CN102633830A - Dihydroxy cage-shaped silsesquioxane and preparation method thereof - Google Patents
Dihydroxy cage-shaped silsesquioxane and preparation method thereof Download PDFInfo
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- CN102633830A CN102633830A CN201210089401XA CN201210089401A CN102633830A CN 102633830 A CN102633830 A CN 102633830A CN 201210089401X A CN201210089401X A CN 201210089401XA CN 201210089401 A CN201210089401 A CN 201210089401A CN 102633830 A CN102633830 A CN 102633830A
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- PXQJVLUOMRMPOI-UHFFFAOYSA-N N=[U]([Si+](O[SiH+]O1)(O[Si+](O[Si+](O)O2)O3)O[Si+]4(c5ccccc5)O[Si+]3(c3ccccc3)O[Si+]2(c2ccccc2)O[Si+]1(c1ccccc1)O4)[U]([U]([U])=N)=N Chemical compound N=[U]([Si+](O[SiH+]O1)(O[Si+](O[Si+](O)O2)O3)O[Si+]4(c5ccccc5)O[Si+]3(c3ccccc3)O[Si+]2(c2ccccc2)O[Si+]1(c1ccccc1)O4)[U]([U]([U])=N)=N PXQJVLUOMRMPOI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of dihydroxy cage-shaped silsesquioxane. The preparation method is characterized by comprising the steps of: reacting T7 sodium salt with trichlorosilane under the protection of nitrogen atmosphere in a stirring manner to prepare monochloropropyl cage-shaped silsesquioxane, and then carrying out substitution reaction with diethanolamine to prepare dihydroxy cage-shaped silsesquioxane, wherein dihydroxy cage-shaped silsesquioxane is an organic-inorganic nanomaterial which has a skeleton structure formed by silicon-oxygen bonds and has two hydroxy groups serving as functional groups, and the structure of dihydroxy cage-shaped silsesquioxane is shown in the specification. The preparation method is simple in process, free from environmental pollution, and can be used for synthesis research of cage-shaped silsesquioxane/polymer hybrid materials.
Description
Technical field
The invention belongs to preparing method's technical field of silsesquioxane, be specifically related to have the preparation method of the cage-type silsesquioxane of two hydroxyls.
Background technology
U.S.'s " materials chemistry " (Chemistry of Materials; 2003; 15 (1) 264-268) reported that preparing interior two fluorine with the cage cleavage method replaces semiclosed cage; And with the synthetic semiclosed cyclopentyl cage-type silsesquioxane of dianiline base of it further replacement, thereby the cage-type silsesquioxane structure is successfully introduced in the polyimide main chain.Because semiclosed cage-type silsesquioxane more totally-enclosed cage-type silsesquioxane on mechanical property and thermal property has gap; Cause the thermal property of institute's synthetic matrix material to improve limited; And this method is owing to needs make cage structure cracked reason; Make its complex process, complex operation, the product of processing also are prone to contaminate environment.
U.S.'s " international polymkeric substance " (Polymer International; 2005; 54 (1): 47-53) reported the hybrid material that the semiclosed seven cyclopentyl cage-type silsesquioxanes that contain three epoxy group(ing) and polyethyleneterephthalate form; Through the fusion in-situ polymerization; Make the epoxy group(ing) of cage-type silsesquioxane and the terminal hydroxy group reaction of polyethylene terephthalate that cage-type silsesquioxane is introduced main polymer chain and made the polymer formation reticulated structure, but semiclosed cage-type silsesquioxane more totally-enclosed cage-type silsesquioxane on mechanical property and thermal property have gap, has limited the embodiment of cage-type silsesquioxane/polymer hybrid material excellent properties; And this method be because cage-type silsesquioxane and polyethyleneterephthalate will form hybrid material, makes its complex process, security low.
Summary of the invention
The purpose of this invention is to provide a kind of cage-type silsesquioxane and preparation method thereof,, make simple, the environmentally safe of technology to overcome prior art complex operation, the low defective of security with two hydroxyls.
