CN102584887A - Preparation method of novel epoxy group functionalized macrocyclic oligomeric silsesquioxane - Google Patents
Preparation method of novel epoxy group functionalized macrocyclic oligomeric silsesquioxane Download PDFInfo
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Abstract
The invention relates to a preparation method of novel epoxy group functionalized macrocyclic oligomeric silsesquioxane. The method comprises three steps of the synthesis of hexaphenyl (methyl) cyclohexa-silicon sodium alkoxide/nickel salt, the synthesis of hexaphenyl (methyl) hexahydro (ethenyl and chloropropyl) cyclosiloxane, and the synthesis of hexaphenyl (methyl) hexa-glycidyl ether group cyclohexasiloxane, and finally the macrocyclic 12-member-contained oligomeric silsesquioxane is prepared. Compared with the prior art, the phenyl (methyl) macrocyclic oligomeric silsesquioxane has the advantages that the preparation period is short and the yield is high, can be stored for a long time under the room temperature, also can be stored for a long time under the low temperature, can be dissolved in organic solvents with low boiling points, such as acetone, benzene, toluene, dichloromethane, chloroform, and tetrahydrofuran. The epoxy group functionalized macrocyclic oligomeric silsesquioxane can be used as a curing agent with excellent performances in thermosetting resin.
Description
Technical field
The present invention relates to a kind of method for preparing silicone compounds, especially relate to the preparation method of a kind of hexaphenyl (methyl) six glycidyl ethers (vinyl, chloropropyl) ring six siloxanes.
Background technology
The annular oligomeric silsesquioxanes is one type of oligomeric silsesquioxanes (MOSS) with three-dimensional ring structure.Its inorganic in nature and polyhedron oligomeric silsesquioxanes (POSS) are similar, have the silsesquioxane skeleton.MOSS has different silica key unit numbers, but and has a characteristic of functionalization widely.Compare with the synthetic of POSS, it is simple that MOSS synthetic has method, and the cycle is short, the characteristics that productive rate is high, and lower to the degree of drying requirement of solvent and environment.Such annular silsesquioxane can be used for the application in a plurality of fields such as preparation of polymer/inorganic matrix material, thermosetting resin modification, cyclic polymer brush, linking agent, gel, pharmaceutical carrier, how empty material.These method synthetic hexaphenyl six glycidyl ether basic rings six siloxanes can use the modification at epoxy resin, benzoxazine, improve its toughness, second-order transition temperature, hydrophobic performance, flame retardant resistance and thermal decomposition performance etc.
The basic structure of hexaphenyl six glycidyl ether basic rings, six siloxanes is following:
Summary of the invention
The object of the invention is exactly the preparation that a kind of available various organic-inorganic hybrid materials are provided for the defective that overcomes above-mentioned prior art existence; To the thermosetting resin modification, the preparation method of the big annular oligomeric silsesquioxanes of novel epoxy base functionalization of synthetic multi-functional ring-type molecular brush.
The object of the invention can be realized through following technical scheme:
The preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization may further comprise the steps:
(1) hexaphenyl (methyl) ring six sodium silanolates/nickel salt is synthetic
Under 0-10 ℃ of condition, phenyl-trichloro-silicane is joined solvent; Solvent can be selected benzene or toluene; The deionized water that adds respective volume then, the phenyl silicone that obtains with the phenyl-trichloro-silicane hydrolysis, again with sodium hydroxide, water, propyl carbinol hybrid reaction after; Add the dichloro hexamine nickel, reaction obtains hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt;
(2) hexaphenyl (methyl) six hydrogen (vinyl, chloropropyl) cyclosiloxane is synthetic
Exsiccant toluene or benzene and pyridine or triethylamine mixing, add a hydrogen dimethylamino base chlorosilane or vinyl-dimethyl base chlorosilane or chloropropyl dimethylchlorosilane, stirred 5-10 minute; Add step (1) synthetic siloxy nickel salt, stirring at room 1-2 days, filter; Washing, anhydrous magnesium sulfate drying removes and desolvates; Obtain heavy-gravity oily product, be hexaphenyl (methyl) six hydrogen (vinyl, chloropropyl) cyclosiloxane.
