CN100345880C - Preparation method of polysilane containing condensed ring radical - Google Patents
Preparation method of polysilane containing condensed ring radical Download PDFInfo
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- CN100345880C CN100345880C CNB2005100613196A CN200510061319A CN100345880C CN 100345880 C CN100345880 C CN 100345880C CN B2005100613196 A CNB2005100613196 A CN B2005100613196A CN 200510061319 A CN200510061319 A CN 200510061319A CN 100345880 C CN100345880 C CN 100345880C
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Abstract
The present invention relates to a new method for preparing polysilane containing condensed nucleus groups, which has the advantages of simple and safe operation, high polymerization degree of the polysilane, and convenient separation of an obtained copolymer. The present invention has the method that vinyl silicane copolymer B carries out an addition reaction with dicyclopentadiene ketone A containing condensed nucleus groups in a solvent alpha-chloronaphthalene with a high boiling point under the protection of nitrogen, and the condensed nucleus groups are led into side chains of the polysilane; thereby, a polysilane product containing condensed nucleus groups is obtained. The vinyl silicane copolymer B of the present invention can also be prepared by the polymerization of alkyl vinyl dichlorosilane, alkyl phenyl dichlorosilane and/or dialkyl dichlorosilane.
Description
Technical field
The present invention relates to the organic high molecular polymer field, specifically is a kind of condensed ring radical polysilane novel preparation method that contains.
Background technology
Polysilane is the new polymers that a class main chain is made up of Siliciumatom fully, and the σDian Zi of its Si-Si main chain is a σ conjugated linear polymer along the extensive delocalization of main chain.Because specific molecule and the electronic structure of polysilane, given the character of its special electronic spectrum, thermochromism, spectral hole burning, photoconductivity, electroluminescence, electroluminescent, electroconductibility and many uniquenesses thus, make its at preparation high strength SiC pottery, as conduction, photoconduction and charge transfer matrix material, as the high resolution photo-resist, as nonlinear optical material, make and obtained using widely aspect the multiple electron device such as photodiode.Yet the synthetic polysilane that obtains also has a lot of problems to need solution badly, as: general less stable, under conditions such as heat, oxygen, easy cleaved and oxidation; Third-order non-linear electric susceptibility χ
(3)Lower, the still not enough optics that uses of making; The kind of energy practical application is few; Charge-transfer complex is subjected to the influence of moisture easily and reduces its electroconductibility or the like.
Because condensed ring radical
All be big πDian Zi conjugated system, the big л key of delocalization is arranged, after it is introduced into the polysilane side group, can d π-p π takes place with Siliciumatom and interact, strengthen the σDian Zi delocalization of Si-Si key with sky 3p electronic orbit.Therefore, contain the condensed ring radical polysilane and have thermo-oxidative stability preferably, excellent performances such as photoelectric characteristic (Du Zuodong, Chen Jianhua, the holy beautiful SCI of Feng, 1986,6,1050; Du Zuodong, Chen Jianhua, the holy beautiful polymer journal of Feng, 1988,2,81).
In the research in early days, all adopt following technological line to containing synthesizing of condensed ring radical polysilane: at first, methyl ethylene dichlorosilane (MeViSiCl
2) go out condensed ring radical dimethyl dichlorosilane (DMCS) monomer with the cyclopentadienone generation Diels-Alder prepared in reaction that contains condensed ring radical; Secondly, the condensed ring radical dimethyl dichlorosilane (DMCS) separately or with dichloromethyl phenylsilane (MePhSiCl
2), dimethyldichlorosilane(DMCS) (Me
2SiCl
2) Wurtz reductive coupling prepared in reaction takes place jointly to contain condensed ring radical silane homopolymer or multipolymer (Du Zuodong, Chen Jianhua, the holy beautiful polymer journal of Feng, 1988,2,81; East, Li Mei rivers and mountains university Ph D dissertation " contain the preparation and the photoelectric characteristic research thereof of condensed ring radical silicon silicon key polymkeric substance, 2003).
Although preparation method in the past can prepare a series of condensed ring radical polysilane that contains, the problem that exists is quite a few: (1) monomeric preparation needs higher temperature and solvent, because MeViSiCl
2Boiling point lower, can't under normal pressure, carry out, must in the tube sealing under the anhydrous condition or in the autoclave, react, operate comparatively loaded down with trivial detailsly, and have potential safety hazard; When (2) adopting the Wurtz method to synthesize the polysilane homopolymer,, make only to obtain oligomeric polysilane (polymerization degree is about 3 or 4) because the condensed ring radical dimethyl dichlorosilane (DMCS) has bigger steric effect; (3) preparation is when containing the condensed ring radical silane copolymer, because the steric effect of condensed ring radical, makes that the content of condensed ring radical is lower in the multipolymer, and the common polysilane that is difficult to simultaneously to generate in the reaction process separates.
