CN105622664A - Environment-friendly preparation method of cyclopolysilane - Google Patents
Environment-friendly preparation method of cyclopolysilane Download PDFInfo
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- CN105622664A CN105622664A CN201610115189.8A CN201610115189A CN105622664A CN 105622664 A CN105622664 A CN 105622664A CN 201610115189 A CN201610115189 A CN 201610115189A CN 105622664 A CN105622664 A CN 105622664A
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- cyclopolysilane
- solvent
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- friendly type
- silane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Abstract
The invention relates to an environment-friendly preparation method of cyclopolysilane. The method comprises the following steps that reactants including monosilane and active metal sodium or lithium are subjected to a dehalogenation reaction in organic solvent to prepare polysilane; after the solvent is removed and alcohol reacts with the residual metal, the cyclopolysilane is efficiently prepared in a cracking kettle in the presence of an oxide of transition metal in the eighth group or the eleventh group in a periodic table. The method has the advantages that the phenomenon that the washing and drying processes in which the consumed time is long and industrial wastewater is generated are performed for many times when products are separated in a cyclopolysilane preparation process route is avoided, and no industrial wastewater containing benzene organic solvent is generated; in the cyclopolysilane preparation process, the solvent and the alcohol which are adsorbed in polysilane are recycled secondarily, and therefore the solvent recycling rate is increased; the target product cyclopolysilane can be effectively obtained by adopting a metal catalyst; the reaction residues are fluffy solid residues and are extremely easy to remove from a reaction kettle.
Description
Technical field
The invention belongs to cyclopolysilane technology of preparing, it is specifically related to adopt the environment-friendly type preparation method of a kind of organosilicon cyclopolysilane.
Background technology
The main chain of poly-silane is Si-Si singly-bound, molecular memory is in �� conjugative effect, electronics is along the extensive delocalization of main chain, there is the characteristics such as special electronic spectrum, electroluminescence, electroconductibility, extensive application prospect in the multiple electron devices such as preparation conduction, photoconductive, nonlinear optics equipment, photodiode. Research shows; its performance is had a significant impact by the structure of poly-silane, for obtaining the poly-silane of ad hoc structure, the cyclopolysilane of ad hoc structure usually can be adopted to prepare as intermediate; it it is the intermediate preparing the poly-silane of ordered structure such as poly-tetrasilane, it is possible to the oligomeric silane that synthesis is symmetrical or asymmetric. In organosilicon chemistry field, cyclopolysilane compound is one of important intermediate.
Wutrz synthesis method is the most frequently used poly-silane synthetic method, such as by basic metal and dimethyldichlorosilane(DMCS) dechlorination reaction, the poly-silane of chain shape and ring six silane can be obtained, when basic metal kind and/or solvent are different, obtain the cyclopolysilane of Different Silicon atomicity. The separation of product cyclopolysilane will through a series of aftertreatments: 1, recycling design; 2, add alcohol and remove excess base metal in reactant; 3, repeatedly washing removes byproduct of reaction halogen; 4, finished product is obtained after seasoning and vacuum drying. Last handling process is length consuming time not only, and containing alkali class, alcohol class and alkyl benzene material in washing product, these materials are the material having emission request in GB GB8978-1996 " integrated wastewater discharge standard ", meet the problem of environmental requirement overriding concern when therefore wastewater treatment is and realizes industrial production. Under non-reactive atmosphere, the poly-silane of direct thermolysis chain shape also can obtain cyclopolysilane in addition, but the receipts rate of the method and purity are all low.
Summary of the invention
The present invention proposes one to be reacted by Wutrz, the method of environmental protection, effectively synthesis cyclopolysilane, the method can shorten the aftertreatment time extracting product greatly, it is to increase the recovery utilization rate of solvent, avoid producing the washing product containing pollutent, there is the advantage of production efficiency height, energy-conserving and environment-protective. And adopt metal oxide to make catalyzer and effectively obtain target product cyclopolysilane.
The technical scheme that the present invention takes is:
(1) in inert atmosphere, taking halogen generation single silane as raw material, becoming with active metal sodium or lithium dehalogenation condensation in a solvent is that the product of main chain gathers silane taking Si-Si;
(2) take out the solvent filtering in product, add alcohol class and remove unreacted active metal, obtain the mixture containing poly-silane, alkoxide, alcohol, halogen and a small amount of solvent of absorption;
(3) in inert atmosphere, under the existence of periodictable the 8th race or the 11st group 4 transition metal oxide compound, poly-for chain shape silane is carried out thermolysis, temperature-rise period progressively distills out alcohol and by product adsorption solvent;
(4) continuing to heat up, high-temperature split product cyclopolysilane between centralized collection 350��450 DEG C, until liquid cyclopolysilane is collected complete. In reactor, residue is white fluffy powder.
