CN105254661A - Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof - Google Patents
Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof Download PDFInfo
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Abstract
The invention relates to cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and a preparation method thereof. Cage-shaped octamer(dimethylsiloxy)silsesquioxane containing a large number of Si-H bonds is prepared by taking low-cost tetraethyl orthosilicate as the raw material through controllable hydrolytic condensation, and then the cage-shaped silsesquioxane with the eight phenolic hydroxyl groups is finally obtained by conducting functional modification on the cage-shaped octamer(dimethylsiloxy)silsesquioxane. The synthesized cage-shaped silsesquioxane with the eight phenolic hydroxyl groups has a Si-O-Si inorganic skeleton structure which is of a nanoscale cage-shaped structure, phenolic hydroxyl functional groups with high reaction activity are arranged on the apex angles, the cage-shaped silsesquioxane can serve as a nanoparticle additive with high reaction activity to be used for resin filler and be bonded in a polymer cross-linked network in a chemical bond mode, the cage-shaped silsesquioxane can serve as a reactive modified additive, and meanwhile the effects of inorganic nanoparticle enhancement and organic chemical crosslinking points are achieved. The preparation technology progress is simple and efficient, and the obtained product is high in yield and high in purity.
Description
Technical field
The present invention relates to a kind of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes and preparation method thereof.
Background technology
Oligomeric polyhedron cagelike silsesquioxane (POSS) molecule itself is the material containing inorganic-organic chemical skeleton structure, a kind of special hybrid molecule.Its inorganic skeleton is made up of Si-O-Si key, form the nuclear structure of POSS molecule, surrounding molecules is coated by institute of organic replacement functional group, and these substituting groups can be hydrocarbon polymers, also can be the functional group with reactive behavior, this constructional feature gives the functional and modifiability of POSS.POSS molecule can be counted as nanoparticle minimum in silica species, diameter is between 1 ~ 3nm, molecular weight is up to 1000, but it is different from silicon dioxide granule again, POSS molecule can react with other monomer or polymkeric substance in any case, carries out copolymerization or graft polymerization.The organo-functional group that molecular surface is coated simultaneously can make it be soluble in organic solvent, and has good consistency with organic polymer and organism.In certain circumstances, people according to the wish of oneself, can cut out POSS molecule, design and synthesize out the POSS macromole of particular functional group, make it have certain reactivity or inertia.In numerous structures of POSS, the hexahedron silsesquioxane (T in cagelike silsesquioxane
8structure POSS, structure is as shown in Figure 1) the most typical, be also a kind of product of most study.
Adding in polymeric system by having reactive POSS molecule, " inlaying " in crosslinked polymer network by chemical reaction POSS molecule, form chemically crosslinked point, the aspects such as the mechanical property of polymer materials, thermal characteristics can be improved.Inorganic Si-O-Si skeleton is wrapped in wherein by the organo-functional group of drift angle, POSS molecule is made to have good solubility, majority of organic solvent can be dissolved in, there is uniform dispersiveness in polymeric system, really can realize the nano-dispersed of molecular level, prepare the polymer nanocomposites that POSS adds.
Synthesis about silsesquioxane has many kinds of methods, Harrison, Pittman and Franck (HarrisonPG.Silicatecages:precursorstonewmaterials.Journa lofOrganometallicChemistry, 1997,542 (2): 141-183; LiG, WangL, NiH, etal.PolyhedralOligomericSilsesquioxane (POSS) PolymersandCopolymers:AReview.JournalofInorganicAndOrgan ometallicPolymers, 2001,11 (3): 123-154; CordesDB, LickissPD, RataboulF.RecentDevelopmentsintheChemistryofCubicPolyhed ralOligosilsesquioxanes.ChemicalReviews, 2010,110 (4): 2081-2173.) at large summarized in summary since POSS development, various synthetic method.The synthetic method of POSS and type siloxane derivative thereof is a lot, and these reactions can be roughly divided into two classes by the difference according to starting raw material:
(1) using small molecules fluorosilane-type materials as initial reactant, siloxane polymer or oligomer is formed by the polystep reaction of complexity.This micromolecular mainly XSiY
3, X is a kind of stable chemical substituents, and Y is the replacement end with high reaction activity, and such as Cl, O or OR are formed linearly by this kind of small molecule monomer hydrolytic condensation, the siloxane type polymers of annular or caged or oligomer, and reaction expression is expressed as follows:
nXSiY
3+1.5H
2O→(XSiO
1.5)
n+3nHY
(2) when not changing Si-O-Si skeleton, by modifying the substituent X of Siliciumatom keyed jointing, novel POSS is synthesized.The kind of the silsesquioxane alkane derivative that this method synthesizes is a lot, also causes the concern of many investigators, can synthesize the silsesquioxane kind of some particular functional groups, as double bond, alkynyl, azido group etc.
