CN1218985C - Preparation method of polydisiloxane - Google Patents
Preparation method of polydisiloxane Download PDFInfo
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- CN1218985C CN1218985C CN 03129694 CN03129694A CN1218985C CN 1218985 C CN1218985 C CN 1218985C CN 03129694 CN03129694 CN 03129694 CN 03129694 A CN03129694 A CN 03129694A CN 1218985 C CN1218985 C CN 1218985C
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- toluene
- polydisiloxane
- dichlorosilane
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Abstract
The present invention discloses a synthesis method of polydisiloxane, which comprises: firstly, alkyl hydrogen-containing dichlorsilane and dialkyl dichlorsilane or a mixed monomer of monoalkyl hydrogen-containing dichlorsilane and dialkyl dichlorsilane and alkali metal are dispersed under the supersonic wave action condition to carry out a Wurtz method reducing coupling reaction; secondly, a hydrolysis reaction is directly carried out to obtain the polydisiloxane through further separation. Experiment results indicate that the product obtained with the synthesis method is in a regular structure. Since the present invention further reduces the temperature of the Wurtz method reducing coupling reaction and improves the product yield, the present invention has the advantages of mild reaction condition, controllable operability improvement of a synthesis reaction, and industrialized production promotion of the functional polydisiloxane, and simultaneously, the research and the application of the novel polymer for functional materials, such as elastomeric materials, ceramic precursors, photoinduced etching agents, semiconductor materials, nonlinear optical materials, photorefractive materials, cavity transmission materials, etc., are pushed.
Description
Technical field: the present invention relates to a kind of preparation method of organosilicon polymer, under the effect of particularly a kind of employing ultrasonic wave alkali-metal dispersion and with the monomeric Wurtz method of dichlorosilane reductive coupling reaction, the method for synthesizing polydisiloxane.
Background technology: the sily oxide polymkeric substance has the potential application prospect, as ceramic forerunner, electronics material, photonics material and heat-resisting elastic-plastic material etc.Be otherwise known as sily oxide polymkeric substance [Poly (oxydisilanes)] or simply be referred to as poly-sila ether [Poly (silaethers)] of polydisiloxane.Owing to both contained the Si-O-Si key in the main chain of this base polymer, contain the Si-Si bond structure again, thereby this base polymer had both possessed good visco-elasticity, the high-low temperature resistant character of polysiloxane, some special propertys that polysilane is arranged again, such as: intensive uv-absorbing, photoluminescence, electroluminescent and high-conductivity etc. had.
People such as J.Chojnowski are successively in [J.Chojnowski in 1979; L.Wilkzek.Makromol.Chem., 1979,180:117] and [L.Wilkzek in 1986; S.Rubinsztajn; J.Chojnowski.Makromol.Chem., 1986,187:39] reported and utilized 2,2,3,3,4,4,5,5,6,6-prestox-1,4-dioxy-2,3,5,6-four silicon hexanaphthenes (are write a Chinese character in simplified form
2D
2) as monomer,, obtained full methyl polydisiloxane by cationic ring-opening polymerization.The above-mentioned monomer of relevant afterwards employing carries out ring-opening polymerization, and the research work such as transformation, thermostability mutually that prepare synthetic method, kinetics of polymerization reaction and the full methyl polydisiloxane of full methyl polydisiloxane have obtained certain concern.
As Poland Patent [Chojnowski, Julian; Scibiorek, Marek; Rubinsztajn, Slawomir; Kurjata, Jan.Manufacture of polyoxydisilylene rubbers.Pol.PL 155375 (1992,2)] described and adopted 2,2,3,3,4,4,5,5,6,6-prestox-1,4-dioxy-2,3,5,6-four silicon hexanaphthenes (are write a Chinese character in simplified form
2D
2) under the strong lewis acid katalysis, carry out ring-opening polymerization, prepare the method for full methyl polydisiloxane, this polymkeric substance also can be used to prepare heat-resisting silicon rubber.