Preferred described cyclopolysilane is ring penta silane, ring hexasilane, ring silane in heptan, the pungent silane of ring, it is possible to be all alkyl cyclosilane. Preferred described inert atmosphere is high-purity N2, Ar. Preferred described solvent is toluene, dimethylbenzene, normal hexane or its mixed solvent. Preferred described alcohol class is methyl alcohol, ethanol. Preferable reaction temperature 400 DEG C; Preferred catalyst kind is ferric oxide or cupric oxide, or more the mixture of two kinds. Preferred catalyst consumption is 0.01wt%.
This operational path is compared with the operational path described in background technology, and tool has the following advantages:
1, the post-processing step repeatedly washing and drying these two length consuming time because decreasing, can greatly shorten the production cycle, it is to increase production efficiency;
2, the trade effluent containing alcohol class and alkyl benzene organism can not be produced without washing;
3, in the process adding catalyst preparing polycyclic silane, low-temperature zone is retortable to be gone out to be adsorbed on the alcohol and solvent alkylbenzene in coarse fodder, and solvent has been carried out secondary recovery, it is to increase the recovery utilization rate of solvent;
4, the residue in post-reactor that reacts completely is mainly salt (principal constituent is halogen), reaction vessel easy to clean.
5, the present invention adopts two-step approach when preparing polycyclic silane, namely first prepares linear polysilanes, then adds catalyst preparing polycyclic silane, adopts specific metal catalyst can efficiently obtain target product cyclopolysilane.
Embodiment
The following examples are used for illustrating the preparation method of the present invention, but the inventive method is not limited to these embodiments.
Embodiment 1
Under the protection of high pure nitrogen, three-necked flask adds anhydrous dimethyl benzene and the sodium Metal 99.5 of refining purification, after being heated to sodium Metal 99.5 melting, opens and stir, drip again after sodium disperses and add dichlorodimethylsilane, the crude product of obtained polydimethyl silane; After being cooled to room temperature, take out filtering solvent xylene, unnecessary sodium washing with alcohol;
Joining in three-necked flask by polydimethyl silane crude product 100g and ferric oxide 1g (0.01wt%), after vacuumizing, logical high pure nitrogen, starts to stir and heats, be warming up to differing temps section and collect ethanol and dimethylbenzene respectively. After system temperature rises to 320 DEG C, occurring white vapor in flask, steam cools through prolong, waits that being warming up to 400 DEG C starts to collect. System temperature, to after 450 DEG C, white vapor reduces, strengthens N2Steam is cooled collection by flow as far as possible, until stopping heating after evaporating point, at N2Protection lower naturally cooling is the liquid cyclopolysilane of water white transparency in reception bottle.
Embodiment 2
Under the protection of high-purity argon gas, three-necked flask adds dry toluene and the sodium Metal 99.5 of refining purification, after being heated to sodium Metal 99.5 melting, opens and stir, drip again after sodium disperses and add dichlorodimethylsilane, the crude product of obtained polydimethyl silane; After being cooled to room temperature, take out filtering solvent toluene, unnecessary sodium methanol wash;
Joining in three-necked flask by polydimethyl silane crude product 100g and cupric oxide 1g (0.01wt%), after vacuumizing, logical high-purity argon gas, starts to stir and heats, be warming up to differing temps section and collect methyl alcohol and toluene respectively. After system temperature rises to 320 DEG C, occurring white vapor in flask, steam cools through prolong, waits that being warming up to 400 DEG C starts to collect. System temperature, to after 450 DEG C, white vapor reduces, strengthens N2 flow and steam cools collection as far as possible, until stopping heating after evaporating point, at N2Protection lower naturally cooling is the liquid cyclopolysilane of water white transparency in reception bottle.
Embodiment 3
Under the protection of high pure nitrogen, three-necked flask adds anhydrous dimethyl benzene and the sodium Metal 99.5 of refining purification, after being heated to sodium Metal 99.5 melting, opens and stir, drip again after sodium disperses and add dichlorodimethylsilane, the crude product of obtained polydimethyl silane; After being cooled to room temperature, take out filtering solvent xylene, unnecessary sodium washing with alcohol;
Joining in three-necked flask by polydimethyl silane crude product 100g and silver suboxide 1g (0.01wt%), after vacuumizing, logical high pure nitrogen, starts to stir and heats, be warming up to differing temps section and collect ethanol and dimethylbenzene respectively. After system temperature rises to 320 DEG C, occurring white vapor in flask, steam cools through prolong, waits that being warming up to 400 DEG C starts to collect. System temperature, to after 450 DEG C, white vapor reduces, strengthens N2 flow and steam cools collection as far as possible, until stopping heating after evaporating point, at N2Protection lower naturally cooling is the liquid cyclopolysilane of water white transparency in reception bottle.