The cage-type silsesquioxane (POSS) synthesized at present is chlorosilane, the hydrolysate of organoalkoxysilane, the multi-band unreactiveness organo-functional group such as have multiple cyclopentyl, cyclohexyl, isobutyl-or trimethoxy silica-based on its drift angle.The POSS molecule of inertia does not have chemical reactivity, when the filler as polymer materials uses, only has nano-filled particle function, and does not have the crosslinking reaction that chemical reaction original position participates in polymkeric substance; Reactive POSS molecule, can not only mix in polymer network as nanoparticle, as chemically crosslinked point, can also increase the cross-linking density of crosslinked polymer network, realize the dispersion on molecular level.The POSS molecule of current phenolic hydroxyl group functional group has no report.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, provide a kind of eight phenolic hydroxyl group cagelike silsesquioxanes and preparation method thereof, the method with the tetraethyl orthosilicate of cheapness for the raw material that sets out, eight phenolic hydroxyl group cagelike silsesquioxanes are prepared first, and preparation process is simply efficient, the products collection efficiency prepared is high, and purity is high.
Above-mentioned purpose of the present invention is mainly achieved by following technical solution:
Eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, its structural formula is as follows:
The preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, specifically comprises the steps:
(1), by tetraethoxy be added drop-wise in the mixing solutions of methyl alcohol, water and Tetramethylammonium hydroxide, first in ice-water bath, be cooled to 0 DEG C, stirring reaction, after 4 ~ 8 hours, rises to room temperature and continues stirring reaction 20 ~ 26 hours;
(2), step (1) reacted mixed solution is added drop-wise in the hexane solution of dimethylchlorosilane, passes into nitrogen or rare gas element, stirring reaction 8 ~ 12 hours in ice-water bath;
(3), by reaction solution pour in separating funnel, divide and get upper organic phase, dry point of organic phase of getting, and revolve steaming removing normal hexane solvent, obtain cage type eight silicon hydrogen silsesquioxane O
8m
8 hpOSS;
(4), by O
8m
8 hpOSS is dissolved in toluene solvant, passes into nitrogen or rare gas element, adds platinum or palladium catalyst and excessive 4-Vinyl phenol, heating reflux reaction 5 ~ 6 hours under nitrogen or protection of inert gas;
(5), revolve and steam except desolventizing, obtain glutinous thick liquid, dissolve again with toluene solvant, be mixed with dilute toluene solution, remove metal catalyst, and then revolve steaming removing toluene solvant, last vacuum-drying obtains product eight phenolic hydroxyl group cagelike silsesquioxane OP-POSS.
The preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, specifically comprises the steps:
(1), by tetraethoxy be added drop-wise in the mixing solutions of methyl alcohol, water and Tetramethylammonium hydroxide, first in ice-water bath, be cooled to 0 DEG C, stirring reaction, after 4 ~ 8 hours, rises to room temperature and continues stirring reaction 20 ~ 26 hours;
(2), step (1) reacted mixed solution is added drop-wise in the hexane solution of dimethylchlorosilane, passes into nitrogen or rare gas element, stirring reaction 8 ~ 12 hours in ice-water bath;
(3), by reaction solution pour in separating funnel, divide and get upper organic phase, dry point of organic phase of getting, and revolve steaming removing normal hexane solvent, obtain cage type eight silicon hydrogen silsesquioxane O
8m
8 hpOSS;
(4), by O
8m
8 hpOSS is dissolved in toluene solvant, passes into nitrogen or rare gas element, adds platinum or palladium catalyst and excessive in acetoxy-styrene, heating reflux reaction 5 ~ 6 hours under nitrogen or protection of inert gas;
(5), revolve and steam except desolventizing, obtain glutinous thick liquid, dissolve again with toluene solvant, be mixed with dilute toluene solution, remove metal catalyst, and then revolve steaming removing toluene solvant, last vacuum-drying;
(6), the product after vacuum-drying is dissolved in THF solvent; to be hydrolyzed under room temperature rare gas element or nitrogen protection reaction by NaOH dilute solution; reaction times is 2 ~ 3 days; neutralize excessive NaOH afterwards; and then except desolventizing, obtain eight phenolic hydroxyl group cagelike silsesquioxane OP-POSS.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, the mol ratio keeping Si element and N element in reaction system in step (1) is between 1 ~ 2:1, H
2the mol ratio of O and Si element is between 1 ~ 16:1, and the volumetric molar concentration of Si element is between 0.1 ~ 1mol/L.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, in step (2), keep the volumetric molar concentration of Si element in reaction system between 0.1 ~ 0.5mol/L.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, reaction solution is poured in separating funnel in (3) by step, with deionized water, aqueous phase is washed till neutrality, leaves standstill, and divides and gets upper organic phase, and use anhydrous MgSO
4dry point of organic phase of getting, and revolve steaming removing normal hexane solvent, obtain solid particulate matter, solid particulate matter will be obtained by methanol wash, filter, obtain cage type eight silicon hydrogen silsesquioxane O
8m
8 hpOSS.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, in step (4), the concentration of toluene solution is between 0.05 ~ 0.1mol/L; The described 4-Vinyl phenol that adds or be O to the molar weight of acetoxy-styrene
8m
8 h1 ~ 3 times of POSS molar weight.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, remove metal catalyst by aluminum oxide column chromatography in step (5), and vacuum drying temperature is 60 ~ 80 DEG C.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, the concrete grammar neutralizing excessive NaOH in step (6) is: reacting after 2 ~ 3 days is that the ether of 1:1 and the mixing solutions of deionized water join in reaction system by volume ratio, then dripping mass concentration is the dilute hydrochloric acid of 3 ~ 10%, be between 7 ~ 8 to pH, finally remove the solvent of reaction system, obtain eight phenolic hydroxyl group cagelike silsesquioxane OP-POSS.
In the preparation method of above-mentioned eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, the Q prepared
8m
8 hsynthetic yield>=50% of POSS, purity is greater than 75%; The synthetic yield of the OP-POSS prepared is not less than 40%, and purity is greater than 80%.
The present invention compared with prior art has following beneficial effect:
(1), the present invention with the tetraethyl orthosilicate of cheapness for the raw material that sets out, prepare poly-(dimethylsilyl bis) silsesquioxane of cage type eight containing a large amount of Si-H key by controlled hydrolysis condensation, then functional modification is carried out to it and finally obtain eight phenolic hydroxyl group cagelike silsesquioxanes;
(2), The present invention gives the preparation process of eight phenolic hydroxyl group cagelike silsesquioxane the bests, processing condition and component proportioning, not only preparation process is simple, and the products collection efficiency prepared is high, and purity is high, and cost is low;
(3) 4-Vinyl phenol can be adopted in the preparation process of, the present invention eight phenolic hydroxyl group cagelike silsesquioxane, also can adopt lower-cost to acetoxy-styrene, only need finally to increase alkalinization, preparation method is versatile and flexible, meets different needs;
(4), the present invention can synthesize highly purified eight phenolic hydroxyl group POSS molecules efficiently by three step chemical reactions, eight phenolic hydroxyl group cagelike silsesquioxanes of synthesis have the Si-O-Si inorganic skeleton structure of nano level cage structure, drift angle is with the phenolic hydroxyl group functional group of high reaction activity, the filler of resin can be used as high reaction activity nano particle additive, be bonded in crosslinked polymer network in the mode of chemical bond, can be used as the effect that reactive property-modifying additive plays inorganic nano-particle enhancing and organic chemistry cross-linking set simultaneously.