Summary of the invention
The technical issues that need to address of the present invention are, a kind of simple to operate, safety is provided, and the polysilane polymerization degree is higher, and the gained multipolymer separates the more convenient condensed ring radical polysilane novel preparation method that contains.
Preparation method of fused ring radical containing polysilane of the present invention, vinyl silanes multipolymer B (Miller R.D.; Michl J.Chem.Rev.1989,89,1359; Huang Shiqiang etc., applied chemistry 2004,11,1196) in high boiling solvent α-chloronaphthalene, condensed ring radical is introduced in the following and condensed ring radical cyclopentadienone A generation addition reaction of nitrogen protection in the side chain of polysilane, must contain condensed ring radical polysilane product, and synthetic route is:
R
1, R
2, R
3, R
4Be methyl, ethyl, propyl group, butyl, hydrogen, vinyl;
A is
Ar is
n＝0-1000；m＝1-1000；P＝0-1000；
Described condensed ring radical cyclopentadienone A is a kind of in tetraphenylcyclopentadienone, luxuriant and rich with fragrance formula cyclopentadienone, the acenaphthene formula cyclopentadienone;
Described condensed ring radical Ar is a tetraphenyl phenyl, 2,9-phenylbenzene-7,8 benzo phenanthryl, 2, a kind of in 9-phenylbenzene-7, the 8 benzo acenaphthenyl.
When preparation vinyl silanes multipolymer, because monomeric active high, steric effect is little, thereby the polymerization degree of the vinyl silanes multipolymer that makes is big, the molecular weight height.Thus, the prepared polymerization degree that contains the condensed ring radical polysilane is big, the molecular weight height.Solved insurmountable problem in early-stage Study effectively.
Preferably one of reaction formula is as follows, gets product,
Preferred two reaction formula is as follows, product,
Preferred three reaction formula is as follows, product,
Vinyl silanes multipolymer B of the present invention can also pass through the alkyl vinyl dichlorosilane, alkyl phenyl dichlorosilane and/or dialkyldichlorosilan,s get with sodium generation condensation reaction in toluene, and then the Diels-Alder addition reaction takes place with the condensed ring radical cyclopentadienone, in the side chain of polysilane, introduce condensed ring radical.
Although the preparation of vinyl silanes multipolymer has bibliographical information, also do not carry out suitability for industrialized production, be difficult to obtain its commodity.
Preferably one of reaction formula is as follows:
Preferred two reaction formula is as follows:
Preferred three reaction formula is as follows:
By changing the monomeric feed ratio of organochlorosilane, can regulate the content of vinyl in the vinyl silanes multipolymer, and then obtain the polysilane of different condensed ring radical content.
The present invention is synthetic, and to contain the step of condensed ring radical polysilane as follows:
1) in reactor, feeds N
2Gas shiled adds dry toluene or dimethylbenzene, sodium, and high-speed stirring breaks into sodium sand when being heated to sodium fusion, and the weight of dry toluene or dimethylbenzene is 2～20 times of sodium weight;
2) under the lucifuge condition, slowly splash into the toluene mixing solutions of organochlorosilane, treat that solution becomes the bluish voilet reflux, is cooled to room temperature; The mol ratio of organochlorosilane and sodium is 1: 1～5;
3) add ethanol and water mixed liquid termination reaction, leach insolubles; Tell the upper strata organic layer, wash with water to non-sodium chloride; Decompression steams solvent and low-boiling-point substance gets thick liquid, after the dissolving of adding tetrahydrofuran (THF), must contain the vinyl silanes multipolymer with methyl alcohol sedimentation purifying again; Water and alcoholic acid mass ratio are 1～10: 1;
4) in proportion with above-mentioned gained contain ethylenic copolymer and the condensed ring radical cyclopentadienone is dissolved in the high boiling solvent, reflux, steaming desolventizes, and obtains containing the condensed ring radical silane copolymer; Vinyl is 2～20: 1 with the mol ratio that contains the condensed ring radical cyclopentadienone.
