CN104672273A - Asymmetric double-deck and trapezoid polysilsesquioxane containing hydroxyl and synthesis method and application of asymmetric double-deck and trapezoid polysilsesquioxane - Google Patents
Asymmetric double-deck and trapezoid polysilsesquioxane containing hydroxyl and synthesis method and application of asymmetric double-deck and trapezoid polysilsesquioxane Download PDFInfo
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Abstract
The invention relates to the technical field of polysilsesquioxane synthesis, aims at solving the problem that existing synthesis of asymmetric polyhedron polysilsesquioxane is mainly concentrated on polyhedron polysilsesquioxane with two different functional groups on the left and the right and cage-type polyhedron polysilsesquioxane with different functional groups on the upper surface and the lower surface, so that random distribution of the functional groups of the product is generated in synthesis, and provides asymmetric double-deck and trapezoid polysilsesquioxane containing hydroxyl and a synthesis method and an application of the asymmetric double-deck and trapezoid polysilsesquioxane. Parallel hydroxyl is formed in one side of the asymmetric double-deck and trapezoid polysilsesquioxane containing hydroxyl; other groups are formed in the other side; the structural formula of the asymmetric double-deck and trapezoid polysilsesquioxane is shown in formula (I) or (II) in the specification. The asymmetric double-deck and trapezoid polysilsesquioxane provided by the invention is relatively wide in application range; and the synthesis method has the advantages of mild reaction condition, low energy consumption, high synthesis efficiency, and simple and feasible product purification process.
Description
Technical field
The present invention relates to oligomeric silsesquioxane synthesis technical field, particularly relate to novel asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane and high-efficiency synthesis method thereof and application.
Background technology
Asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane have important use, as developing bead type, ladder-cage type, trapezoidal, hyperbranched with new polysiloxanes such as large rings; Development of new coupling agent; Development of new support of the catalyst etc.So far, the asymmetric oligomeric silsesquioxane seeing report has two types.The first asymmetric oligomeric silsesquioxane is the polyhedral oligomeric silsesquioxane of left and right with two kinds of different functional groups, as the people such as Y.Kawakami are published in paper (the Advanced Polymer Science of Advanced Polymer Science, 2011, 235, 185-228), describe respectively with dimethylsilyl bis and the silica-based polyhedral oligomeric silsesquioxane of cyclobutyl, this asymmetric polyhedral oligomeric silsesquioxane can only for the synthesis of linear polymer, be of limited application, and do not provide the characterization data of this asymmetric polyhedral oligomeric silsesquioxane in paper.Another kind of asymmetric oligomeric silsesquioxane is the cage type polyhedral oligomeric silsesquioxanes of upper and lower surfaces with different functional groups, mostly this kind of asymmetric polyhedral oligomeric silsesquioxane is that by two kinds of cyclotetrasiloxane four silanols with different functional groups be that raw material cocondensation obtains, but often generates the polyhedral oligomeric silsesquioxane of the random arrangement of functional group in building-up process.As the people such as S.Tateyama are published in paper (Journal of Organometallic Chemistry, 2010,695 of Journal of Organometallic Chemistry, 898-902), with 1,3,5,7-tetraphenyl-1,3,5,7-tetrahydroxy cyclotetrasiloxane and 1,3, the deuterated phenyl-1,3 of 5,7-tetra-, 5,7-tetrahydroxy cyclotetrasiloxane is the cage type polyhedral oligomeric silsesquioxane that raw material obtains Liang Zhong functional group random distribution under the catalysis of quaternary ammonium hydroxide.
In a word, the synthesis of existing asymmetric polyhedral oligomeric silsesquioxane to focus mostly in left and right with the polyhedral oligomeric silsesquioxane of two kinds of different functional groups and upper and lower surfaces with on the cage type polyhedral oligomeric silsesquioxane of different functional groups, synthesis aspect also exists the problem of product functional group random distribution, and application aspect is only applicable to develop linear polymeric.