(3) hexaphenyl (methyl) six glycidyl ether basic rings six siloxanes is synthetic
Select to use hexaphenyl six silicon hydrogen, six siloxanes or hexamethyl six silicon hydrogen six siloxanes to continue next step and synthesize, the group with the glycidyl ether that contains two keys carries out hydrosilylation addition reaction; Use toluene or benzene as solvent; Under the platinum catalyst effect, under the anhydrous and oxygen-free condition, 70-80 ℃ was reacted 15-25 hour; Remove excessive solvent and reactant, obtain containing annular ten binary oligomeric silsesquioxanes.
Step (1) specifically may further comprise the steps: with phenyl three n-butoxy silane or methyl three n-butoxy silane is precursor, adds sodium hydroxide and water then, and the mol ratio of precursor and sodium hydroxide and water is 6-10: 8-11: 7-10; Place propyl carbinol again, backflow 2-3 hour, after the cooling; Disposable adding hexamine Nickel Chloride catalyzer, the mol ratio of the silane of front and hexamine Nickel Chloride catalyzer is 6-10: 2-5, continues backflow 2-3 hour; Stopped reaction filters, and revolves to steam to remove the part propyl carbinol; Low temperature is placed a night, obtains the yellowish-orange crystal settling, promptly obtains hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt.
Step (1) can also adopt following steps: phenyl-trichloro-silicane or METHYL TRICHLORO SILANE equal-volume are dissolved in toluene or the benzene, then to wherein slowly dripping mixed solvent, violent stirring 10 hours; Isolate organic layer, washing is to neutral, behind the anhydrous magnesium sulfate drying; Filtration is also removed solvent wherein, and vacuum-drying obtains phenyl sesquisiloxane resin or methyl sesquisiloxane resin; For 1-3: 2-4 phenyl sesquisiloxane resin or methyl sesquisiloxane resin are joined in the propyl carbinol with sodium hydroxide in molar ratio, are back to mixture and become homogeneous phase, be cooled to about 50 the degree after; Add sodium Metal 99.5, the mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and sodium Metal 99.5 is 1-3: 0.5-2, continues backflow 1-2 hour; Last property adding hexamine Nickel Chloride, the mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and hexamine Nickel Chloride is 2-4: 0.5-3, refluxes then 2-3 hour; Remove by filter salt, revolve to steam and remove the part propyl carbinol, low temperature is placed a night; Yellow crystals is settled out, suction filtration and vacuum-drying.Hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt.
The volume ratio of described phenyl-trichloro-silicane or METHYL TRICHLORO SILANE and mixed solvent is 1: (5-7).
Described mixed solvent is that water and benzene or water and toluene are 4 by volume: mixture (1-2).
Step (2) specifically may further comprise the steps: with mol ratio is 10-20: a 12-30 dry pyridine and a hydrogen dimethylamino base chlorosilane or vinyl-dimethyl base chlorosilane or chloropropyl dimethylchlorosilane; Join together in exsiccant toluene or the benzene solvent; Stirring at room 5-20 minute; Add hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt again; The mol ratio of above-mentioned chlorosilane and hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt is 50-100: 1, at room temperature reaction 1-3 days, remove by filter deposition.Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove toluene or benzene and obtain transparent oily matter and get final product the about 94-98% of productive rate.
Step (3) specifically may further comprise the steps: with the mol ratio of hexaphenyl six silicon hydrogen, six siloxanes or hexamethyl six silicon hydrogen, six siloxanes and glycidyl allyl ether is 1: 2-5 joins in exsiccant toluene or the benzene, under the nitrogen protection condition, adds the Karstedt catalyzer; Under 70-90 ℃ of condition; Reacted 15-30 hour, and removed excessive solvent and reactant through decompression, after the vacuum-drying; The thickness oily matter that obtains is product and contains annular ten binary oligomeric silsesquioxanes, productive rate 95-98%.
