CN104447850A - Preparation method for double-splint type divinyl oligomeric silsesquioxane - Google Patents
Preparation method for double-splint type divinyl oligomeric silsesquioxane Download PDFInfo
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- CN104447850A CN104447850A CN201410612556.6A CN201410612556A CN104447850A CN 104447850 A CN104447850 A CN 104447850A CN 201410612556 A CN201410612556 A CN 201410612556A CN 104447850 A CN104447850 A CN 104447850A
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Abstract
The invention discloses a preparation method for double-splint type divinyl oligomeric silsesquioxane. The method comprises the following steps of: (1) adding isopropanol into phenyltrimethoxysilane and sodium hydroxide, heating and reflowing for 4-24 hours, stopping the heating and reducing the temperature to the room temperature, reacting for 10-24 hours again, filtering after the reaction is finished, collecting a solid product and drying for later use; (2) adding the solid product prepared in the step (1) into an aprotic solvent so as to be dissolved, adding methyl vinyl dichloromethylsilane and an acid-binding agent again and reacting for 2-24 hours, and evaporating to remove the solvent after the reaction is finished to obtain a product. The preparation method has the advantages of easily-available raw materials, mild synthetic method, simple and efficient synthesizing routes, easiness for purification of the product, high yield and the like; the obtained product D-VPOSS contains active vinyl and can directly participate in polymerization reaction; meanwhile, vinyl can be further functionalized by various modification means.
Description
Technical field
The present invention relates to chemosynthesis technical field, particularly relate to a kind of preparation method of double fastener template divinyl oligomeric silsesquioxane.
Background technology
Existing polysilsesquioxane (POSS) mostly is a functional group or multiple functional group, in its use procedure, can only exist as end-capping reagent (monofunctional) or star/crosslinked inorganic core (multiple functional radical), greatly limit its range of application.Foreign literature reports the synthetic method of double fastener template dihydro base oligomeric silsesquioxane (D-HPOSS), but functionalized to D-HPOSS, need to adopt with the hydrosilylation addition reaction of platinum-ligand catalysis.To D-HPOSS success modified (functionalized), modified product can be used as difunctional monomer and carry out condensation reaction, obtains the hybrid material that main polymer chain contains inorganic component.But, because hydrosilylation addition reaction has particular requirement to the structure of monomer and chemical property, so limit the further application of the functionalized of D-HPOSS and modification POSS.
First Kakimoto has synthesized double-deck type D-HPOSS (patent, Jpn.KokaiTokkyo Koho 2006265243A, 2006; Publish an article Macromolecules, and 2008,41,3481 – 3487.), Chemistry and Chemical Engineering College of Shanghai Communications University Zheng Si professors Xun etc. use hydrosilylation addition reaction modification D-HPOSS, obtain containing bis-epoxy base and two hydroxyl D-POSS (J.Mater.Chem., 2011,21,19344; Polym.Chem., 2013,4,1491) and for the synthesis of hydridization polyester and hybrid polyurethane.
There is following shortcoming in modification (functionalized) method of existing D-HPOSS:
1) due to the shortcoming of hydrosilylation addition reaction self, cause that to can be used for functionalized monomeric species few;
2) use expensive transition-metal catalyst, these catalyzer are harmful to organism, limit the biology of product, the purposes of field of medicaments;
3) modification (functionalized) process is complicated, needs to remove catalyzer, reduces the yield of modified product;
4) modification (functionalized) condition is strict.As, need under anhydrous, anaerobic conditions, temperature of reaction is usually at 100-110 DEG C, and use the toxic organic solvents such as toluene, obtaining the protic functional group such as hydroxyl needs to protect-go protection process etc.
Summary of the invention
The present invention proposes a kind of method of synthesis double fastener template divinyl oligomeric silsesquioxane (D-VPOSS), have raw material to be easy to get, synthesis condition is gentle, and synthetic route is simple, efficient, product purification (purification) is easy, yield advantages of higher.And the product D-VPOSS itself obtained can participate in polyreaction directly containing active ethylene group, meanwhile, vinyl can be functionalized further by multiple modified method.
The present invention adopts following technical scheme:
The concrete steps of the preparation method of double fastener template divinyl oligomeric silsesquioxane of the present invention are as follows:
(1) in phenyltrimethoxysila,e and sodium hydroxide, Virahol is added, the weight ratio of phenyltrimethoxysila,e and sodium hydroxide is 25-35:4.0-4.5, the weightmeasurement ratio of phenyltrimethoxysila,e and Virahol is 25-35:150-250g/mL, then reflux 4-24h, stops heating, be down to room temperature, react 10-24h again, reaction terminates, and filters, collect solid product, drying for standby;
(2) solid product prepared by step (1) is joined in aprotic solvent, make it dissolve, add methylvinyldichlorosilane and acid binding agent again, the weightmeasurement ratio of methylvinyldichlorosilane and acid binding agent is 5-10:4-8g/mL, then 2-24h is reacted, reaction terminates, and boils off solvent, namely obtains double fastener template divinyl oligomeric silsesquioxane of the present invention.