Accompanying drawing explanation
Fig. 1 is T8 structure POSS molecular structure;
Fig. 2 is OP-POSS molecule Fourier infrared spectrum (FTIR) of the present invention;
Fig. 3 is O of the present invention
8m
8 hpOSS molecule
1h nuclear magnetic spectrogram (NMR);
Fig. 4 is O of the present invention
8m
8 hpOSS molecule
29si nuclear magnetic spectrogram (NMR);
Fig. 5 is O of the present invention
8m
8 hfourier's infrared spectrum (FTIR) of POSS molecule.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
The present invention contains the cagelike silsesquioxane (OP-POSS) of eight phenolic hydroxyl groups, and its structural formula is as follows:
The synthesis of above-mentioned eight phenolic hydroxyl group cagelike silsesquioxanes, comprises poly-(dimethylsilyl bis) silsesquioxane (Q of cage type eight
8m
8 hpOSS) synthesis two steps of synthesis and eight phenolic hydroxyl group cagelike silsesquioxanes (OP-POSS).Concrete preparation method is as follows:
(1) tetraethoxy is added drop-wise in the mixing solutions of methyl alcohol, water and Tetramethylammonium hydroxide, 0 DEG C is cooled in ice-water bath, stirring reaction is after 4 ~ 8 hours, rise to room temperature and continue stirring reaction 20 ~ 26 hours, the mol ratio keeping Si element and N element in reaction system is between 1 ~ 2:1, H
2the mol ratio of O and Si element is between 1 ~ 16:1, and the volumetric molar concentration of Si element is between 0.1 ~ 1mol/L.
(2) step (1) reacted mixed solution is added drop-wise in the hexane solution of dimethylchlorosilane, pass into nitrogen or rare gas element, stirring reaction 8 ~ 12 hours in ice-water bath, keeps the volumetric molar concentration of Si element between 0.1 ~ 0.5mol/L.
(3) after completion of the reaction, solution presents layering, is poured into by reaction solution in separating funnel, with deionized water, aqueous phase is washed till neutrality, leaves standstill, and divides and gets upper organic phase.Use anhydrous MgSO
4dry point of organic phase of getting, revolves and steams except desolventizing, obtain white solid particulate matter, methanol wash, filter, obtain O
8m
8 hpOSS.
(4) by O
8m
8 hpOSS is dissolved in dry toluene solvant; concentration is between 0.05 ~ 0.1mol/L; pass into nitrogen or inert protective gas, add the 4-Vinyl phenol of platinum or palladium catalyst and excessive (mol ratio 1 ~ 3 times) or (4-Vinyl phenol namely added or the molar weight to acetoxy-styrene are O to acetoxy-styrene
8m
8 h1 ~ 3 times of POSS molar weight), heating reflux reaction 5 ~ 6 hours under nitrogen or protection of inert gas.
(5) after completion of the reaction, revolve and steam except desolventizing, obtain yellow glutinous thick liquid, dissolve again with toluene solvant, be mixed with dilute toluene solution, remove metal catalyst by aluminum oxide column chromatography, and then revolve steaming removing toluene solvant, last 60 ~ 80 DEG C of vacuum-dryings obtain yellow sticky shape product liquid (OP-POSS) or sticky shape white eight acetoxyl group phenyl POSS (AP-POSS);
If above-mentioned steps adds 4-Vinyl phenol in (4), then step (5) obtains yellow sticky shape product liquid (OP-POSS), and reaction terminates.
If above-mentioned steps adds acetoxy-styrene in (4), then step (5) obtains sticky shape white eight acetoxyl group phenyl POSS (AP-POSS), needs the product by step (5) obtains to be handled as follows:
The product that step (5) prepares is dissolved in THF solvent; to be hydrolyzed under room temperature rare gas element or nitrogen protection reaction by the NaOH dilute solution that mass concentration is 0.5% ~ 1%; reacting after 2 ~ 3 days joins in reaction system by the mixing solutions (volume ratio is 1:1) of ether and deionized water; then slowly dripping mass concentration is the dilute hydrochloric acid of 3 ~ 10%, is between 7 ~ 8 to pH.Finally remove the solvent of reaction system, obtain eight phenolic hydroxyl group cagelike silsesquioxane, i.e. OP-POSS.