Described product is six epoxy group(ing) annular, ten binary oligomeric silsesquioxanes, contains six vinyl annular ten binary oligomeric silsesquioxanes or contain chlordene propyl group annular ten binary oligomeric silsesquioxanes.
Compared with prior art, prepared phenyl (methyl) the ring-type polysilsesquioxane of the present invention can at room temperature be preserved the long period, can prolonged preservation under coldcondition; Can be dissolved in acetone, benzene, toluene; Methylene dichloride, chloroform is in the low boiling point organic solvents such as THF.The annular oligomeric silsesquioxanes is one type of oligomeric silsesquioxanes (MOSS) with three-dimensional ring structure.Its inorganic in nature and polyhedron oligomeric silsesquioxanes (POSS) are similar, have the silsesquioxane skeleton.MOSS has different silica key unit numbers, but and has a characteristic of functionalization widely.Compare with the synthetic of POSS, it is simple that MOSS synthetic has method, and the cycle is short, the characteristics that productive rate is high, and lower to the degree of drying requirement of solvent and environment.Such annular silsesquioxane can be used for the application in a plurality of fields such as preparation of polymer/inorganic matrix material, thermosetting resin modification, cyclic polymer brush, linking agent, gel, pharmaceutical carrier, how empty material.These method synthetic hexaphenyl six glycidyl ether basic rings six siloxanes can use the modification at epoxy resin, benzoxazine, improve its toughness, second-order transition temperature, hydrophobic performance, flame retardant resistance and thermal decomposition performance etc.
Description of drawings
Fig. 1 is the hydrogen spectrogram of hexaphenyl six silicon hydrogen six siloxanes;
Fig. 2 is the silicon spectrogram of hexaphenyl six silicon hydrogen six siloxanes;
Fig. 3 is the hydrogen spectrogram of hexaphenyl six glycidyl ether basic rings six siloxanes.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Hexaphenyl six glycidyl ether basic rings, six siloxanes and epoxy resin (DGEBA) with different ratios on hot platform stir.Disposable then adding solidifying agent can be selected solidifying agent not of the same race for use, as 4 ', and 4 diaminodiphenyl-methanes (DDM), two adjacent chlorodiphenyl amine methane (MOCA) etc.Under 80 degree, mix, to solidify two hours at 150 degree and 180 degree respectively, arriving of the toughness of epoxy resin and hydrophobic performance improves.
Hexaphenyl six glycidyl ether basic rings, six siloxanes and double A type benzoxazine monomer with different ratios on hot platform are dissolved in a spot of methylene dichloride, in 40 degree baking ovens, slowly volatilize to remove and desolvate.And then remove remaining methylene dichloride in the vacuum drying oven of 90 degree.180 degree solidified 4 hours then.It is bolarious translucent that the gained sample is, and sample is carried out the DMA test, and the glass transition of thermosetting resin is along with first the increasing afterwards of the adding of hexaphenyl six glycidyl ether basic rings six siloxanes reduces, and the mechanical property of material is well improved.
Hexaphenyl (methyl) six glycidyl ether basic rings six siloxanes under suitable condition, can convert epoxy group(ing) to hydroxyl or other groups, so just can on the ring-type silsesquioxane, connect different polymer.Synthetic novel high molecular polymer with brush shape structure.
Hexaphenyl (methyl) six ethene basic rings six siloxanes can be used as the multi-group crosslink agent, are used for the synthetic of gel.
