CN106866969A - A kind of preparation method of incomplete condensation phenylsilsesquioxane lithium salts - Google Patents
A kind of preparation method of incomplete condensation phenylsilsesquioxane lithium salts Download PDFInfo
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- CN106866969A CN106866969A CN201710030218.5A CN201710030218A CN106866969A CN 106866969 A CN106866969 A CN 106866969A CN 201710030218 A CN201710030218 A CN 201710030218A CN 106866969 A CN106866969 A CN 106866969A
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- phenylsilsesquioxane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
The present invention relates to a kind of not exclusively condensation phenylsilsesquioxane lithium salts (T7POSS Li salt) synthetic method, belong to organic-inorganic hybrid material technical field.By solvent, lithium hydroxide and deionized water are added in reactor, heating stirring, after there is withdrawing fluid in system, phenyl trialkoxysilane are added dropwise, and the reaction time is 16 24 hours, has solid to produce, and forms suspension；Suspension suction filtration, a large amount of solvent washings, air blast are dried, drying temperature is 50 100 DEG C, finally obtain not exclusively condensation phenylsilsesquioxane lithium salts.Mild condition of the invention, it is reproducible, with yield is high, cycle is short, it is simple to operate the characteristics of, be adapted to expanding production；Products therefrom possesses three groups with high reaction activity, can be reacted with the compound (such as many chlorine metallic compounds, chlorosilane and alkoxy silane) of many active functional groups as presoma (such as presoma of unfilled corner closed loop method), form POSS derivatives.
Description
Technical field
The present invention relates to a kind of not exclusively condensation phenylsilsesquioxane lithium salts (T7POSS-Li salt) preparation method, category
In hybrid inorganic-organic materials scientific domain.
Background technology
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane, POSS) refers to molecule
Formula is (RSiO1.5)nPolysiloxanes, on POSS molecular structures both containing inorganic siloxanes " skeleton " structure, can pass through again
Side base has introduced organic group.The larger inorganic siliceous interior nuclear energy of density suppresses its chain movement and assigns its good heat resistance
Can, corresponding organic side base then assigns its good toughness and machinability, and this typical Inorganic-Organic Hybrid Material is simultaneously
Possesses the essential characteristic of organic polymer and inorganic ceramic.
Not exclusively condensation silsesquioxane has irregular cagelike structure and multiple active group (Si-OX, X=H, Na
Deng), species, number are various, it is known that the main of structure type has R4T4(OX)4、R6T6(OX)4And R7T7(OX)3Three kinds；Not exclusively
It is condensed the regular structures of POSS, nano-scale, excellent compatibility and modifiability and becomes Molecular Design and material
Modified most potential selection, is one of focus of present material scientific domain research.
Because stronger reactive and higher mutability these features of not exclusively condensation phenylsilsesquioxane cause it
More difficult synthesis and separation, the existing research on such silsesquioxane are less.The present invention by introducing phenyl alkoxysilane,
The phenyl trichlorosilane hydrolysis a large amount of HCl gases of release are solved the problems, such as, while by improving solvent so that reaction time contracts
Short, solvent-oil ratio reduction has finally given the silsesquioxane of one-component.
The content of the invention
The invention aims to propose a kind of not exclusively condensation phenylsilsesquioxane lithium salts (T7POSS-Li salt)
Preparation method, not exclusively condensation phenylsilsesquioxane lithium salts is a kind of new poly-phenyl silsesquioxane derivative, is possessed
Three groups with high reaction activity, can be used as presoma (such as presoma of unfilled corner closed loop method) and many active functions
Compound (such as many chlorine metallic compounds, the chlorosilane and alkoxy silane) reaction of group, forms POSS derivatives.
The purpose of the present invention is achieved through the following technical solutions.
The present invention is a kind of not exclusively condensation phenylsilsesquioxane lithium salts (T7POSS-Li salt) preparation method, its tool
Preparation step is as follows：
1) by solvent, lithium hydroxide, deionized water is added in reactor, and inert gas shielding, heating stirring is treated in system
After there is backflow, phenyl trialkoxysilane is added dropwise, is reacted 16-24 hours under reflux state, there is solid to produce, formed and suspended
Liquid, by suspension suction filtration, a large amount of solvent washings, air blast is dried, and drying temperature is 50-100 DEG C, finally obtains not exclusively condensation benzene
Base silsesquioxane lithium salts.
Inert gas is nitrogen or argon gas in above-mentioned steps.