The Q that the present invention prepares
8m
8 hsynthetic yield>=50% of POSS, purity is greater than 75%; The synthetic yield of the OP-POSS prepared is not less than 40%, and purity is greater than 80%.
The chemical reaction process involved by preparation method (synthetic route) as follows of the present invention eight phenolic hydroxyl group cagelike silsesquioxane:
(1), 4-Vinyl phenol is added
(2), add acetoxy-styrene
Embodiment 1
Weigh five water Tetramethylammonium hydroxide 8.2g, methyl alcohol 45ml, 8.1g deionized water, be positioned in 100ml there-necked flask, pass into nitrogen or argon gas, water of condensation, magnetic agitation 30 minutes in ice-water bath, add 10ml tetraethyl orthosilicate, be added drop-wise in said mixture, ice-water bath rises to room temperature and continues reaction 24 hours after reacting 6 hours.After reaction terminates, above-mentioned mixed solution being added drop-wise to dimethylchlorosilane volume fraction is in the 60ml hexane solution of 20vol%; pass into nitrogen or argon shield gas, in ice-water bath, stirring reaction stopped reaction after 12 hours, pours into reaction mixture in the separating funnel of 1000ml; deionized water is washed till neutrality; leave standstill, divide and get upper organic phase, use anhydrous magnesium sulfate drying organic phase; revolve and steam except desolventizing obtains white granular crystallite 3.32g; methanol wash, filters, obtains Q
8m
8 hpOSS, mass yield is 58.2%.
Be illustrated in figure 3 O of the present invention
8m
8 hpOSS molecule
1h nuclear magnetic spectrogram (NMR); Figure 4 shows that O of the present invention
8m
8 hpOSS molecule
29si nuclear magnetic spectrogram (NMR) is O of the present invention described in Fig. 5
8m
8 hfourier's infrared spectrum (FTIR) of POSS molecule, FTIR spectrum characterizes (FTIR, cm as seen from the figure
-1): 2964 (vCH
3), 1255 (δ Si (CH
3)
2), 068 (vSi-O-Si), 890 (δ SiH), 2140 (vSi-H);
29si nucleus magnetic resonance characterizes (NMR, ppm) :-1.3 ,-108.5, and area ratio is 1:1;
1h nuclear magnetic spectrogram (NMR): 0.3,4.7, area ratio is about 1:6.
Weigh 3gQ
8m
8 hpOSS is dissolved in 60ml dry toluene solvent, adds 4-Vinyl phenol 5g, drips Pt (dvs) catalyzer that 3 ~ 5 massfractions are 1wt%, N
2back flow reaction 5 hours under atmosphere protection.After completion of the reaction, revolve and steam except desolventizing, obtain sticky shape yellow substance, add 80ml toluene solvant, be mixed with dilute toluene solution, by aluminum oxide column chromatographic separation removing Pt catalyzer, revolve and steam removing toluene solvant, and then remove excessive 4-Vinyl phenol through underpressure distillation, finally except desolventizing 80 DEG C of vacuum-dryings obtain yellow eight phenolic hydroxyl group POSS (OP-POSS) 3.2g of sticky shape, mass yield 54.6%.Be illustrated in figure 2 OP-POSS molecule Fourier infrared spectrum (FTIR) of the present invention.
Embodiment 2
Weigh five water Tetramethylammonium hydroxide 5g, methyl alcohol 40ml, 5.0g deionized water, be positioned in 100ml there-necked flask, pass into nitrogen or argon gas, water of condensation, magnetic agitation 30 minutes in ice-water bath, add 6g tetraethyl orthosilicate, be added drop-wise in said mixture, ice-water bath rises to room temperature and continues reaction 24 hours after reacting 6 hours.After reaction terminates, above-mentioned mixed solution being added drop-wise to dimethylchlorosilane volume fraction is in the 40ml hexane solution of 20vol%; pass into nitrogen or argon shield gas, in ice-water bath, stirring reaction stopped reaction after 12 hours, pours into reaction mixture in the separating funnel of 1000ml; deionized water is washed till neutrality; leave standstill, divide and get upper organic phase, use anhydrous magnesium sulfate drying organic phase; revolve and steam except desolventizing obtains white granular crystallite 2.10g; methanol wash, filters, obtains Q
8m
8 hpOSS, mass yield 57.4%.