In step (1), the weight ratio of preferred phenyltrimethoxysila,e and sodium hydroxide is 30:4.2, and the weightmeasurement ratio of phenyltrimethoxysila,e and Virahol is 30:200g/mL.
In step (1), preferred reflux 12h, stops heating being down to room temperature, then reacts 18h.
In step (2), described aprotic solvent is tetrahydrofuran (THF).
In step (2), described acid binding agent is triethylamine.
In step (2), the weightmeasurement ratio of preferred vinyl dichlorosilane and acid binding agent is 8:6g/ml.
In step (2), preferred reaction 12h.
Positively effect of the present invention is as follows:
The preparation method of double fastener template divinyl oligomeric silsesquioxane of the present invention can be functionalized further functional group's kind many, can directly obtain containing protic active group (as hydroxyl, carboxyl etc.);
Preparation method's reaction conditions of double fastener template divinyl oligomeric silsesquioxane of the present invention is gentle, and speed of response is fast, does not need metal catalyst and noxious solvent, and purify simple, modification is easy, and product Application Areas is wide.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of double fastener template divinyl oligomeric silsesquioxane prepared by the embodiment of the present invention 3.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1
The concrete steps of the preparation method of double fastener template divinyl oligomeric silsesquioxane of the present invention are as follows:
(1) in phenyltrimethoxysila,e (25g) and sodium hydroxide (4.0g), add Virahol (150mL), then reflux 4h, stop heating being down to room temperature, react 10h again, reaction terminates, and filters, collect solid product, drying for standby;
(2) solid product prepared by step (1) is joined in aprotic solvent, make it dissolve, add methylvinyldichlorosilane (5g) and acid binding agent (4mL) again, then 2h is reacted, reaction terminates, boil off solvent, after process, namely obtain double fastener template divinyl oligomeric silsesquioxane of the present invention.
In step (2), described aprotic solvent is tetrahydrofuran (THF).
In step (2), described acid binding agent is triethylamine.
Reaction yield is 72%.
Embodiment 2
The concrete steps of the preparation method of double fastener template divinyl oligomeric silsesquioxane of the present invention are as follows:
(1) in phenyltrimethoxysila,e (35g) and sodium hydroxide (4.5g), add Virahol (250mL), then reflux 24h, stop heating being down to room temperature, react 24h again, reaction terminates, and filters, collect solid product, drying for standby;
(2) solid product prepared by step (1) is joined in aprotic solvent, make it dissolve, add methylvinyldichlorosilane (10g) and acid binding agent (8mL) again, then 24h is reacted, reaction terminates, boil off solvent, after process, namely obtain double fastener template divinyl oligomeric silsesquioxane of the present invention.
In step (2), described aprotic solvent is tetrahydrofuran (THF).
In step (2), described acid binding agent is triethylamine.
Reaction yield is 75%.
Embodiment 3
The concrete steps of the preparation method of double fastener template divinyl oligomeric silsesquioxane of the present invention are as follows:
(1) in phenyltrimethoxysila,e (30g) and sodium hydroxide (4.2g), add Virahol (200mL), then reflux 12h, stop heating being down to room temperature, react 18h again, reaction terminates, and filters, collect solid product, drying for standby;
(2) solid product prepared by step (1) is joined in aprotic solvent, make it dissolve, add methylvinyldichlorosilane (8g) and acid binding agent (6mL) again, then 12h is reacted, reaction terminates, boil off solvent, after process, namely obtain double fastener template divinyl oligomeric silsesquioxane of the present invention.
In step (2), described aprotic solvent is tetrahydrofuran (THF).
In step (2), described acid binding agent is triethylamine.
Reaction yield is 76%.
As shown in Figure 1, at wave number 3078 and 3048cm
-1place is the hydrocarbon absorption peak of vinyl, 1596 and 1427cm
-1place is the absorption peak of silicon-phenyl ring, 1409cm
-1locate as the hydrocarbon absorption peak of vinyl, 1120cm
-1place is the absorption peak of siloxane bond, 810cm
-1place is the hydrocarbon absorption peak of phenyl ring; 731cm
-1place is CH
2absorption peak, 694cm
-1place is the absorption peak of siloxane bond.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (6)
1. a preparation method for double fastener template divinyl oligomeric silsesquioxane, is characterized in that: the concrete steps of described preparation method are as follows:
(1) in phenyltrimethoxysila,e and sodium hydroxide, Virahol is added, the weight ratio of phenyltrimethoxysila,e and sodium hydroxide is 25-35:4.0-4.5, the weightmeasurement ratio of phenyltrimethoxysila,e and Virahol is 25-35:150-250g/ml, then reflux 4-24h, stops heating being down to room temperature, then reacts 10-24h, reaction terminates, filter, collect solid product, drying for standby;
(2) solid product prepared by step (1) is joined in aprotic solvent, make it dissolve, add hydridovinyldichlorosilane and acid binding agent again, the weightmeasurement ratio of hydridovinyldichlorosilane and acid binding agent is 5-10:4-8g/ml, then 2-24h is reacted, reaction terminates, and boils off solvent, namely obtains double fastener template divinyl oligomeric silsesquioxane of the present invention.