In relating to the effective preparation method of total hydrocarbon base polydisiloxane, mainly contain following report in addition: Japanese Patent [Kokuni, Nobuki; Nakagawa, Tasuji; Yoshida, Keisuke.Preparation oforganosiloxane-polysilanes.JP 05271419 (1993.10)] described by tetraalkyl dihalo sily oxide and basic metal and in THF, reacted, obtained the preparation method of total hydrocarbon base polydisiloxane with the methyl alcohol alcoholysis; Japanese Patent [Iwasa, Shigeyuki; Nakano, Kaichiro; Maeda, Katsumi; Hasegawa, Etsuo.Silicon-containing sulfonium salts and photoresist compositions.JP06342209 (1994.12)] the photoresist material synthetics that contains sulfonium salt and many silicon of oxa-chain link described.
Above in the described existing research work, all be stability of only having reported in full methyl polydisiloxane and synthetic method thereof, polymerization mechanism, polymkeric substance etc.Although the synthetic of this base polymer can be by 2,2,3,3,4,4,5,5,6 in theory, 6-prestox-1,4-dioxy-2,3,5,6-four silicon hexanaphthenes (are write a Chinese character in simplified form
2D
2) ring-opening polymerization, tetraalkyl dihalo sily oxide and dichlorosilane monomer and alkali-metal condensation reaction etc., synthetic route more than at least three kinds, however the synthesis technique of this base polymer is all having all difficulties on concrete enforcement.
Adopting dichlorosilane and basic metal to carry out Wurtz method reductive coupling reaction, in the method for synthetic polydisiloxane, especially when employed dichlorosilane boiling point is low, as methyl hydrogen dichlorosilane, dimethyldichlorosilane(DMCS) etc., then, thereby aspect industrializing implementation, still have certain deficiency carrying out alkali-metal dispersion and can not better controlled with monomeric coupling reaction process.
Summary of the invention: but the objective of the invention is to propose the synthetic method that a kind of industrially scalable is implemented, also significantly reduced the polydisiloxane of synthetic cost.Synthetic polydisiloxane of the present invention has regularity, the good repeatability of height.
The preparation method of the polydisiloxane that the present invention proposes has adopted the sonochemistry synthetic method, has further improved the yield of polymkeric substance, up to more than 90%.A large amount of experimental studies show that ultrasonic wave not only can be improved reaction conditions, fast reaction speed and raising reaction yield, and the chemical reaction that can also make some be difficult to carry out is achieved.The ultrasonic wave radiating capacity quickens various organic homogeneous phases and out-phase reaction, the particularly reaction of metal participation, therefore adopt the sonochemistry method, further improve reaction conditions, explore the synthetic route of a relatively cheap polydisiloxane, industrialization and the scale operation that realizes polydisiloxane is early had important Practical significance.
The preparation method of polydisiloxane of the present invention, be by the ultrasonic wave effect, make basic metal carry out ultra-fine dispersion in toluene, and carry out Wurtz method reductive coupling reaction with the dichlorosilane monomer under the ultrasonic wave effect, direct hydrolysis reaction afterwards, separation obtain polydisiloxane.Concrete steps are as follows: at N
2Under the gas shiled; metal K or Na and toluene joined installed agitator additional; the reflux condensate device that has moisture eliminator; in the reactor of constant pressure funnel; the add-on of above-mentioned toluene is 150ml toluene/3.53g Na; or 150ml toluene/6.0gK; be heated to 80-100 ℃ and make metal K or Na fusion; by wavelength region is that ultrasonic wave and the mechanical stirring acting in conjunction of 40-80KHz is separated into ultra-fine grain with metal K or Na fusion; react at 30-90 ℃; in 15-20 minute, drip the mixture of dichlorosilane monomer and toluene to reactor; wherein dichlorosilane monomer and alkali-metal mol ratio are 1: 1; when basic metal is Na; the add-on of toluene is 20ml toluene/21.3g dichlorosilane monomer; when basic metal is K; the add-on of toluene is 20ml toluene/19.9g dichlorosilane monomer; insulation reaction 4-8 hour afterwards; at room temperature stir then; drip deionized water; when basic metal is Na; the dripping quantity of above-mentioned deionized water is a 40ml/21.3g dichlorosilane monomer; when basic metal is K; the dripping quantity of above-mentioned deionized water is a 40ml/19.9g dichlorosilane monomer; be hydrolyzed; condensation reaction; after the reacting liquid filtering separating inorganic salts; be washed to neutrality; drying, isolating polymer then.