Preparing method with cage-type silsesquioxane of two hydroxyls of the present invention is characterized in that:
Earlier by seven phenyl, three siloxy sodium salt (T
7Sodium salt) be 1 with the trichlorosilane mol ratio: (1.1～1.5) are made into T in solvent
7Sodium salt and trichlorosilane total mass/volume by volume concentration are the solution of 0.1～0.3g/mL, with the T that is made into
7The solution of sodium salt and trichlorosilane adds in the nitrogen atmosphere reactor drum, and under agitation, elder generation makes T 0 ℃ temperature
7Sodium salt and trichlorosilane stirring reaction 2～4h, at temperature continuation stirring reaction 2～4h of 20～30 ℃, reaction back elimination precipitates again, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Be 1 by monochloro propyl group cage-type silsesquioxane and diethylolamine mol ratio again: (1.0～30.0); Total mass/the volume by volume concentration that in solvent, is made into monochloro propyl group cage-type silsesquioxane and diethylolamine is the solution of 0.05～0.15g/mL; Make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 24～48h 80～100 ℃ temperature of reaction down with stirring, the reaction back is precipitated to separate out and filter in deionized water and is obtained pair hydroxyl cage-type silsesquioxanes;
Said solvent is THF or N, dinethylformamide.
The present invention adopts the cage-type silsesquioxane with two hydroxyls of method for preparing, is the organic-inorganic nano material that is made up of skeleton structure siliconoxygen bond; It is characterized in that structure is:
It is that functional group is a hydroxyl, and the hydroxy functional group number is two a cage-type silsesquioxane.
The above-mentioned synthetic route with cage-type silsesquioxane of two hydroxyls of the present invention can be represented as follows:
Method of the present invention its essence is earlier stir and the condition of nitrogen atmosphere protection under with T
7Sodium salt and trichlorosilane reaction make monochloro propyl group cage-type silsesquioxane, again monochloro propyl group cage-type silsesquioxane and diethylolamine have been synthesized a kind of new compound under stirring and heating condition--have the cage-type silsesquioxane of two hydroxyls.
According to U.S.'s " chemistry summary " (Chemical Reviews; 2010; 110 (4): 2081-2173) report can be known; Semiclosed cage-type silsesquioxane does not have the height of totally-enclosed cage-type silsesquioxane on mechanical property and thermal property, this has limited the embodiment of cage-type silsesquioxane/polymer hybrid material excellent properties, and its key then is the synthetic of the definite polyfunctional group dead front type cage-type silsesquioxane of functional group's number.Comparatively ripe about the cage-type silsesquioxane research of eight functional groups at present; But eight functional groups cage-type silsesquioxanes introduce the excessively crosslinked uncertainty with level of response of polymkeric substance etc. make its on performance not even like the simple function group cage-type silsesquioxane, thereby the substituted cage-type silsesquioxane of synthetic bifunctional has unique significance because.Through infrared spectrum, hydrogen spectrum nuclear magnetic spectrogram, silicon spectrum nuclear magnetic spectrogram, proved and adopted method of the present invention to prepare two hydroxyl cage-type silsesquioxanes.The hydrogen proton peak position of this pair hydroxyl cage-type silsesquioxane is following: δ=8.33-6.33 (
Ph SiO
3), 3.45 (N (CH
2C
H 2OH)
2), 2.49 (N (C
H 2C H
2OH)
2And SiCH
2CH
2C
H 2N)), 1.73 (SiCH
2C
H 2CH
2N), 1.37 (N (CH
2CH
2O
H )
2), 0.56 (SiC
H 2CH
2CH
2N).
The present invention adopt stir and the condition of nitrogen atmosphere protection under with T
7But the reaction of sodium salt and trichlorosilane make monochloro propyl group cage-type silsesquioxane the way imagery be referred to as " drift angle-block method ".Because the present invention has adopted " drift angle-block method ", and adopt functional group to change method, thereby prepared the cage-type silsesquioxane of two hydroxyls.Compare with the method for simple function group cage-type silsesquioxane with existing synthetic semiclosed cage-type silsesquioxane; The present invention overcome because the restriction that semiclosed cage-type silsesquioxane is used former thus make its complex process, trivial operations, security is low and the defective of contaminate environment, has obtained can be applicable to the two more widely hydroxyl cage-type silsesquioxanes of cage-type silsesquioxane/polymer nanocomposites.
Description of drawings
Fig. 1 is the hydrogen spectrum nuclear magnetic spectrogram of monochloro propyl group cage-type silsesquioxane.
Fig. 2 is the silicon spectrum nuclear magnetic spectrogram of monochloro propyl group cage-type silsesquioxane.
Fig. 3 is the infrared spectrum of monochloro propyl group cage-type silsesquioxane (a) and two hydroxyl cage-type silsesquioxanes (b).
Fig. 4 is the hydrogen spectrum nuclear magnetic spectrogram of two hydroxyl cage-type silsesquioxanes.