The preparation method of phenyl provided by the invention and methyl six glycidyl ethers (chloropropyl) ring six siloxanes is:
The first step: hexaphenyl (methyl) encircles the synthetic of six sodium silanolates/nickel salt
With precursor phenyl (methyl) three n-butoxy silane, adding is 6-10 (precursor) with the mol ratio of precursor then: the sodium hydroxide of 8-11: 7-10 and water, as go in the propyl carbinol backflow 2-3 hour.After the cooling, the mol ratio of disposable adding and precursor is the hexamine Nickel Chloride catalyzer of 6-10 (precursor): 2-5, continues backflow 2-3 hour.Stopped reaction filters, and revolves to steam to remove the part propyl carbinol, and low temperature is placed a night, obtains the yellowish-orange crystal settling, filters.In addition, can also adopt following method, be dissolved in about 100 milliliters phenyl (methyl) trichlorosilane in isopyknic toluene (benzene), under condition of ice bath, slowly be added drop-wise in the mixture of 400 milliliters/150 milliliters toluene (benzene), and violent stirring 10 hours.Isolate organic layer, washing is to neutral, behind the anhydrous magnesium sulfate drying; Filter, remove and desolvate, and vacuum-drying; Obtain phenyl (methyl) polysilsesquioxane resins; Getting above-mentioned polyphenylene polysilsesquioxane resins, is that the sodium hydroxide of 1-3: 2-4 joins in the propyl carbinol with its mol ratio, is back to mixture and changes homogeneous phase into.After being cooled to about 50 degree, adding and gathering silsesquioxane resin mol ratio with phenyl (methyl) is the sodium Metal 99.5 of 1-3: 0.5-2, continues backflow 1-2 hour.Last property adding and phenyl (methyl) polysilsesquioxane resins mol ratio are the hexamine Nickel Chloride of 2-4: 0.5-3, reflux then 2-3 hour.Remove by filter salt, revolve to steam and remove the part propyl carbinol, low temperature is placed a night, and yellow crystals is settled out.Suction filtration, and vacuum-drying.Obtain product.
Second step: hexaphenyl (methyl) six hydrogen (vinyl, chloropropyl) cyclosiloxane synthetic
With mol ratio is 10-20: a 12-30 dry pyridine and a hydrogen dimethylamino base chlorosilane (vinyl-dimethyl base chlorosilane, chloropropyl dimethylchlorosilane); Join together in exsiccant toluene (benzene) solvent; Stirring at room 5-20 minute, adding was 50-100 (chlorosilane) with corresponding chlorosilane mol ratio again: 1 hexaphenyl (methyl), six sodium silanolates/nickel salt.Room temperature reaction 1-3 days, remove by filter deposition.Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove toluene (benzene) and obtain transparent oily matter.The about 94-98% of productive rate.
The 3rd step: hexaphenyl (methyl) six glycidyl ether basic rings six siloxanes synthetic
With the mol ratio of hexaphenyl (methyl) six silicon hydrogen ring six siloxanes and glycidyl allyl ether is 1: 2-5 joins in the exsiccant toluene (benzene), under the nitrogen protection condition, adds the Karstedt catalyzer of trace.Under 70-90 degree condition, reacted 15-30 hour.Remove excessive solvent and reactant through decompression.After the vacuum-drying, obtain thickness oily matter, productive rate 95-98%.
Reaction process can be as follows:
The preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization may further comprise the steps:
(1) hexaphenyl ring six sodium silanolates/nickel salt is synthetic
Under 0-10 ℃ of condition, be precursor with phenyl three n-butoxy silane, add sodium hydroxide and water then, the mol ratio of precursor and sodium hydroxide and water is 6: 8: 7; Place propyl carbinol again, refluxed 2 hours, after the cooling, disposable adding hexamine Nickel Chloride catalyzer; The mol ratio of precursor and hexamine Nickel Chloride catalyzer is 6: 5, continues to reflux stopped reaction 2 hours; Filter, revolve to steam and remove the part propyl carbinol, one night of coldcondition held; Obtain the yellowish-orange crystal settling, filter, promptly obtain hexaphenyl ring six sodium silanolates/nickel salt;
(2) hexaphenyl six hydrogen cyclosiloxane is synthetic
With mol ratio be 10: 12 with a dry pyridine and a hydrogen dimethylamino base chlorosilane; Join together in the exsiccant toluene solvant; Stirring at room 5 minutes, to wherein adding hexaphenyl ring six sodium silanolates/nickel salt, the mol ratio of a hydrogen dimethylamino base chlorosilane and hexaphenyl ring six sodium silanolates/nickel salt is 50: 1 again; Room temperature reaction 1 day, remove by filter deposition.Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove toluene and obtain transparent oily matter and promptly obtain hexaphenyl six hydrogen cyclosiloxane, the about 94-98% of productive rate.