Claims (8)
1. the environment-friendly type preparation method of a cyclopolysilane, it is characterised in that:
(1) taking halogen generation single silane as raw material, being dissolved in a solvent by single for halogen generation silane, under the protection of inert atmosphere, generating with the reaction of basic metal dehalogenation condensation taking Si-Si is the linear polysilanes of main chain, and described linear polysilanes general formula is:
(2) take out the solvent filtering in product, add alcohol class and remove unreacted basic metal, obtain the mixture containing poly-silane, alcohol, halogen and a small amount of solvent of absorption;
(3) in inert atmosphere, under the existence of periodictable the 8th race or the 11st group 4 transition metal oxide compound, poly-for chain shape silane is carried out thermolysis, temperature-rise period progressively distills out alcohol and by product adsorption solvent;
(4) continuing to heat up, centralized collection 350��450 DEG C of high-temperature split product cyclopolysilanes, until liquid cyclopolysilane is collected complete, in reactor, residue is white fluffy powder.
In the general formula of described linear polysilanes, R1And R2Represent identical or different C1��C6Alkyl, aromatic base or aromatic base alkyl; X represents hydrogen atom, halogen atom, hydroxyl, C1��C6Alkyl, C1��C6Alkoxyl group or aromatic base, n represents >=3 in any integer.
2. the environment-friendly type preparation method of cyclopolysilane according to claim 1, it is characterised in that: in above-mentioned linear polysilanes general formula, R1And R2Represent identical or different C2��C5Alkyl, aromatic base or aromatic base alkyl. X represents hydrogen atom, halogen atom, hydroxyl, C2��C5Alkyl, C2��C5Alkoxyl group, aromatic base, n represents >=3 in any integer.
3. the environment-friendly type preparation method of cyclopolysilane described in 1 is required according to claim, it is characterised in that: described basic metal is Na, Li, K, or the wherein alloy of two kinds.
4. the environment-friendly type preparation method of cyclopolysilane according to claim 1, it is characterised in that: described solvent is the mixed solvent of toluene, dimethylbenzene, normal hexane class non-polar solvent and these solvents.
5. the environment-friendly type preparation method of cyclopolysilane according to claim 1, it is characterised in that: described alcohol class is methyl alcohol and/or ethanol.
6. the environment-friendly type preparation method of cyclopolysilane according to claim 1, it is characterised in that: the temperature of reaction of described condensation reaction is 350��450 DEG C.
7. the environment-friendly type preparation method of cyclopolysilane according to claim 1, it is characterised in that: as periodictable the 8th race transition element oxide compound of catalyzer, it is chosen as the oxide compound of iron, ruthenium, osmium; As periodictable the 11st race's transition element of catalyzer, it is chosen as the oxide compound of copper, silver, gold.
8. the environment-friendly type preparation method of cyclopolysilane according to claim 7, it is characterised in that: the consumption of the transition element of catalyzer is 1000ppm��0.2wt%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108006A (en) * | 1985-10-24 | 1987-04-22 | 中国人民解放军国防科技大学 | Synthesis method of polycarbosilane |
| CN1161969A (en) * | 1996-01-30 | 1997-10-15 | 拜尔公司 | Multifunctional cyclic organic siloxane, preparation method and usage thereof |
| CN103554504A (en) * | 2013-11-21 | 2014-02-05 | 宿迁澳鑫斯新材料有限公司 | Novel method for environmentally and efficiently preparing polycarbosilane |
| CN104086588A (en) * | 2009-04-13 | 2014-10-08 | 日本曹达株式会社 | Process for production of cyclic silane compound and/or cyclic carbosilane compound |
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2016
- 2016-03-01 CN CN201610115189.8A patent/CN105622664A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108006A (en) * | 1985-10-24 | 1987-04-22 | 中国人民解放军国防科技大学 | Synthesis method of polycarbosilane |
| CN1161969A (en) * | 1996-01-30 | 1997-10-15 | 拜尔公司 | Multifunctional cyclic organic siloxane, preparation method and usage thereof |
| CN104086588A (en) * | 2009-04-13 | 2014-10-08 | 日本曹达株式会社 | Process for production of cyclic silane compound and/or cyclic carbosilane compound |
| CN103554504A (en) * | 2013-11-21 | 2014-02-05 | 宿迁澳鑫斯新材料有限公司 | Novel method for environmentally and efficiently preparing polycarbosilane |
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Application publication date: 20160601 |