Solvent in above-mentioned steps is in methyl alcohol, ethanol, isopropanol, isobutanol, n-butanol, acetone, tetrahydrofuran
Plant or its mixture, solvent is preferably acetone；Phenyl trialkoxysilane is phenyltrimethoxysila,e or phenyl triethoxy
Silane；The ratio of phenyl trialkoxysilane and solvent is 1g：3~9mL；
Phenyl trialkoxysilane and the mol ratio of lithium hydroxide are 1 in above-mentioned steps：0.3-0.6；
Above-mentioned steps phenyl trialkoxysilane is 1 with the mol ratio ratio of deionized water：0.8-1.5；
Through incomplete condensation phenylsilsesquioxane prepared by the above method, shown in its typical structure formula such as formula (1)：
It is a kind of three-dimensional hybrid inorganic-organic materials with nano-scale, and it has the hydroxyl compared with high reaction activity
Block can further occur with lithia group and be changed into the various one jiaos phenyl POSS derivatives containing activity functional groups.
Beneficial effect
Reaction condition of the invention is gentle, reproducible, with yield is high, cycle is short, it is simple to operate the characteristics of, be adapted to expand
Big production；The structural stability of product is good, under conditions of cage structure is kept, obtains containing 3 POSS of high reaction activity
Compound.
Brief description of the drawings
Fig. 1 is T prepared by embodiment 17The FT-IR spectrograms of POSS-Li salt；
Fig. 2 is T prepared by embodiment 17POSS-Li salt29Si NMR spectras；
Fig. 3 is T prepared by embodiment 17The MALDI-TOF-MS spectrograms of POSS-Li salt；
Fig. 4 is T prepared by embodiment 17The TG spectrograms of POSS-Li salt.
Specific embodiment
Below by example, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
Embodiment 1
By 90ml acetone, 30ml methyl alcohol is added to equipped with reflux condensing tube, constant pressure funnel, temperature regulating device, nitrogen
In the 250ml there-necked flasks of gas shielded and magnetic agitation, 1gLiOH and 2ml deionized waters are added under stirring, intensification makes body
Occur backflow in system, phenyltrimethoxysila,e 20g is added dropwise, about 30min is dripped off, and back flow reaction 12 hours, have after completion of dropping
Solid is produced, and forms suspension, and by suspension suction filtration, a large amount of acetone washings, 60 DEG C of air blast drying finally obtain not exclusively condensation
Phenylsilsesquioxane lithium salts, yield is about 85.7%.
Fig. 1 is the FT-IR spectrograms for being not exclusively condensed phenylsilsesquioxane lithium salts, 3709 and 3672cm-1It is lithia key
Absworption peak, 3051cm-1It is C-H stretching vibration absworption peaks, 1720,1590,1435cm on phenyl ring-1For phenyl ring skeletal vibration absorbs
Peak, 1074cm-1It is Si-O-Si key chattering absworption peaks.Fig. 2 is not exclusively to be condensed phenylsilsesquioxane lithium salts29Si H NMR spectroscopies
Figure, appearance is located in -69.54, -77.42 and -77.69ppm.
Wherein spectral data is：
FT-IR (KBr, cm-1)：3709,3672 (- OLi), 3051 (C-H), 1720,1590,1435 (Ph), 1074 (Si-
O-Si)；29Si NMR(CDCl3,δ,ppm)：-69.54(OSiPhOLi/OSiPhOH),-77.42,-77.69(O3SiPh)；
Fig. 3 is the MALDI-TOF-MS spectrograms for being not exclusively condensed phenylsilsesquioxane lithium salts, 937.3 (T7POSS-Li salt
+H+)；The TG images of not exclusively condensation phenylsilsesquioxane lithium salts show its T95%It it is 413 DEG C, carbon left is 52.28%；
Embodiment 2
By 180ml acetone, 60ml methyl alcohol is added to equipped with reflux condensing tube, constant pressure funnel, temperature regulating device, nitrogen
In the 500ml there-necked flasks of gas shielded and magnetic agitation, 2gLiOH and 4ml deionized waters are added under stirring, intensification makes body
Occur backflow in system, phenyltrimethoxysila,e 40g is added dropwise, about 40min is dripped off, and back flow reaction 16 hours, have after completion of dropping
Solid is produced, and forms suspension, and by suspension suction filtration, a large amount of acetone washings, 60 DEG C of air blast drying finally obtain not exclusively condensation
Phenylsilsesquioxane lithium salts, yield is about 83.2%.
Embodiment 3
By 80ml acetone, 20ml methyl alcohol is added to equipped with reflux condensing tube, constant pressure funnel, temperature regulating device, nitrogen
In the 250ml there-necked flasks of gas shielded and magnetic agitation, 1gLiOH and 2ml deionized waters are added under stirring, intensification makes body
Occur backflow in system, phenyl triethoxysilane 25g is added dropwise, about 30min is dripped off, and back flow reaction 12 hours, have after completion of dropping
Solid is produced, and forms suspension, and by suspension suction filtration, a large amount of acetone washings, 60 DEG C of air blast drying finally obtain not exclusively condensation
Phenylsilsesquioxane lithium salts, yield is about 84.3%.