(3) hexaphenyl six glycidyl ether basic rings six siloxanes is synthetic
With the mol ratio of hexaphenyl six hydrogen cyclosiloxane and glycidyl allyl ether is to join in exsiccant toluene at 1: 2, under the nitrogen protection condition, adds the Karstedt catalyzer; Under 70 ℃ of conditions; Reacted 30 hours, and removed excessive solvent and reactant through decompression, after the vacuum-drying; The thickness oily matter that obtains is product six epoxy group(ing) annular ten binary oligomeric silsesquioxanes, productive rate 95-98%.
The preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization may further comprise the steps:
(1) pregnancy basic ring six sodium silanolates/nickel salt is synthetic
Under 0-10 ℃ of condition, be precursor with methyl three n-butoxy silane, add sodium hydroxide and water then, the mol ratio of precursor and sodium hydroxide and water is 10: 11: 10; Place propyl carbinol again, refluxed 3 hours, after the cooling, disposable adding hexamine Nickel Chloride catalyzer; The mol ratio of precursor and hexamine Nickel Chloride catalyzer is 10: 5, continues backflow 2-3 hour, stopped reaction; Filter, revolve to steam and remove the part propyl carbinol, one night of coldcondition held; Obtain the yellowish-orange crystal settling, filter, promptly obtain pregnancy basic ring six sodium silanolates/nickel salt;
(2) hexamethyl six vinyl cyclosiloxane is synthetic
With mol ratio is that 200: 300 dry pyridines and vinyl-dimethyl base chlorosilane join in the exsiccant benzene solvent together; Stirring at room 20 minutes; Again to wherein adding pregnancy basic ring six sodium silanolates/nickel salt; The mol ratio of vinyl-dimethyl base chlorosilane and pregnancy basic ring six sodium silanolates/nickel salt is 100: 1, room temperature reaction 2 days, removes by filter deposition.Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove benzene and obtain transparent oily matter hexamethyl six vinyl cyclosiloxane, the about 94-98% of productive rate.
The preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization may further comprise the steps:
(1) hexaphenyl ring six sodium silanolates/nickel salt is synthetic
Phenyl-trichloro-silicane or METHYL TRICHLORO SILANE volume are dissolved in the toluene, and to wherein slowly dripping mixed solvent, this mixed solvent is that water and benzene are 4: 1 mixture by volume then; The volume ratio of phenyl-trichloro-silicane and mixed solvent is 1: 5, and violent stirring 10 hours is isolated organic layer; Washing is to neutral, utilize anhydrous magnesium sulfate drying after, filter and remove solvent wherein; Vacuum-drying obtains phenyl sesquisiloxane resin or methyl sesquisiloxane resin, is in molar ratio phenyl sesquisiloxane resin or methyl sesquisiloxane resin to be joined in the propyl carbinol with sodium hydroxide in 1: 2; Be back to mixture and change homogeneous phase into, be cooled to about 50 degree after, add sodium Metal 99.5; The mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and sodium Metal 99.5 is 1: 0.5, continues backflow 1-2 hour, last property adding hexamine Nickel Chloride; The mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and hexamine Nickel Chloride is 2: 0.5, refluxes then 2-3 hour, removes by filter salt; Revolve to steam and remove the part propyl carbinol, low temperature is placed a night, and yellow crystals is settled out; The suction filtration final vacuum is dry, obtains hexaphenyl ring six sodium silanolates/nickel salt.