In the above-mentioned synthetic method, building-up reactions thing dichlorosilane monomer can be structurally to meet following (1)-(2) formula to require:
R
1SiHCl
2 (1)
R
1R
2SiCl
2 (2)
R wherein
1, R
2Represent methylidene, ethyl, phenyl, wherein R in (2) formula monomer
1, R
2Be above-mentioned group identical or inequality, be the combination that meets any one dichlorosilane monomer in describing as above-mentioned (1)-(2) formula or two kinds and two or more dichlorosilane mix monomers on forming.
In the above-mentioned synthetic method, the reaction unit during building-up reactions carries out in ultrasonic generator, and employed ultrasonic wave wavelength scope is the above any ultrasonic frequency of 20KHz, is preferably and uses the 40-80KHz ultrasonic wave.
In the above-mentioned synthetic method, the reaction process of dichlorosilane monomer and metal K or Na can be the mixture with above-mentioned monomer and toluene, under 30-90 ℃, ultrasonic wave, agitation condition, carries out in the toluene that has been added drop-wise to the basic metal ultra-sonic dispersion; Also can be with ultra-sonic dispersion alkali-metal toluene mixture, under 30-90 ℃, ultrasonic wave and stirring acting in conjunction, be added drop-wise in above-mentioned monomer and the toluene mixture and carry out.
Synthetic polydisiloxane compound with regular structure of the present invention, product synthesizes good reproducibility, products therefrom carried out TF-IR,
1H NMR characterizes.The present invention is owing to adopted the ultrasonic dispersing technology, further reduced Wurtz method reductive coupling reaction temperature, has the reaction conditions gentleness, improved the controllability of building-up reactions operation, can greatly promote the suitability for industrialized production of functional polyalkylene sily oxide, promote of research and the application of this new polymers simultaneously at functional materialss such as elastomer material, ceramic forerunner, photo-induced etching agent, semiconductor material, nonlinear optical material, photorefractive material and hole mobile materials.
Description of drawings: figure-1 is the infrared spectra of embodiment 1 target product polydisiloxane;
Figure-2 is the proton magnetic spectrum of embodiment 1 target product polydisiloxane;
Figure-3 is the GPC molecular weight determination curve of poly-two silica of embodiment 1 target product.
Specific implementation method: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: 3.53 gram metal Na are joined fill the 150mL solvent toluene, and installed agitator additional, the reflux condensate device that has moisture eliminator, in the reactor of constant pressure funnel, reactor places ultrasonic generator, be heated to 100 ℃ and make the metal Na fusion, by ultrasonic wave and mechanical stirring acting in conjunction, the metal Na fusion is separated into ultra-fine grain, under 80 ℃, the mixture that drips 21.3 gram dimethyldichlorosilane(DMCS) monomers and 20mL toluene in 20 minutes reacts to reactor, insulation reaction is 4 hours afterwards, at room temperature stir then, drip the deionized water of 40mL, be hydrolyzed, condensation reaction is after the reacting liquid filtering separating inorganic salts, be washed to neutrality, anhydrous sodium sulfate drying with 3.0 grams, distillation then, separate, obtain 9.5 gram oyster white thickness polymer pastes, yield 93%.IR (KBr compressing tablet, cm
-1): SiSi stretching vibration 413cm
-1, SiOSi stretching vibration 1000-1100,750-850cm
-1, SiCH
3Formation vibration 700-800,1264,1407cm
-1, CH
3Stretching vibration 2796,2893,2963cm
-1 1H NMR (CDCl
3, δ, ppm): 5.27 (Si-OH), 0.02 (Si-CH
3); Recording number-average molecular weight is 23,435, and weight-average molecular weight is 32,215, and distribution coefficient is 1.37.