Embodiment
Embodiment 1:
Earlier with 10g seven phenyl three siloxy sodium salt (T
7Sodium salt) and the 3.2g trichlorosilane be dissolved in wiring solution-forming in the 150mL anhydrous tetrahydro furan, the reactor drum that places nitrogen atmosphere 0 ℃ with magnetic agitation under make T
7Sodium salt and trichlorosilane reaction 3h makes reaction system continue reaction 3h at 25 ℃ down with stirring again, reaction back elimination deposition, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Again with 1g monochloro propyl group cage-type silsesquioxane and 1g diethylolamine wiring solution-forming in the anhydrous N of 15mL, dinethylformamide; Under 90 ℃ temperature of reaction and magnetic agitation, make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 36h; Reaction back deposition in deionized water is separated out and is filtered, and has obtained two hydroxyl cage-type silsesquioxanes at last.
The checking explanation of products therefrom:
Fig. 1 has provided the hydrogen spectrum nuclear magnetic spectrogram of monochloro propyl group cage-type silsesquioxane.Can analyze the peak that draws chemical shift δ=3.52,1.87 and 0.80 place from Fig. 1 and correspond to three kinds of hydrogen (H) proton on the chloropropyl, δ=7.74-7.80 and 7.31-7.52 are corresponding to the H proton on the phenyl ring.
In order further to seal the success that react at the angle in the proof said process of the present invention, monochloro propyl group cage-type silsesquioxane has been carried out the silicon nuclear-magnetism detected.Fig. 2 is the silicon spectrum nuclear magnetic spectrogram of monochloro propyl group cage-type silsesquioxane.Can analyze from Fig. 2 and to draw δ=-65.5 and correspond to the Si atom that links to each other with chloropropyl, δ=-78.5 correspond to the Si atom that links to each other with phenyl ring.Above analytical results instruction book chloropropyl cage-type silsesquioxane is successfully synthetic.
Fig. 3 is that monochloro propyl group cage-type silsesquioxane (is labeled as a) infrared spectrum with two hydroxyl cage-type silsesquioxanes (being labeled as b).Can find with the position of the characteristic stretching vibration peak of two hydroxyl cage-type silsesquioxane infrared line b through the monochloro propyl group cage-type silsesquioxane infrared line a in the comparison diagram 3: two hydroxyl cage-type silsesquioxanes are at 1132cm
-1The characteristic stretching vibration peak of appearance Si-O-Si at place, simultaneously 2940,2874cm
-1The peak intensity at place obviously strengthens with respect to monochloro propyl group cage-type silsesquioxane, this mainly be since in the diethylolamine introducing of 4 methylene radical caused 2940,2874cm
-1The peak intensity at place increases, and owing to the appearance of hydroxy functional group makes at 3392cm
-1Hydroxyl peak occurs, proved the synthetic of two hydroxyl cage-type silsesquioxanes thus.
Fig. 4 is the proton magnetic spectrum figure of two hydroxyl cage-type silsesquioxanes.The hydrogen proton peak position of two hydroxyl cage-type silsesquioxanes is following: δ=8.33-6.33 (
Ph SiO
3), 3.45 (N (CH
2C
H 2OH)
2), 2.49 (N (C
H 2C H
2OH)
2And SiCH
2CH
2C
H 2N)), 1.73 (SiCH
2C
H 2CH
2N), 1.37 (N (CH
2CH
2O
H )
2), 0.56 (SiC
H 2CH
2CH
2N).Through above analysis, can reach a conclusion: two hydroxyl cage-type silsesquioxanes are successfully synthetic.It is that functional group is a hydroxyl, and the hydroxy functional group number is two a cage-type silsesquioxane.
Adopted among the present invention stir and the condition of nitrogen atmosphere protection under with T
7But the reaction of sodium salt and trichlorosilane make monochloro propyl group cage-type silsesquioxane the way imagery be referred to as " drift angle-block method ".Because the present invention has adopted " drift angle-block method ", and adopt functional group to change method, thereby prepared the cage-type silsesquioxane of two hydroxyls.Compare with the method for simple function group cage-type silsesquioxane with existing synthetic semiclosed cage-type silsesquioxane; The reason that the present invention has overcome the restriction of using owing to semiclosed cage-type silsesquioxane makes its complex process, trivial operations, security is low and the defective of contaminate environment, has obtained can be applicable to the two more widely hydroxyl cage-type silsesquioxanes of cage-type silsesquioxane/polymer nanocomposites.