(2) hexaphenyl chlordene propyl group cyclosiloxane is synthetic
With mol ratio is 10: 30 dry pyridines and chloropropyl dimethylchlorosilane; Join together in exsiccant toluene or the benzene solvent, stirring at room 20 minutes is chlorosilane to be mixed with hexaphenyl ring six sodium silanolates/nickel salt in 80: 1 more in molar ratio; Room temperature reaction 3 days, remove by filter deposition.Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove toluene or benzene obtains transparent oily matter hexaphenyl chlordene propyl group cyclosiloxane, the about 94-98% of productive rate.
The preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization may further comprise the steps:
(1) pregnancy basic ring six sodium silanolates/nickel salt is synthetic
The METHYL TRICHLORO SILANE equal-volume is dissolved in the benzene, and to wherein slowly dripping mixed solvent, this mixed solvent is that water and toluene are 4: 2 mixture by volume then; The volume ratio of phenyl-trichloro-silicane and mixed solvent is 1: 7, and violent stirring 10 hours is isolated organic layer; Washing is to neutral, utilize anhydrous magnesium sulfate drying after, filter and remove solvent wherein; Vacuum-drying obtains phenyl sesquisiloxane resin or methyl sesquisiloxane resin, is in molar ratio phenyl sesquisiloxane resin or methyl sesquisiloxane resin to be joined in the propyl carbinol with sodium hydroxide in 3: 4; Be back to mixture and change homogeneous phase into, be cooled to about 50 degree after, add sodium Metal 99.5; The mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and sodium Metal 99.5 is 3: 2, continues to reflux 2 hours, last property adding hexamine Nickel Chloride; The mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and hexamine Nickel Chloride is 4: 3, refluxes then 3 hours, removes by filter salt; Revolve to steam and remove the part propyl carbinol, low temperature is placed a night, and yellow crystals is settled out; Suction filtration and vacuum-drying obtain pregnancy basic ring six sodium silanolates/nickel salt.
(2) hexamethyl six hydrogen cyclosiloxane is synthetic
With mol ratio is that 20: 24 dry pyridines and a hydrogen dimethylamino base chlorosilane join in the exsiccant benzene solvent together; Stirring at room 10 minutes; Be a hydrogen dimethylamino base chlorosilane to be mixed with pregnancy basic ring six sodium silanolates/nickel salt in 100: 1 more in molar ratio,, remove by filter deposition room temperature reaction 3 days.Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove toluene or benzene obtains transparent oily matter hexamethyl six hydrogen cyclosiloxane, the about 94-98% of productive rate.
(3) hexamethyl six glycidyl ether basic rings six siloxanes is synthetic
With the mol ratio of hexamethyl six silicon hydrogen, six siloxanes and glycidyl allyl ether is to join in exsiccant toluene at 1: 5, under the nitrogen protection condition, adds the Karstedt catalyzer; Under 90 ℃ of conditions; Reacted 15 hours, and removed excessive solvent and reactant through decompression, after the vacuum-drying; The thickness oily matter that obtains is product six epoxy group(ing) annular ten binary oligomeric silsesquioxanes, productive rate 95-98%.
Respectively hexaphenyl six silicon hydrogen six siloxanes have been carried out hydrogen spectrum and levied with the silicon stave, hexaphenyl six glycidyl ether basic rings six siloxanes have carried out the hydrogen stave to be levied, and is the phenyl characteristic peak near chemical shift 7 among Fig. 1,0.2 neighbouring be the methyl characteristic peak; Two characteristic peaks appear in the silicon spectrogram of Fig. 2, respectively-81, and-5.1 and-5.4.-81 for encircling the characteristic peak of going up silicon, and-5.1 and-5.4 is the characteristic peak of side group silicon, and branch has taken place to split herein, explains that silicon hydrogen or siliconoxygen bond occurred conformation change.Fig. 3 is the hydrogen spectrum of hexaphenyl six glycidyl ether basic rings six siloxanes, explains to successfully synthesize this product.
