 80 ℃ then, adding 3g mass concentration is 50% Tetramethylammonium hydroxide methanol solution, stirring and refluxing 24h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, adding ethanol in filtrate precipitates, leave standstill 3h, suction filtration, normal hexane washing are 3 times then, and vacuum-drying obtains the 7.64g poly-phenyl silsesquioxane, and its structural representation as shown in Figure 1, poly-phenyl silsesquioxane is white spheroidal particle, particle diameter is 0.5～1 μ m, and weight-average molecular weight is 5700, and molecular weight distribution is 1.1.

The poly-phenyl silsesquioxane that aforesaid method obtains is tested with Nicolet 6700 type infrared spectrometers, and condition is total reflection, scanning times 32, and resolving power is 4cm ^-1, the infrared spectrum that obtains as shown in Figure 2;

Test with RFS100 fourier Raman spectrometer (Raman), scanning times 100, resolving power is 4cm ^-1, the Raman spectrogram that obtains as shown in Figure 3;

Test with X ' Pert PRO MPD type pressed powder X-ray diffractometer (XRD), adopt Cu K α 1 ray, pipe is pressed 40kV, pipe stream 40mA, and scanning step footpath 0.033 (2 θ), the step is 20s/step frequently, and the XRD spectra that obtains is as shown in Figure 4;

With ²⁹Si nuclear magnetic resonance method BRUKER AV600 liquid NMR spectrometer with superconducting magnet, solvent C ₆D ₆, circulation delay time 5.0sec, pulse width 5.00 μ sec, experimental temperature 293.7K obtains ²⁹The SiNMR spectrogram as shown in Figure 5;

Test with the German NETZSCH F209 of company type thermogravimetric analyzer, temperature range is 40 ℃～850 ℃, nitrogen and air atmosphere, and temperature rise rate is 10 ℃/min, the hot analysis of spectra that obtains is as shown in Figure 6;

With HITACHI S650 type scanning electronic microscope, sample is carried out metal spraying handle, to observe under the high vacuum condition, the SEM photo that obtains is as shown in Figure 7.

Embodiment 2

1) under 0 ℃, 21.2g phenyl-trichloro-silicane and 100ml benzene are joined in the there-necked flask, stir, add the 200ml deionized water then, continue to stir and make phenyl-trichloro-silicane hydrolysis 5h, layering after hydrolysis is finished, it is stand-by to get upper organic phase;

2) in the organic phase that step 1) obtains, add 10ml and contain 2.38g MgCl ₂The aqueous solution, stirring at normal temperature; Be warming up to 110 ℃ then, add the 3g mass concentration then and be 30% Tetramethylammonium hydroxide methanol solution, stir, backflow 24h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, in filtrate, add normal hexane and precipitate, leave standstill 3h, suction filtration, normal hexane washing 3 times, vacuum-drying obtain the 5.20g poly-phenyl silsesquioxane then.

Embodiment 3

1) under 0 ℃, 21.2g phenyl-trichloro-silicane and 100ml dimethylbenzene are joined in the there-necked flask, stir, add the 200ml deionized water then, continue to stir and make phenyl-trichloro-silicane hydrolysis 8h, layering after hydrolysis is finished, it is stand-by to get upper organic phase;

2) in the organic phase that step 1) obtains, add 10ml and contain 1.39g CaCl ₂The aqueous solution, stirring at normal temperature; Be warming up to 100 ℃ then, add the 3g mass concentration then and be 50% potassium hydroxide methanol solution, stirring and refluxing 36h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, in filtrate, add sherwood oil and precipitate, leave standstill 3h, suction filtration, normal hexane washing 3 times, vacuum-drying obtain the 4.20g poly-phenyl silsesquioxane then.

Embodiment 4

1) under 0 ℃, 21.2g phenyl-trichloro-silicane and 100ml benzene are joined in the there-necked flask, stir, add the 200ml deionized water then, continue to stir and make phenyl-trichloro-silicane hydrolysis 4h, layering after hydrolysis is finished, it is stand-by to get upper organic phase;

2) in the organic phase that step 1) obtains, add the aqueous solution that 10ml contains 1.17g NaCl, stirring at normal temperature; Be warming up to 80 ℃ then, add the 6g mass concentration then and be 50% ammoniacal liquor methanol solution, stirring and refluxing 24h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, in filtrate, add deionized water and precipitate, leave standstill 3h, suction filtration, normal hexane washing 3 times, vacuum-drying obtain the 2.20g poly-phenyl silsesquioxane then.