Summary of the invention
For the synthesis solving existing asymmetric polyhedral oligomeric silsesquioxane to focus mostly in left and right with the polyhedral oligomeric silsesquioxane of two kinds of different functional groups and upper and lower surfaces with on the cage type polyhedral oligomeric silsesquioxane of different functional groups, synthesis aspect also exists the problem of product functional group random distribution, the present invention proposes asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane and synthetic method thereof and application, asymmetric hydroxyl double-deck shape of the present invention and trapezoidal oligomeric silsesquioxane range of application wider, synthetic method has reaction conditions gentleness, energy consumption is low, combined coefficient is high, the advantages such as product purification process is simple.
The present invention is achieved through the following technical solutions: asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane, and with parallel hydroxyl, while with other groups, its structural formula is as shown in (I), (II):
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of.
Described asymmetric hydroxyl double-deck shape and the synthetic method of trapezoidal oligomeric silsesquioxane are following steps: with double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or cyclotetrasiloxane four silanol of structural formula as shown in (IV) with the sily oxide containing two reactive functionality for raw material, and under the effect of catalyzer, react in organic solvent, again through last handling process, obtain structural formula respectively as (I), (II) the asymmetric hydroxyl double-deck shape shown in and trapezoidal oligomeric silsesquioxane, reaction process is as follows:
In reaction formula, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of, X is separately selected from hydrogen, fluorine, chlorine, bromine, iodine, alkoxyl group a kind of.
As preferably, cyclotetrasiloxane four silanol of structural formula as shown in (IV) is selected from complete in-cyclotetrasiloxane four silanol or suitable, anti-, cis-cyclotetrasiloxane four silanol.
Described organic solvent is selected from one or more in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone, as preferably, organic solvent is selected from hexane, hexanaphthene, toluene, chlorobenzene, 1,3, in 5-Three methyl Benzene, ether, butyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, acetone, butanone, pimelinketone, methyl iso-butyl ketone (MIBK) one or more.Organic solvent amount used is for making the amount of solute dissolves.
Described catalyzer is selected from inorganic ammonia, organic amine, quaternary ammonium hydroxide, metal simple-substance, metal oxide, metal-salt, complex compound a kind of, as preferably, catalyzer is selected from the simple substance of a kind of metal in ammonia, ammoniacal liquor, dimethylamine, diethylamine, Trimethylamine 99, triethylamine, pyridine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetra-tert ammonium hydroxide and iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, osmium, iridium, gold and silver, copper, tin, zinc, titanium, pick, chromium, manganese, lanthanide series metal or corresponding compound.
The mass ratio of cyclotetrasiloxane four silanol as shown in (IV) of double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or structural formula and catalyzer is 1: 0.001 ~ 1, is 1: 0.001 ~ 1 with the mass ratio containing two reactive functionality sily oxide.
As preferably, temperature of reaction is-20 ~ 140 DEG C, and the reaction times is 30 minutes ~ 24 hours.
As preferably, last handling process is recrystallization, precipitation, column chromatography or vacuum drying.
The present invention with double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or cyclotetrasiloxane four silanol of structural formula as shown in (IV) with containing two reactive functionality sily oxide for raw material, under the existence of inorganic ammonia, organic amine, quaternary ammonium hydroxide or metal catalyst, there is condensation reaction or dehydrogenation/dealcoholysis linked reaction, realize the efficient synthesis of asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane, productive rate can reach 60 ~ 95%.Product structure is characterized by infrared spectra and proton nmr spectra etc.Infrared spectra with match containing functional group in theory, proton nmr spectra and theoretical proton number and chemical shift match.
Containing multiple functional group in asymmetric oligomeric silsesquioxane molecule of the present invention, can be used for exploitation bead type, ladder-cage type, trapezoidal, hyperbranched with large ring etc. new polysiloxanes; Development of new coupling agent; Development of new support of the catalyst etc.