Embodiment 2:
Earlier with 10g T
7Sodium salt and 3.2g trichlorosilane are dissolved in wiring solution-forming in the anhydrous N of 150mL, the dinethylformamide, the reactor drum that places nitrogen atmosphere 0 ℃ with magnetic agitation under make T
7Sodium salt and trichlorosilane reaction 3h makes reaction system continue reaction 4h at 20 ℃ down with stirring again, reaction back elimination deposition, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Again with 1g monochloro propyl group cage-type silsesquioxane and 1g diethylolamine wiring solution-forming in the anhydrous N of 15mL, dinethylformamide; Under 80 ℃ temperature of reaction and magnetic agitation, make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 48h, reaction back deposition in deionized water is separated out and is filtered and obtains two hydroxyl cage-type silsesquioxanes.
Embodiment 3:
Earlier with 10g T
7Sodium salt and 3.2g trichlorosilane are dissolved in wiring solution-forming in the anhydrous N of 150mL, the dinethylformamide, the reactor drum that places nitrogen atmosphere 0 ℃ with magnetic agitation under make T
7Sodium salt and trichlorosilane reaction 3h makes reaction system continue reaction 2h at 30 ℃ down with stirring again, reaction back elimination deposition, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Again with 1g monochloro propyl group cage-type silsesquioxane and 1g diethylolamine wiring solution-forming in the anhydrous N of 15mL, dinethylformamide; Under 100 ℃ temperature of reaction and magnetic agitation, make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 24h, reaction back deposition in deionized water is separated out and is filtered and obtains two hydroxyl cage-type silsesquioxanes.
Embodiment 4:
Earlier with 10g T
7Sodium salt and 3.2g trichlorosilane are dissolved in wiring solution-forming in the 150mL anhydrous tetrahydro furan, the reactor drum that places nitrogen atmosphere 0 ℃ with magnetic agitation under make T
7Sodium salt and trichlorosilane reaction 3h makes reaction system continue reaction 2h at 30 ℃ down with stirring again, reaction back elimination deposition, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Again with 1g monochloro propyl group cage-type silsesquioxane and 3g diethylolamine wiring solution-forming in the anhydrous N of 15mL, dinethylformamide; Under 100 ℃ temperature of reaction and magnetic agitation, make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 24h, reaction back deposition in deionized water is separated out and is filtered and obtains two hydroxyl cage-type silsesquioxanes.
Embodiment 5:
Earlier with 15g T
7Sodium salt and 4.8g trichlorosilane are dissolved in wiring solution-forming in the anhydrous N of 150mL, the dinethylformamide, the reactor drum that places nitrogen atmosphere 0 ℃ with magnetic agitation under make T
7Sodium salt and trichlorosilane reaction 3h makes reaction system continue reaction 2h at 30 ℃ down with stirring again, reaction back elimination deposition, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Again with 1g monochloro propyl group cage-type silsesquioxane and 3g diethylolamine wiring solution-forming in the anhydrous N of 15mL, dinethylformamide; Under 90 ℃ temperature of reaction and magnetic agitation, make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 36h, reaction back deposition in deionized water is separated out and is filtered and obtains two hydroxyl cage-type silsesquioxanes.
Embodiment 6:
Earlier with 15g T
7Sodium salt and 4.8g trichlorosilane are dissolved in wiring solution-forming in the 150mL anhydrous tetrahydro furan, the reactor drum that places nitrogen atmosphere 0 ℃ with magnetic agitation under make T
7Sodium salt and trichlorosilane reaction 3h makes reaction system continue reaction 3h at 25 ℃ down with stirring again, reaction back elimination deposition, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Again with 1g monochloro propyl group cage-type silsesquioxane and 3g diethylolamine wiring solution-forming in the anhydrous N of 15mL, dinethylformamide; Under 100 ℃ temperature of reaction and magnetic agitation, make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 24h, reaction back deposition in deionized water is separated out and is filtered and obtains two hydroxyl cage-type silsesquioxanes.
In the foregoing description resulting product and verification method thereof all with embodiment 1 in basic identical.
Adopt other T
7Sodium salt pressing under the foregoing description identical condition and experimental technique with trichlorosilane mole proportioning and monochloro propyl group cage-type silsesquioxane and diethylolamine mole proportioning, also can both prepare the cage-type silsesquioxane with two hydroxyls.