Embodiment 5

1) under 0 ℃, 21.2g phenyl-trichloro-silicane and 100ml toluene are joined in the there-necked flask, stir, add the 200ml deionized water then, continue to stir and make phenyl-trichloro-silicane hydrolysis 6h, layering after hydrolysis is finished, it is stand-by to get upper organic phase;

2) in the organic phase that step 1) obtains, add 10ml and contain 3.25g FeCl ₃The aqueous solution, stirring at normal temperature; Be warming up to 95 ℃ then, add the 6g mass concentration then and be 40% Tetramethylammonium hydroxide methanol solution, stir, backflow 24h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, in filtrate, add ethanol and precipitate, leave standstill 3h, suction filtration, normal hexane washing 3 times, vacuum-drying obtain the 3.24g poly-phenyl silsesquioxane then.

Embodiment 6

2) in the organic phase that step 1) obtains, add the aqueous solution that 10ml contains 2.49g KCl, stirring at normal temperature; Be warming up to 120 ℃ then, add the 3g mass concentration then and be 20% Tetramethylammonium hydroxide methanol solution, stir, backflow 12h; Obtain solidliquid mixture;

3) with step 2) the solidliquid mixture suction filtration that obtains, in filtrate, add deionized water and precipitate, leave standstill 3h, suction filtration, normal hexane washing 3 times, vacuum-drying obtain the 3.92g poly-phenyl silsesquioxane then.

Claims

1. a preparation method of highly regular trapezoidal polyphenylsilsesquioxane, is characterized in that concrete steps are:

1) Add phenyltrichlorosilane and solvent into the reactor, stir, then add deionized water, continue stirring to hydrolyze phenyltrichlorosilane, the hydrolysis time is 2 to 8 hours, and the hydrolysis temperature is -5 to 5°C; After the hydrolysis is completed, the layers are separated, and the upper organic phase is taken for use; the metal chloride aqueous solution is added to the organic phase, and stirred at room temperature; then the temperature is raised to 80-120°C, the catalyst is added to react, and the mixture is stirred and refluxed for 12-36 hours; a solid-liquid mixture is obtained;

2) Suction filtration of the solid-liquid mixture obtained in step 1), adding a precipitant to the filtrate for precipitation, standing for 3 to 12 hours, then suction filtration, washing with n-hexane, and vacuum drying to obtain polyphenylsilsesquioxane, which is obtained The polyphenylsilsesquioxane is a white spherical particle with a particle diameter of 0.5-1 μm and a weight-average molecular weight of 3000-8000;

The solvent in the above step 1) is one of benzene, toluene or xylene; the ratio of phenyltrichlorosilane to solvent is 18～42g: 100ml; the ratio of phenyltrichlorosilane to deionized water is 5～20g: 100ml;

The metal chloride in the above step 1) is one of AlCl ₃ , MgCl ₂ , CaCl ₂ , NaCl, KCl or FeCl ₃ ; the molar ratio of phenyltrichlorosilane to metal chloride is 3-10; the aqueous solution of metal chloride The content of water in the medium is sufficient to dissolve the solid metal chloride; the catalyst is a methanol solution of an alkaline substance, and the alkaline substance is one of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia, or a mixture thereof, The mass concentration of the methanol solution of the alkaline substance is 5% to 50%; the mass ratio of the catalyst to phenyltrichlorosilane is 0.03 to 0.3:1;

The precipitating agent in the above step 2) is one of ethanol, methanol, n-hexane, petroleum ether, deionized water, cyclohexane or a mixture thereof.

2. The preparation method of a highly regular trapezoidal polyphenylsilsesquioxane according to claim 1, characterized in that: the reaction temperature in step 1) is 80-90°C.

3 . The method for preparing highly regular trapezoidal polyphenylsilsesquioxane according to claim 1 , wherein the metal chloride is AlCl ₃ or MgCl ₂ .

4. the preparation method of a kind of highly regular trapezoidal polyphenylsilsesquioxane according to claim 1, is characterized in that: alkaline substance is tetramethylammonium hydroxide, tetramethylammonium hydroxide methanol solution The mass concentration is 50%.

5. The preparation method of a kind of highly regular trapezoidal polyphenylsilsesquioxane according to claim 1, characterized in that: the precipitating agent is ethanol.