Embodiment 4
By 80ml acetone, 20ml isopropanols be added to equipped with reflux condensing tube, constant pressure funnel, temperature regulating device,
Nitrogen is protected in the 250ml there-necked flasks with magnetic agitation, 1gLiOH and 2.5ml deionized waters are added under stirring, is heated up
Make occur backflow in system, phenyl triethoxysilane 28g is added dropwise, about 30min is dripped off, and back flow reaction 14 is small after completion of dropping
When, there is solid to produce, suspension is formed, by suspension suction filtration, a large amount of acetone washings, 60 DEG C of air blast drying cannot not finally obtained completely
Full reduced conjunction phenylsilsesquioxane lithium salts, yield is about 84.0%.
Embodiment 5
By 160ml acetone, 40ml isopropanols be added to equipped with reflux condensing tube, constant pressure funnel, temperature regulating device,
Nitrogen is protected in the 500ml there-necked flasks with magnetic agitation, 2gLiOH and 5ml deionized waters are added under stirring, and intensification makes
Occur backflow in system, phenyltrimethoxysila,e 56g be added dropwise, about 40min is dripped off, back flow reaction 18 hours after completion of dropping,
There is solid to produce, form suspension, by suspension suction filtration, a large amount of acetone washings, 60 DEG C of air blast drying finally obtain not exclusively contracting
Phenylsilsesquioxane lithium salts is closed, yield is about 82.6%.
Claims (5)
1. it is a kind of to be not exclusively condensed phenylsilsesquioxane lithium salts (T7POSS-Li salt) preparation method, it is characterised in that preparation side
Method is as follows：
1) by solvent, lithium hydroxide and deionized water are added in reactor, and heating stirring treats occur withdrawing fluid in system
Afterwards, phenyl trialkoxysilane is added dropwise, the reaction time is 16-24 hours, has solid to produce, and forms suspension；Suspension is taken out
Filter, a large amount of solvent washings, air blast drying, drying temperature is 50-100 DEG C, finally obtains not exclusively condensation phenylsilsesquioxane
Lithium salts.
The ratio of above-mentioned steps phenyl trialkoxysilane and solvent is 1g：3~9mL；Phenyl trialkoxysilane and lithium hydroxide
Mol ratio be 1：0.3-0.6；Phenyl trialkoxysilane is 1 with the mol ratio ratio of deionized water：0.8-1.5；
Solvent in above-mentioned steps for the one kind in methyl alcohol, ethanol, isopropanol, isobutanol, n-butanol, acetone, tetrahydrofuran or
Its mixture；
Through incomplete polycondensation silsesquioxane lithium salts prepared by the above method, shown in its general structure such as formula (1)：
2. the preparation method of a kind of incomplete condensation phenylsilsesquioxane lithium salts according to claim 1, its feature exists
In：Reactor in step carries temperature regulating device, condensation reflux unit, inert gas shielding and magnetic stirring apparatus.
3. the preparation method of a kind of incomplete condensation phenylsilsesquioxane lithium salts according to claim 2, its feature exists
In：Inert gas is nitrogen or argon gas.
4. the preparation method of a kind of incomplete condensation phenylsilsesquioxane lithium salts according to claim 1, its feature exists
In：The metal hydroxides of use is lithium hydroxide.
5. the preparation method of a kind of incomplete condensation phenylsilsesquioxane lithium salts according to claim 1, its feature exists
In：Solvent is acetone+methanol/isopropanol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452385A (en) * | 2019-08-29 | 2019-11-15 | 北京理工大学 | A kind of incomplete polycondensation cage type phenyl silsesquioxane of alkali metal containing sodium and preparation method thereof |
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| CN104610342A (en) * | 2013-11-04 | 2015-05-13 | 浙江省海洋开发研究院 | Hepta-polyhedral oligomeric silsesquioxane preparation method |
| CN104610341A (en) * | 2013-11-04 | 2015-05-13 | 浙江省海洋开发研究院 | Simple function group octamer-cage type silsesquioxane preparation method |
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- 2017-01-17 CN CN201710030218.5A patent/CN106866969A/en active Pending
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| CN104610342A (en) * | 2013-11-04 | 2015-05-13 | 浙江省海洋开发研究院 | Hepta-polyhedral oligomeric silsesquioxane preparation method |
| CN104610341A (en) * | 2013-11-04 | 2015-05-13 | 浙江省海洋开发研究院 | Simple function group octamer-cage type silsesquioxane preparation method |
Non-Patent Citations (1)
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| CN110452385A (en) * | 2019-08-29 | 2019-11-15 | 北京理工大学 | A kind of incomplete polycondensation cage type phenyl silsesquioxane of alkali metal containing sodium and preparation method thereof |
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Application publication date: 20170620 |