2. the preparation method of double fastener template divinyl oligomeric silsesquioxane as claimed in claim 1, it is characterized in that: in step (1), the weight ratio of phenyltrimethoxysila,e and sodium hydroxide is 30:4.2, and the weightmeasurement ratio of phenyltrimethoxysila,e and Virahol is 30:200g/ml.
3. the preparation method of double fastener template divinyl oligomeric silsesquioxane as claimed in claim 1, is characterized in that: in step (1), reflux 12h, stops heating being down to room temperature, then reacts 18h.
4. the preparation method of double fastener template divinyl oligomeric silsesquioxane as claimed in claim 1, is characterized in that: in step (2), described aprotic solvent is tetrahydrofuran (THF).
5. the preparation method of double fastener template divinyl oligomeric silsesquioxane as claimed in claim 1, is characterized in that: in step (2), described acid binding agent is triethylamine.
6. the preparation method of double fastener template divinyl oligomeric silsesquioxane as claimed in claim 1, it is characterized in that: in step (2), the weightmeasurement ratio of methylvinyldichlorosilane and acid binding agent is 8:6g/ml.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294754A (en) * | 2015-11-11 | 2016-02-03 | 上海交通大学 | Synthesis method of diamine-phenyl-based double-splint type cagesilsesquioxane |
| CN105694045A (en) * | 2016-03-16 | 2016-06-22 | 烟台大学 | Functionalization method of divinyl double-plywood type oligomeric silsesquioxane |
| CN115960357A (en) * | 2022-12-18 | 2023-04-14 | 四川大学 | Vinyl T 8 ，T 10 And T 12 Macro separation method of POSS |
| CN116289228A (en) * | 2023-03-16 | 2023-06-23 | 山东大学 | Alkoxy-functionalized double-splint type POSS super-hydrophobic coating, and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| US20040249103A1 (en) * | 2001-09-18 | 2004-12-09 | Yoshitaka Morimoto | Silsesquioxane derivatives and process for production thereof |
| JP2012012754A (en) * | 2010-06-04 | 2012-01-19 | Jnc Corp | Fiber obtained from polymer containing silsesquioxane skeleton, fiber assembly and methods for producing them |
| US20120178894A1 (en) * | 2003-03-13 | 2012-07-12 | Inagaki Jyun-Ichi | Compound having silsesquioxane skeleton and its polymer |
| CN103665863A (en) * | 2012-09-13 | 2014-03-26 | 北京化工大学 | Thermosetting resin composition containing double-tower type epoxy silsesquioxane |
-
2014
- 2014-11-04 CN CN201410612556.6A patent/CN104447850A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040249103A1 (en) * | 2001-09-18 | 2004-12-09 | Yoshitaka Morimoto | Silsesquioxane derivatives and process for production thereof |
| US20120178894A1 (en) * | 2003-03-13 | 2012-07-12 | Inagaki Jyun-Ichi | Compound having silsesquioxane skeleton and its polymer |
| JP2012012754A (en) * | 2010-06-04 | 2012-01-19 | Jnc Corp | Fiber obtained from polymer containing silsesquioxane skeleton, fiber assembly and methods for producing them |
| CN103665863A (en) * | 2012-09-13 | 2014-03-26 | 北京化工大学 | Thermosetting resin composition containing double-tower type epoxy silsesquioxane |
Non-Patent Citations (1)
| Title |
|---|
| MAKOTO SEINO等: "Hydrosilylation Polymerization of Double-Decker-Shaped Silsesquioxane Having Hydrosilane with Diynes", 《MACROMOLECULES》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294754A (en) * | 2015-11-11 | 2016-02-03 | 上海交通大学 | Synthesis method of diamine-phenyl-based double-splint type cagesilsesquioxane |
| CN105294754B (en) * | 2015-11-11 | 2018-06-29 | 上海交通大学 | The synthetic method of diamines phenyl double plate cage-type silsesquioxane |
| CN105694045A (en) * | 2016-03-16 | 2016-06-22 | 烟台大学 | Functionalization method of divinyl double-plywood type oligomeric silsesquioxane |
| CN115960357A (en) * | 2022-12-18 | 2023-04-14 | 四川大学 | Vinyl T 8 ，T 10 And T 12 Macro separation method of POSS |
| CN115960357B (en) * | 2022-12-18 | 2023-10-31 | 四川大学 | Vinyl T 8 ，T 10 And T 12 Macroscopic quantity separation method of POSS |
| CN116289228A (en) * | 2023-03-16 | 2023-06-23 | 山东大学 | Alkoxy-functionalized double-splint type POSS super-hydrophobic coating, and preparation method and application thereof |
| CN116289228B (en) * | 2023-03-16 | 2024-09-27 | 山东大学 | Alkoxy-functionalized double-splint type POSS super-hydrophobic coating, and preparation method and application thereof |
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