Compared with prior art, the invention has the beneficial effects as follows:
(1) advantages such as synthetic method has reaction conditions gentleness, energy consumption is low, combined coefficient is high, product purification process is simple;
(2) asymmetric hydroxyl double-deck shape of the present invention and trapezoidal oligomeric silsesquioxane range of application wider.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane in embodiment 1;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of asymmetric hydroxyl double-deck shape oligomeric silsesquioxane in embodiment 1;
Fig. 3 is the infrared spectrogram of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl in embodiment 2.
Embodiment
Embodiment 1: the preparation of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing methyl, phenyl and hydrogen
At-20 DEG C of temperature, by 10 milliliter 1 containing 3 gram of 1,3-dimethyl-1,3-dichloro sily oxide, 4-dioxane solution is slowly added drop-wise to and 3 grams of side bases are housed is double-deck shape oligomeric silsesquioxane four silanol of phenyl, 3 grams of diethylamine and 10 milliliter 1, in 50 milliliters of there-necked flasks of 4-dioxane, then stirring reaction 30 minutes, washes organic layer with water to neutral, after adding anhydrous sodium sulfate drying, vacuum drying, except desolventizing, obtains white solid, productive rate 78%.
As shown in Figure 1, the hydrogen nuclear magnetic resonance spectrogram of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing methyl, phenyl and hydrogen as shown in Figure 2 for the infrared spectra of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing methyl, phenyl and hydrogen.
Embodiment 2: the preparation of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing methyl, phenyl and hydrogen
At 60 DEG C of temperature, will containing 2 gram 1,3-dimethyl-1,20 milliliters of tetrahydrofuran solutions of 3-dichloro sily oxide be slowly added drop-wise to be equipped with 200 grams of side bases be phenyl all-cis-500 milliliters of there-necked flasks of cyclotetrasiloxane four silanol, 2 grams of triethylamines and 300 milliliters of tetrahydrofuran (THF)s in, then stirring reaction 8 hours, after question response solution is down to room temperature, add 300 ml n-hexanes, wash organic layer with water to neutral, after adding anhydrous sodium sulfate drying, vacuum drying, except desolventizing, obtains white solid, productive rate 85%.
The infrared spectra of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing methyl, phenyl and hydrogen as shown in Figure 3.
Embodiment 3: the preparation containing vinyl, ethyl propenoate base and allylic asymmetric hydroxyl double-deck shape oligomeric silsesquioxane
At 90 DEG C of temperature, will containing 16 gram 1,3-divinyl-1,3-ethyl diacrylate base-1,20 milliliters of methyl isobutyl ketone solution of 3-dichloro sily oxide are slowly added drop-wise to and 100 grams of side bases are housed is in 500 milliliters of there-necked flasks of allylic double-deck shape oligomeric silsesquioxane four silanol, 0.1 gram of Tetramethylammonium hydroxide and 200 milliliters of methyl iso-butyl ketone (MIBK), then stirring reaction 16 hours, after being down to room temperature, wash organic layer with water to neutral, after adding anhydrous sodium sulfate drying, vacuum drying, except desolventizing, obtains white solid, productive rate 78%.
Embodiment 4: the preparation of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing p-chloromethyl phenyl, ethyl and hydrogen
At 120 DEG C of temperature, will containing 5 gram 1,3-bis-(p-chloromethyl phenyl)-1,20 milliliters of chlorobenzene solutions of 3-dichloro sily oxide are slowly added drop-wise to and 50 grams of side bases are housed is in 500 milliliters of there-necked flasks of double-deck shape oligomeric silsesquioxane four silanol of ethyl, 2 grams of pyridines and 100 milliliters of chlorobenzenes, then stirring reaction 16 hours, after question response solution is down to room temperature, wash organic layer with water to neutral, after adding anhydrous sodium sulfate drying, vacuum drying is except desolventizing, obtain white solid, productive rate 95%.