Preparation method of the present invention, owing to there is not sterically hindered influence during the vinyl silanes copolymer, obtain to contain vinyl silanes copolymer polymerization degree bigger, and then the condensed ring radical content height, the polymerization degree that contain the condensed ring radical polysilane that obtain are big, efficiently solve the problem that exists in the early stage research.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1.Multipolymer (Miller R.D. with 4.5g dichloromethyl phenylsilane and methyl ethylene dichlorosilane; Michl J.Chem.Rev.1989,89,1359), be dissolved in 100mL α-chloronaphthalene with 0.8g tetraphenyl phenyl cyclopentadienone, behind the reflux 10h, remove solvent under reduced pressure, obtain containing the tetraphenyl phenyl silane copolymer.
Embodiment 2.Multipolymer (Huang Shiqiang etc. with 6.3g dimethyldichlorosilane(DMCS), dichloromethyl phenylsilane and methyl ethylene dichlorosilane, applied chemistry 2004,11,1196), be dissolved in 100mL α-chloronaphthalene, behind the reflux 10h with the luxuriant and rich with fragrance formula cyclopentadienone of 1.2g, remove solvent under reduced pressure, obtain containing 2,9-phenylbenzene-7,8-benzophenanthrene base silane multipolymer.
Embodiment 3.Take into account and feed the N2 gas shiled in the four-hole bottle of gas operated device in that electric mixer, reflux condensing tube, constant pressure funnel, temperature are housed; add 100mL dry toluene (reflux was distilled after 24 hours in sodium), 12.1g sodium (chemical pure; Shanghai reagent four factories); start agitator when being heated to sodium fusion, the about 30min of high-speed stirring breaks into sodium sand to sodium.Under the lucifuge condition, splash into 14mLMeViSiCl in the 15min
2(Jilin chemical research institute heavily steams with preceding), 20mL MePhSiCl
2(preparing according to document: Liao Xuewei, Shi Baochuan, Zhang Mao's root, organosilicon material, 2000,5,1) and 12mL Me
2SiCl
2The toluene mixing solutions of (Xinanjiang River, Zhejiang chemical industry limited liability company heavily steams with preceding), solution becomes bluish voilet very soon, behind the reflux 12h, is cooled to room temperature.Add 50mL ethanol and 250mL water termination reaction, leach insolubles.Tell the upper strata organic layer, wash with water to non-sodium chloride.Decompression steams solvent and low-boiling-point substance, gets thick liquid, adds the dissolving of 40mL tetrahydrofuran (THF), gets 8.5g with 250mL methyl alcohol sedimentation purifying again and contains the vinyl silanes multipolymer.5.0g is contained the vinyl silanes multipolymer and the 1.0g tetraphenylcyclopentadienone is dissolved in 100ml α-chloronaphthalene, behind the reflux 10h, remove solvent under reduced pressure, obtain containing the tetraphenyl phenyl silane copolymer.
Embodiment 4.Take into account and feed the N2 gas shiled in the four-hole bottle of gas operated device in that electric mixer, reflux condensing tube, constant pressure funnel, temperature are housed; add 100mL dry toluene, 12.1g sodium; start agitator when being heated to sodium fusion, the about 30min of high-speed stirring breaks into sodium sand to sodium.Under the lucifuge condition, splash into 14mL MeViSiCl in the 15min
2With 20mL MePhSiCl
2The toluene mixing solutions, solution becomes bluish voilet very soon, behind the reflux 12h, is cooled to room temperature.Add 50mL ethanol and 250mL water termination reaction, leach insolubles.Tell the upper strata organic layer, wash with water to non-sodium chloride.Decompression steams solvent and low-boiling-point substance, gets thick liquid, adds the dissolving of 40mL tetrahydrofuran (THF), gets 6.8g with 250mL methyl alcohol sedimentation purifying again and contains the vinyl silanes multipolymer.5.0g is contained the luxuriant and rich with fragrance formula cyclopentadienone of vinyl silanes multipolymer and 1.0g be dissolved in 100ml α-chloronaphthalene, behind the reflux 10h, remove solvent under reduced pressure, obtain containing 2,9-phenylbenzene-7,8-benzophenanthrene base silane multipolymer.