Weigh 1.5gQ
8m
8 hpOSS is dissolved in 35ml dry toluene solvent, adds 4-Vinyl phenol 2g, drips Pt (dvs) catalyzer that 4 massfractions are 1wt%, N
2back flow reaction 5 hours under atmosphere protection.After completion of the reaction, revolve and steam except desolventizing, obtain sticky shape yellow substance, add 50ml toluene solvant, be mixed with dilute toluene solution, by aluminum oxide column chromatographic separation removing Pt catalyzer, revolve and steam removing toluene solvant, and then removing excessive 4-Vinyl phenol through underpressure distillation, last 80 DEG C of vacuum-dryings obtain faint yellow eight phenolic hydroxyl group POSS (OP-POSS) 1.4g of sticky shape, mass yield 47.8%.
Embodiment 3
Weigh five water Tetramethylammonium hydroxide 41g, methyl alcohol 225ml, 40.5g deionized water, be positioned in 100ml there-necked flask, pass into nitrogen or argon gas, water of condensation, magnetic agitation 30 minutes in ice-water bath, add 45g tetraethyl orthosilicate, be added drop-wise in said mixture, ice-water bath rises to room temperature and continues reaction 24 hours after reacting 8 hours.After reaction terminates, above-mentioned mixed solution being added drop-wise to dimethylchlorosilane volume fraction is in the 1000ml hexane solution of 20vol%; pass into nitrogen or argon shield gas; stirring reaction stopped reaction after 10 hours in ice-water bath; poured in batches in the separating funnel of 1000ml by reaction mixture, deionized water is washed till neutrality, leaves standstill; divide and get upper organic phase; use anhydrous magnesium sulfate drying organic phase, revolve and steam except desolventizing obtains white granular crystallite 12.8g, be Q
8m
8 hpOSS.
Weigh 5gQ
8m
8 hpOSS is dissolved in 125ml dry toluene solvent, adds acetoxy-styrene 20g, drips Pt (dvs) catalyzer that 6 massfractions are 1wt%, N
2back flow reaction 6 hours under atmosphere protection.After completion of the reaction, revolve and steam except desolventizing, obtain sticky shape yellow substance, add 300ml toluene solvant, revolve after removing Pt catalyzer by aluminum oxide column chromatographic separation and steam removing toluene solvant, last 80 DEG C of vacuum-dryings remove desolventizing and obtain sticky shape white eight acetoxyl group phenyl POSS (AP-POSS) 5.4g, and mass yield is 47.4%.
The 5.4gAP-POSS of preparation is dissolved in the THF solvent of 100ml; drip the NaOH dilute solution 25ml that mass concentration is 1%; dropping limit, limit is stirred; under protection of inert gas, room temperature is hydrolyzed reaction; reacting after 2 days joins in reaction solution by the ether of volume fraction 1:1 and deionized water mixing solutions 150ml; then slowly dripping mass concentration is the dilute hydrochloric acid of 10%; be 8 to ph value of aqueous phase; finally remove the solvent in reaction system; obtain thick yellow OP-POSS4.1g, mass yield is 92.6%.
The above; be only the embodiment of the best of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
The content be not described in detail in specification sheets of the present invention belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes, is characterized in that: its structural formula is as follows:
2. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to claim 1, is characterized in that: specifically comprise the steps:
(1), by tetraethoxy be added drop-wise in the mixing solutions of methyl alcohol, water and Tetramethylammonium hydroxide, first in ice-water bath, be cooled to 0 DEG C, stirring reaction, after 4 ~ 8 hours, rises to room temperature and continues stirring reaction 20 ~ 26 hours;
(2), step (1) reacted mixed solution is added drop-wise in the hexane solution of dimethylchlorosilane, passes into nitrogen or rare gas element, stirring reaction 8 ~ 12 hours in ice-water bath;
(3), by reaction solution pour in separating funnel, divide and get upper organic phase, dry point of organic phase of getting, and revolve steaming removing normal hexane solvent, obtain cage type eight silicon hydrogen silsesquioxane O
8m
8 hpOSS;
(4), by O
8m
8 hpOSS is dissolved in toluene solvant, passes into nitrogen or rare gas element, adds platinum or palladium catalyst and excessive 4-Vinyl phenol, heating reflux reaction 5 ~ 6 hours under nitrogen or protection of inert gas;
(5), revolve and steam except desolventizing, obtain glutinous thick liquid, dissolve again with toluene solvant, be mixed with dilute toluene solution, remove metal catalyst, and then revolve steaming removing toluene solvant, last vacuum-drying obtains product eight phenolic hydroxyl group cagelike silsesquioxane OP-POSS.
3. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to claim 1, is characterized in that: specifically comprise the steps:
(1), by tetraethoxy be added drop-wise in the mixing solutions of methyl alcohol, water and Tetramethylammonium hydroxide, first in ice-water bath, be cooled to 0 DEG C, stirring reaction, after 4 ~ 8 hours, rises to room temperature and continues stirring reaction 20 ~ 26 hours;
(2), step (1) reacted mixed solution is added drop-wise in the hexane solution of dimethylchlorosilane, passes into nitrogen or rare gas element, stirring reaction 8 ~ 12 hours in ice-water bath;
(3), by reaction solution pour in separating funnel, divide and get upper organic phase, dry point of organic phase of getting, and revolve steaming removing normal hexane solvent, obtain cage type eight silicon hydrogen silsesquioxane O
8m
8 hpOSS;
(4), by O
8m
8 hpOSS is dissolved in toluene solvant, passes into nitrogen or rare gas element, adds platinum or palladium catalyst and excessive in acetoxy-styrene, heating reflux reaction 5 ~ 6 hours under nitrogen or protection of inert gas;
(5), revolve and steam except desolventizing, obtain glutinous thick liquid, dissolve again with toluene solvant, be mixed with dilute toluene solution, remove metal catalyst, and then revolve steaming removing toluene solvant, last vacuum-drying;
(6), the product after vacuum-drying is dissolved in THF solvent; to be hydrolyzed under room temperature rare gas element or nitrogen protection reaction by NaOH dilute solution; reaction times is 2 ~ 3 days; neutralize excessive NaOH afterwards; and then except desolventizing, obtain eight phenolic hydroxyl group cagelike silsesquioxane OP-POSS.
4. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to Claims 2 or 3, is characterized in that: the mol ratio keeping Si element and N element in reaction system in described step (1) is between 1 ~ 2:1, H
2the mol ratio of O and Si element is between 1 ~ 16:1, and the volumetric molar concentration of Si element is between 0.1 ~ 1mol/L.
5. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to Claims 2 or 3, is characterized in that: keep the volumetric molar concentration of Si element in reaction system in described step (2) between 0.1 ~ 0.5mol/L.
6. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to Claims 2 or 3, it is characterized in that: reaction solution is poured in separating funnel in (3) by described step, with deionized water, aqueous phase is washed till neutrality, leave standstill, divide and get upper organic phase, and use anhydrous MgSO
4dry point of organic phase of getting, and revolve steaming removing normal hexane solvent, obtain solid particulate matter, solid particulate matter will be obtained by methanol wash, filter, obtain cage type eight silicon hydrogen silsesquioxane O
8m
8 hpOSS.
7. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to Claims 2 or 3, is characterized in that: in described step (4), the concentration of toluene solution is between 0.05 ~ 0.1mol/L; The described 4-Vinyl phenol that adds or be O to the molar weight of acetoxy-styrene
8m
8 h1 ~ 3 times of POSS molar weight.
8. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to Claims 2 or 3, it is characterized in that: remove metal catalyst by aluminum oxide column chromatography in described step (5), and vacuum drying temperature is 60 ~ 80 DEG C.
9. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to claim 3, it is characterized in that: the concrete grammar neutralizing excessive NaOH in described step (6) is: reacting after 2 ~ 3 days is that the ether of 1:1 and the mixing solutions of deionized water join in reaction system by volume ratio, then dripping mass concentration is the dilute hydrochloric acid of 3 ~ 10%, be between 7 ~ 8 to pH, finally remove the solvent of reaction system, obtain eight phenolic hydroxyl group cagelike silsesquioxane OP-POSS.