Embodiment 5: the preparation containing vinyl, itrile group and the trapezoidal oligomeric silsesquioxane of allylic asymmetric hydroxyl
At 30 DEG C of temperature, will containing 3 gram 1, 3-divinyl-1, 3-dinitrile-1, 10 milliliters of acetone solns of 3-dichloro sily oxide are slowly added drop-wise to and 30 grams of side bases are housed is allylic suitable, instead, cis-cyclotetrasiloxane four silanol, in 500 milliliters of there-necked flasks of 0.3 gram of ammoniacal liquor and 100 milliliters of acetone, then stirring reaction 20 hours, add 300 ml n-hexanes, wash organic layer with water to neutral, after adding anhydrous sodium sulfate drying, by in solution impouring methyl alcohol, adularescent solid is separated out, filtration obtains white solid, vacuum drying, obtain target product, productive rate 65%.
Embodiment 6: the preparation of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing 3-chloropropyl, naphthyl and hydrogen
At 140 DEG C of temperature, will containing 0.2 gram 1, 3-bis-(3-chloropropyl)-1, 50 milliliters of cyclohexanone solution of 3-dichloro sily oxide are slowly added drop-wise to and double-deck shape oligomeric silsesquioxane four silanol that 200 grams of side bases are naphthyl are housed, in 1000 milliliters of there-necked flasks of 20 grams of tetra-tert ammonium hydroxide and 300 milliliters of pimelinketone, then stirring reaction 24 hours, after question response solution is down to room temperature, wash organic layer with water to neutral, after adding anhydrous sodium sulfate drying, by solution impouring ethanol, adularescent solid is separated out, filtration obtains white solid and vacuum drying, obtain target product, productive rate 90%.
Embodiment 7: the preparation of the trapezoidal oligomeric silsesquioxane of asymmetric hydroxyl containing phenyl, butyl and epoxy group(ing)
At 20 DEG C of temperature, will containing 6 gram of 1,3-phenylbenzene-1,3-dibutyl-1,60 milliliters of Isosorbide-5-Nitrae-dioxane solution of 3-dimethoxy sily oxide be slowly added drop-wise to be equipped with 30 grams of side bases be epoxy group(ing) all-cis-500 milliliters of there-necked flasks of cyclotetrasiloxane four silanol, 3 grams of Palladous chlorides and 60 milliliters of Isosorbide-5-Nitrae-dioxane in, then stirring reaction 3 hours, after question response liquid is down to room temperature, remove Palladous chloride by column chromatography, vacuum drying is except desolventizing, obtain white solid, productive rate 81%.
Embodiment 8: the preparation of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing epoxy group(ing), allyl group and ethyl propenoate base
At 30 DEG C of temperature, will containing 30 gram 1,3-bicyclic oxygen-1,60 milliliters of butanone solutions of 3-diallyl-1,3-diethoxy sily oxide are slowly added drop-wise to and 50 grams of side bases are housed is in 250 milliliters of there-necked flasks of double-deck shape oligomeric silsesquioxane four silanol of ethyl propenoate base, 3 grams of palladium/carbon and 60 milliliters of butanone, then stirring reaction 15 hours, palladium/carbon is removed by column chromatography, after carrying out recrystallization with ethanol as solvent, obtain clear crystal, productive rate 78%.
Embodiment 9: the preparation of the asymmetric hydroxyl double-deck shape oligomeric silsesquioxane containing p-chloromethyl phenyl, n-octyl and normal-butyl
At 10 DEG C of temperature, will containing 5 gram 1,3-bis-(p-chloromethyl phenyl)-1,3-di-n-octyl-1,20 milliliter 1 of 3-dimethoxy sily oxide, 3,5-trimethylbenzene solution is slowly added drop-wise to and 20 grams of side bases are housed is in 250 milliliters of there-necked flasks of double-deck shape oligomeric silsesquioxane four silanol of normal-butyl, 2 grams of Platinic chlorides and 50 milliliters of 1，3，5-trimethyl-benzene, then stirring reaction 16 hours, after question response solution rises to room temperature, remove Platinic chloride by column chromatography, vacuum drying is except desolventizing, obtain white solid, productive rate 75%.
Claims (10)
1. asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane, it is characterized in that, described double-deck shape is with trapezoidal oligomeric silsesquioxane while with parallel hydroxyl, and with other groups, its structural formula is as shown in (I), (II):
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of.