Embodiment 2: 6.0 gram metal K are joined fill the 150mL solvent toluene, and installed agitator additional, the reflux condensate device that has moisture eliminator, in the reactor of constant pressure funnel, reactor places ultrasonic generator, be heated to 80 ℃ and make the metal K fusion, by ultrasonic wave and mechanical stirring acting in conjunction, the metal K fusion is separated into ultra-fine grain, under 50 ℃, the mixture that drips 19.9 gram dimethyldichlorosilane(DMCS) monomers and 20mL toluene in 20 minutes reacts to reactor, insulation reaction is 4 hours afterwards, at room temperature stir then, drip the deionized water of 40mL, be hydrolyzed, condensation reaction is after the reacting liquid filtering separating inorganic salts, be washed to neutrality, anhydrous sodium sulfate drying with 3.5 grams, distillation then, separate, obtain 9.38 gram oyster white thickness polymer pastes, yield 92%.IR (KBr compressing tablet, cm
-1): SiSi stretching vibration 413cm
-1, SiOSi stretching vibration 1000-1100,750-850cm
-1, SiCH
3Formation vibration 700-800,1264,1407cm
-1, CH
3Stretching vibration 2796,2893,2963cm
-1 1HNMR (CDCl
3, δ, ppm): 5.27 (Si-OH), 4.72,4.67 (Si-H), 0.21 (Si-CH
3).
Claims (2)
1. the preparation method of polydisiloxane, it is characterized in that making basic metal in toluene, carry out ultra-fine dispersion by the ultrasonic wave effect, and under the ultrasonic wave effect, carry out Wurtz method reductive coupling reaction with the dichlorosilane monomer, direct hydrolysis reaction afterwards, separation obtain polydisiloxane, and concrete steps are as follows: at N
2Under the gas shiled; metal K or Na and toluene joined installed agitator additional; the reflux condensate device that has moisture eliminator; in the reactor of constant pressure funnel; the add-on of above-mentioned toluene is 150ml toluene/3.53gNa; or 150ml toluene/6.0gK; be heated to 80-100 ℃ and make metal K or Na fusion; by wavelength region is that ultrasonic wave and the mechanical stirring acting in conjunction of 40-80KHz is separated into ultra-fine grain with metal K or Na fusion; react at 30-90 ℃; in 15-20 minute, drip the mixture of dichlorosilane monomer and toluene to reactor; wherein dichlorosilane monomer and alkali-metal mol ratio are 1: 1; when basic metal is Na; the add-on of toluene is 20ml toluene/21.3g dichlorosilane monomer; when basic metal is K; the add-on of toluene is 20ml toluene/19.9g dichlorosilane monomer; insulation reaction 4-8 hour afterwards; at room temperature stir then; drip deionized water; when basic metal is Na; the dripping quantity of above-mentioned deionized water is a 40ml/21.3g dichlorosilane monomer; when basic metal is K; the dripping quantity of above-mentioned deionized water is a 40ml/19.9g dichlorosilane monomer; be hydrolyzed; condensation reaction; after the reacting liquid filtering separating inorganic salts; be washed to neutrality; drying, isolating polymer then.
2. the preparation method of polydisiloxane according to claim 1 is characterized in that the dichlorosilane monomer is structurally to meet following (1)-(2) formula:
R
1SiHCl
2 (1)
R
1R
2SiCl
2 (2)
R wherein
1, R
2Represent methylidene, ethyl, phenyl, wherein R in (2) formula monomer
1, R
2It is above-mentioned group identical or inequality; It on forming the combination that meets any one dichlorosilane monomer in describing as above-mentioned (1)-(2) formula or two kinds and two or more dichlorosilane mix monomers.
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|---|---|---|---|
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| CN109867788A (en) * | 2019-03-18 | 2019-06-11 | 台州学院 | A kind of preparation method of organosilicon-composite titania material |
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