10. the preparation method of eight phenolic hydroxyl group polyhedral oligomeric polyhedral silsesquioxanes according to Claims 2 or 3, is characterized in that: described in the Q for preparing
8m
8 hsynthetic yield>=50% of POSS, purity is greater than 75%; The synthetic yield of the OP-POSS prepared is not less than 40%, and purity is greater than 80%.
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| CN106279694A (en) * | 2016-07-28 | 2017-01-04 | 北京化工大学 | Nanometer cage-type silsesquioxane coupling agent and the method preparing hybrid silica aeroge |
| CN106894009A (en) * | 2017-02-24 | 2017-06-27 | 武汉大学 | A kind of epoxy radicals POSS modified metal surface pretreating reagent and preparation method thereof, application |
| CN110483777A (en) * | 2019-09-10 | 2019-11-22 | 哈尔滨工业大学 | A kind of synthetic method of more silicone hydroxyl POSS |
| CN110520430A (en) * | 2017-04-20 | 2019-11-29 | 国立研究开发法人产业技术综合研究所 | The manufacturing method of silanol compound and silanol compound |
| CN111116869A (en) * | 2019-05-28 | 2020-05-08 | 杭州师范大学 | Liquid epoxy group functionalized POSS modified epoxy resin and preparation method thereof |
| CN111423586A (en) * | 2020-05-12 | 2020-07-17 | 哈尔滨工业大学 | Synthesis method of polyhedral oligomeric silsesquioxane with silicon-hydrogen functional groups |
| CN112795015A (en) * | 2021-02-04 | 2021-05-14 | 浙江大学 | Four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and preparation method and application thereof |
| CN112940257A (en) * | 2021-02-04 | 2021-06-11 | 浙江大学 | Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279694A (en) * | 2016-07-28 | 2017-01-04 | 北京化工大学 | Nanometer cage-type silsesquioxane coupling agent and the method preparing hybrid silica aeroge |
| CN106279694B (en) * | 2016-07-28 | 2019-03-29 | 北京化工大学 | Nanometer cage-type silsesquioxane coupling agent and the method for preparing hybrid silica aeroge |
| CN106894009A (en) * | 2017-02-24 | 2017-06-27 | 武汉大学 | A kind of epoxy radicals POSS modified metal surface pretreating reagent and preparation method thereof, application |
| CN106894009B (en) * | 2017-02-24 | 2019-03-15 | 武汉大学 | A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application |
| CN110520430B (en) * | 2017-04-20 | 2023-09-05 | 国立研究开发法人产业技术综合研究所 | Silanol compound and process for producing silanol compound |
| CN110520430A (en) * | 2017-04-20 | 2019-11-29 | 国立研究开发法人产业技术综合研究所 | The manufacturing method of silanol compound and silanol compound |
| CN111116869A (en) * | 2019-05-28 | 2020-05-08 | 杭州师范大学 | Liquid epoxy group functionalized POSS modified epoxy resin and preparation method thereof |
| CN110483777B (en) * | 2019-09-10 | 2022-02-08 | 哈尔滨工业大学 | Synthesis method of poly-silicon hydroxyl POSS |
| CN110483777A (en) * | 2019-09-10 | 2019-11-22 | 哈尔滨工业大学 | A kind of synthetic method of more silicone hydroxyl POSS |
| CN111423586A (en) * | 2020-05-12 | 2020-07-17 | 哈尔滨工业大学 | Synthesis method of polyhedral oligomeric silsesquioxane with silicon-hydrogen functional groups |
| CN112795015A (en) * | 2021-02-04 | 2021-05-14 | 浙江大学 | Four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and preparation method and application thereof |
| CN112940257A (en) * | 2021-02-04 | 2021-06-11 | 浙江大学 | Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof |
| CN112795015B (en) * | 2021-02-04 | 2022-05-20 | 浙江大学 | Four-functionality eugenol epoxy functionalized cage-type silsesquioxane, and preparation method and application thereof |
| CN112940257B (en) * | 2021-02-04 | 2022-07-22 | 浙江大学 | Eugenol epoxy group double-splint type cage-like silsesquioxane as well as preparation method and application thereof |
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