2. the synthetic method of an asymmetric hydroxyl double-deck shape as claimed in claim 1 and trapezoidal oligomeric silsesquioxane, it is characterized in that, described synthetic method be with double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or cyclotetrasiloxane four silanol of structural formula as shown in (IV) with the sily oxide containing two reactive functionality for raw material, and under the effect of catalyzer, react in organic solvent, again through last handling process, obtain structural formula respectively as (I), (II) the asymmetric hydroxyl double-deck shape shown in and trapezoidal oligomeric silsesquioxane, reaction process is as follows:
Wherein, R
1, R
2, R
3, R
4, R
5separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of, X is separately selected from hydrogen, fluorine, chlorine, bromine, iodine, alkoxyl group a kind of.
3. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, it is characterized in that, cyclotetrasiloxane four silanol of structural formula as shown in (IV) is selected from complete in. cyclotetrasiloxane four silanol or suitable, anti-, suitable. cyclotetrasiloxane four silanol.
4. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, is characterized in that, organic solvent is selected from one or more in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone.
5. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 4 and trapezoidal oligomeric silsesquioxane, it is characterized in that, organic solvent is selected from hexane, hexanaphthene, toluene, chlorobenzene, 1,3,5. Three methyl Benzene, ether, butyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae. in dioxane, acetone, butanone, pimelinketone, methyl iso-butyl ketone (MIBK) one or more.
6. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, it is characterized in that, double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or cyclotetrasiloxane four silanol of structural formula as shown in (IV) are 1: 0.001 ~ 1 with the mass ratio containing two reactive functionality sily oxide.
7. the synthetic method of asymmetric hydroxyl double-deck shape and trapezoidal oligomeric silsesquioxane according to claim 2, it is characterized in that, described catalyzer to be selected from inorganic ammonia, organic amine, quaternary ammonium hydroxide, metal simple-substance, metal oxide, metal-salt, complex compound a kind of, and the mass ratio of cyclotetrasiloxane four silanol as shown in (IV) of double-deck shape oligomeric silsesquioxane four silanol of structural formula as shown in (III) or structural formula and catalyzer is 1: 0.001 ~ 1.
8. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, is characterized in that, temperature of reaction is .20 ~ 140 DEG C, and the reaction times is 30 minutes ~ 24 hours.
9. the synthetic method of asymmetric hydroxyl double-deck shape according to claim 2 and trapezoidal oligomeric silsesquioxane, is characterized in that, last handling process is recrystallization, precipitation, column chromatography or vacuum drying.
10. an asymmetric hydroxyl double-deck shape as claimed in claim 1 and trapezoidal oligomeric silsesquioxane are developing bead type, ladder. and cage type, trapezoidal, hyperbranched with new polysiloxanes such as large rings, development of new coupling agent, the application in development of new support of the catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018131565A1 (en) * | 2017-01-10 | 2018-07-19 | Jnc株式会社 | Silsesquioxane derivative having radical polymerizable functional group, composition thereof, and cured film having low cure shrinkage |
| CN108473514A (en) * | 2016-01-22 | 2018-08-31 | 信越化学工业株式会社 | Novel carbomethoxyisopropyl isonitrate and hydrosilylation reaction catalyst |
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| MASAFUMI UNNO ET AL.: "Nonacyclic Ladder Silsesquioxanes and Spectral Features of Ladder Polysilsesquioxanes", 《INTERNATIONAL JOURNAL OF POLYMER SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108473514A (en) * | 2016-01-22 | 2018-08-31 | 信越化学工业株式会社 | Novel carbomethoxyisopropyl isonitrate and hydrosilylation reaction catalyst |
| CN108473514B (en) * | 2016-01-22 | 2021-08-31 | 信越化学工业株式会社 | Novel isonitrile compound and hydrosilylation catalyst |
| WO2018131565A1 (en) * | 2017-01-10 | 2018-07-19 | Jnc株式会社 | Silsesquioxane derivative having radical polymerizable functional group, composition thereof, and cured film having low cure shrinkage |
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