Embodiment 5.Take into account and feed the N2 gas shiled in the four-hole bottle of gas operated device in that electric mixer, reflux condensing tube, constant pressure funnel, temperature are housed; add 100mL dry toluene, 12.1g sodium; start agitator when being heated to sodium fusion, the about 30min of high-speed stirring breaks into sodium sand to sodium.Under the lucifuge condition, splash into 14mL MeViSiCl in the 15min
2With 20mL MePhSiCl
2The toluene mixing solutions, solution becomes bluish voilet very soon, behind the reflux 12h, is cooled to room temperature.Add 50mL ethanol and 250mL water termination reaction, leach insolubles.Tell the upper strata organic layer, wash with water to non-sodium chloride.Decompression steams solvent and low-boiling-point substance, gets thick liquid, adds the dissolving of 40mL tetrahydrofuran (THF), gets 6.8g with 250mL methyl alcohol sedimentation purifying again and contains the vinyl silanes multipolymer.5.0g is contained the vinyl silanes multipolymer and 1.0g acenaphthene formula cyclopentadienone is dissolved in 100ml α-chloronaphthalene, behind the reflux 10h, remove solvent under reduced pressure, obtain containing 2,9-phenylbenzene-7,8-benzo acenaphthenyl silane copolymer.
Embodiment 6.Take into account and feed the N2 gas shiled in the four-hole bottle of gas operated device in that electric mixer, reflux condensing tube, constant pressure funnel, temperature are housed; add 100mL dry toluene, 13.8g sodium; start agitator when being heated to sodium fusion, the about 30min of high-speed stirring breaks into sodium sand to sodium.Under the lucifuge condition, splash into 14mL MeViSiCl in the 15min
2, 30mL MePhSiCl
2With 12mL Me
2SiCl
2The toluene mixing solutions, solution becomes bluish voilet very soon, behind the reflux 12h, is cooled to room temperature.Add 50mL ethanol and 250mL water termination reaction, leach insolubles.Tell the upper strata organic layer, wash with water to non-sodium chloride.Decompression steams solvent and low-boiling-point substance, gets thick liquid, adds the dissolving of 40mL tetrahydrofuran (THF), gets 12.0g with 250mL methyl alcohol sedimentation purifying again and contains the vinyl silanes multipolymer.5.0g is contained the vinyl silanes multipolymer and the 0.8g tetraphenylcyclopentadienone is dissolved in 100ml α-chloronaphthalene, behind the reflux 10h, remove solvent under reduced pressure, obtain containing the tetraphenyl phenyl silane copolymer.
Claims (7)
1, a kind of Preparation method of fused ring radical containing polysilane; vinyl silanes multipolymer B is in high boiling solvent α-chloronaphthalene; following and the condensed ring radical cyclopentadienone A generation addition reaction of nitrogen protection; in the side chain of polysilane, introduce condensed ring radical Ar; must contain condensed ring radical polysilane product; described vinyl silanes multipolymer is B1, and its reaction formula is:
R
1, R
2Be methyl, ethyl, propyl group, butyl, hydrogen or vinyl;
A is
Ar is
n＝0-1000；m＝1-1000；P＝0-1000；
Described condensed ring radical cyclopentadienone A is a kind of in tetraphenylcyclopentadienone, luxuriant and rich with fragrance formula cyclopentadienone, the acenaphthene formula cyclopentadienone;
Described Ar is a tetraphenyl phenyl, 2,9-phenylbenzene-7,8 benzo phenanthryl, 2, a kind of in 9-phenylbenzene-7, the 8 benzo acenaphthenyl.
2, a kind of Preparation method of fused ring radical containing polysilane; vinyl silanes multipolymer B is in high boiling solvent α-chloronaphthalene; following and the condensed ring radical cyclopentadienone A generation addition reaction of nitrogen protection; in the side chain of polysilane, introduce condensed ring radical Ar; must contain condensed ring radical polysilane product; described vinyl silanes multipolymer is B2, and its reaction formula is:
R
1, R
2, R
3, R
4Be methyl, ethyl, propyl group, butyl, hydrogen or vinyl;
A is
Ar is
n＝0-1000；m＝1-1000；P＝0-1000；
Described condensed ring radical cyclopentadienone A is a kind of in tetraphenylcyclopentadienone, luxuriant and rich with fragrance formula cyclopentadienone, the acenaphthene formula cyclopentadienone;
Described Ar is a tetraphenyl phenyl, 2,9-phenylbenzene-7,8 benzo phenanthryl, 2, a kind of in 9-phenylbenzene-7, the 8 benzo acenaphthenyl.