Can know that by top embodiment the present invention takes under the condition of stirring and nitrogen atmosphere protection T
7" drift angle-block method " and functional group that sodium salt and trichlorosilane reaction make monochloro propyl group cage-type silsesquioxane change method, have obtained the cage-type silsesquioxane of two hydroxyls.It is that functional group is a hydroxyl, and the hydroxy functional group number is two a cage-type silsesquioxane.
Compare with the method for simple function group cage-type silsesquioxane with the semiclosed cage-type silsesquioxane of existing synthetic; The reason that the present invention has overcome the restriction of using owing to semiclosed cage-type silsesquioxane in the prior art makes its complex process, trivial operations, security is low and the defective of contaminate environment, and compound method finally simple through technology, environmentally safe has obtained can be applicable to the two more widely hydroxyl cage-type silsesquioxanes of cage-type silsesquioxane/polymer nanocomposites.
Claims (2)
1. preparation method with cage-type silsesquioxane of two hydroxyls is characterized in that:
Earlier by seven phenyl, three siloxy sodium salt (T
7Sodium salt) be 1 with the trichlorosilane mol ratio: (1.1～1.5) are made into T in solvent
7Sodium salt and trichlorosilane total mass/volume by volume concentration are the solution of 0.1～0.3g/mL, with the T that is made into
7The solution of sodium salt and trichlorosilane adds in the nitrogen atmosphere reactor drum, and under agitation, elder generation makes T 0 ℃ temperature
7Sodium salt and trichlorosilane stirring reaction 2～4h, at temperature continuation stirring reaction 2～4h of 20～30 ℃, reaction back elimination precipitates again, and evaporate to dryness filtrating is recrystallization also, obtains monochloro propyl group cage-type silsesquioxane;
Be 1 by monochloro propyl group cage-type silsesquioxane and diethylolamine mol ratio again: (1.0～30.0); Total mass/the volume by volume concentration that in solvent, is made into monochloro propyl group cage-type silsesquioxane and diethylolamine is the solution of 0.05～0.15g/mL; Make monochloro propyl group cage-type silsesquioxane and diethylolamine reaction 24～48h 80～100 ℃ temperature of reaction down with stirring, the reaction back is precipitated to separate out and filter in deionized water and is obtained pair hydroxyl cage-type silsesquioxanes;
Said solvent is THF or N, dinethylformamide.
2. the cage-type silsesquioxane with two hydroxyls by the said method preparation of claim 1 is the organic-inorganic nano material that is made up of skeleton structure siliconoxygen bond; It is characterized in that structure is:
It is that functional group is a hydroxyl, and the hydroxy functional group number is two a cage-type silsesquioxane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204872A (en) * | 2013-04-14 | 2013-07-17 | 吉林大学 | Dyhydroxyl cage-type silsesquioxane monomer and preparation method thereof |
| CN109679104A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of eight amino pyrene propyl cage-type silsesquioxane silicon rubber heat-resisting auxiliary agents |
| CN117430937A (en) * | 2023-11-24 | 2024-01-23 | 新兴际华(北京)材料技术研究院有限公司 | Polycarbonate modified plastic for limiting ambient temperature and preparation method thereof |
-
2012
- 2012-03-29 CN CN201210089401XA patent/CN102633830A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| KWAN HAN YOON ET AL.: "Properties of poly(ethylene terephthalate) containing epoxy-functionalized polyhedral oligomeric silsesquioxane", 《POLYMER INTERNATIONAL》 * |
| MICHAEL E. WRIGHT ET AL.: "Synthesis and Thermal Curing of Aryl-Ethynyl-Terminated coPOSS Imide Oligomers: New Inorganic/Organic Hybrid Resins", 《CHEMISTRY OF MATERIALS》 * |
| 费明: "不同拓扑结构POSS/聚合物纳米复合材料的制备及其热性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204872A (en) * | 2013-04-14 | 2013-07-17 | 吉林大学 | Dyhydroxyl cage-type silsesquioxane monomer and preparation method thereof |
| CN109679104A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of eight amino pyrene propyl cage-type silsesquioxane silicon rubber heat-resisting auxiliary agents |
| CN117430937A (en) * | 2023-11-24 | 2024-01-23 | 新兴际华(北京)材料技术研究院有限公司 | Polycarbonate modified plastic for limiting ambient temperature and preparation method thereof |
| CN117430937B (en) * | 2023-11-24 | 2024-05-28 | 新兴际华(北京)材料技术研究院有限公司 | Polycarbonate modified plastic for limiting ambient temperature and preparation method thereof |
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Application publication date: 20120815 |