3, a kind of Preparation method of fused ring radical containing polysilane; vinyl silanes multipolymer B is in high boiling solvent α-chloronaphthalene; following and the condensed ring radical cyclopentadienone A generation addition reaction of nitrogen protection; in the side chain of polysilane, introduce condensed ring radical Ar; must contain condensed ring radical polysilane product; described vinyl silanes multipolymer is B3, and its reaction formula is:
R
1, R
2, R
3Be methyl, ethyl, propyl group, butyl, hydrogen or vinyl;
A is
Ar is
n＝0-1000；m＝1-1000；P＝0-1000；
Described condensed ring radical cyclopentadienone A is a kind of in tetraphenylcyclopentadienone, luxuriant and rich with fragrance formula cyclopentadienone, the acenaphthene formula cyclopentadienone;
Described Ar is a tetraphenyl phenyl, 2,9-phenylbenzene-7,8 benzo phenanthryl, 2, a kind of in 9-phenylbenzene-7, the 8 benzo acenaphthenyl.
4, Preparation method of fused ring radical containing polysilane according to claim 1, it is characterized in that the alkyl vinyl dichlorosilane, the alkyl phenyl dichlorosilane contains vinyl silanes multipolymer B1 with sodium generation condensation reaction preparation earlier in toluene, with the condensed ring radical cyclopentadienone Diels-Alder addition reaction takes place again:
5, Preparation method of fused ring radical containing polysilane according to claim 2, it is characterized in that the alkyl vinyl dichlorosilane, alkyl phenyl dichlorosilane and dialkyldichlorosilan,s contain vinyl silanes multipolymer B2 with sodium generation condensation reaction preparation earlier in toluene, with the condensed ring radical cyclopentadienone Diels-Alder addition reaction takes place again:
6, Preparation method of fused ring radical containing polysilane according to claim 3, it is characterized in that the alkyl vinyl dichlorosilane, dialkyldichlorosilan,s contains vinyl silanes multipolymer B3 with sodium generation condensation reaction preparation earlier in toluene, with the condensed ring radical cyclopentadienone Diels-Alder addition reaction takes place again:
7,, it is characterized in that preparation process is according to claim 4 or 5 or 6 described Preparation method of fused ring radical containing polysilane:
1) in reactor, feeds N
2Gas shiled adds dry toluene or dimethylbenzene, sodium, and high-speed stirring breaks into sodium sand when being heated to sodium fusion, and the weight of organic solvent is 2～20 times of sodium weight;
2) under the lucifuge condition, slowly splash into the toluene mixing solutions of organochlorosilane, treat that solution becomes the bluish voilet reflux, is cooled to room temperature; The mol ratio of organochlorosilane and sodium is 1: 1～5;
3) add ethanol and water mixed liquid termination reaction, leach insolubles; Tell the upper strata organic layer, wash with water to non-sodium chloride; Decompression steams solvent and low-boiling-point substance gets thick liquid, after the dissolving of adding tetrahydrofuran (THF), must contain the vinyl silanes multipolymer with methyl alcohol sedimentation purifying again; Water and alcoholic acid mass ratio are 1～10: 1;
4) in proportion with above-mentioned gained contain ethylenic copolymer and the condensed ring radical cyclopentadienone is dissolved in the high boiling solvent, reflux, steaming desolventizes, and obtains containing the condensed ring radical silane copolymer; Vinyl is 2～20: 1 with the mol ratio that contains the condensed ring radical cyclopentadienone.
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| CN106751863A (en) * | 2016-12-26 | 2017-05-31 | 沈阳化工大学 | A kind of silicon rubber radiation hardness auxiliary agent and preparation method thereof |
| CN106810832A (en) * | 2016-12-26 | 2017-06-09 | 沈阳化工大学 | Modified polyethylene terephthalate of isomerism containing condensed cyclic structure crosslinking agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4879334A (en) * | 1986-03-11 | 1989-11-07 | The Foundation: The Research Institute For Special Inorganic Materials | Organopolyarylsilanes, process for manufacturing the same and fibers comprising the same |
| CN1240459A (en) * | 1996-12-27 | 2000-01-05 | 大阪瓦斯株式会社 | Process for preparing polysilanes |
-
2005
- 2005-10-31 CN CNB2005100613196A patent/CN100345880C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4879334A (en) * | 1986-03-11 | 1989-11-07 | The Foundation: The Research Institute For Special Inorganic Materials | Organopolyarylsilanes, process for manufacturing the same and fibers comprising the same |
| CN1240459A (en) * | 1996-12-27 | 2000-01-05 | 大阪瓦斯株式会社 | Process for preparing polysilanes |
Non-Patent Citations (2)
| Title |
|---|
| 新型功能聚硅烷的研究进展 李效东等，材料研究学报，第16卷第4期 2002 * |
| 聚硅烷Wurtz合成及β-SiC纤维制备的机理 董占能等，昆明理工大学学报(理工版)，第28卷第2期 2003 * |
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