Claims (8)
1. the preparation method of the big annular oligomeric silsesquioxanes of novel epoxy base functionalization is characterized in that, this method may further comprise the steps:
(1) hexaphenyl (methyl) ring six sodium silanolates/nickel salt is synthetic
Under 0-10 ℃ of condition, phenyl-trichloro-silicane is joined solvent; Solvent can be selected benzene or toluene; The deionized water that adds respective volume then, the phenyl silicone that obtains with the phenyl-trichloro-silicane hydrolysis, again with sodium hydroxide, water, propyl carbinol hybrid reaction after; Add the dichloro hexamine nickel, reaction obtains hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt;
(2) hexaphenyl (methyl) six hydrogen (vinyl, chloropropyl) cyclosiloxane is synthetic
Exsiccant toluene or benzene and pyridine or triethylamine mixing, add a hydrogen dimethylamino base chlorosilane or vinyl-dimethyl base chlorosilane or chloropropyl dimethylchlorosilane, stirred 5-10 minute; Add step (1) synthetic siloxy nickel salt, stirring at room 1-2 days, filter; Washing, anhydrous magnesium sulfate drying removes and desolvates; Obtain heavy-gravity oily product, be hexaphenyl (methyl) six hydrogen (vinyl, chloropropyl) cyclosiloxane.
(3) hexaphenyl (methyl) six glycidyl ether basic rings six siloxanes is synthetic
Select to use hexaphenyl six silicon hydrogen, six siloxanes or hexamethyl six silicon hydrogen six siloxanes to continue the synthetic of next step, the glycidyl ether with containing two keys carries out hydrosilylation addition reaction; Use toluene or benzene as solvent; Under the platinum catalyst effect, under the anhydrous and oxygen-free condition, 70-80 ℃ was reacted 15-25 hour; Remove excessive solvent and reactant, obtain product and contain annular ten binary oligomeric silsesquioxanes.
2. the preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization according to claim 1 is characterized in that step (1) specifically may further comprise the steps: with phenyl three n-butoxy silane or methyl three n-butoxy silane is precursor; Add sodium hydroxide and water then, the mol ratio of precursor and sodium hydroxide and water is 6-10: 8-11: 7-10, places propyl carbinol again; Backflow 2-3 hour, after the cooling, disposable adding hexamine Nickel Chloride catalyzer; The mol ratio of precursor and hexamine Nickel Chloride catalyzer is 6-10: 2-5, continues backflow 2-3 hour, stopped reaction; Filter, revolve to steam and remove the part propyl carbinol, in refrigerator, place a night; Obtain the yellowish-orange crystal settling, filter, promptly obtain hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt.
3. the preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization according to claim 1 is characterized in that step (1) can also adopt following steps: phenyl-trichloro-silicane or METHYL TRICHLORO SILANE equal-volume are dissolved in toluene or the benzene; Slowly be added drop-wise to then in the mixed solvent of water and toluene (benzene), violent stirring 10 hours is isolated organic layer; Washing is to neutral, utilize anhydrous magnesium sulfate drying after, filter and remove solvent wherein; Vacuum-drying obtains phenyl sesquisiloxane resin or methyl sesquisiloxane resin, for 1-3: 2-4 phenyl sesquisiloxane resin or methyl sesquisiloxane resin is joined in the propyl carbinol with sodium hydroxide in molar ratio; Be back to mixture and change homogeneous phase into, be cooled to about 50 degree after, add sodium Metal 99.5; The mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and sodium Metal 99.5 is 1-3: 0.5-2, continues backflow 1-2 hour, last property adding hexamine Nickel Chloride; The mol ratio of phenyl sesquisiloxane resin or methyl sesquisiloxane resin and hexamine Nickel Chloride is 2-4: 0.5-3, refluxes then 2-3 hour, removes by filter salt; Revolve to steam and remove the part propyl carbinol; Low temperature is placed a night, and yellow crystals is settled out, suction filtration and vacuum-drying.Obtain hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt.
4. the preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization according to claim 3 is characterized in that the volume ratio of described phenyl-trichloro-silicane or METHYL TRICHLORO SILANE and mixed solvent is 1: (5-7).
5. according to the preparation method of claim 3 or the big annular oligomeric silsesquioxanes of 4 described a kind of novel epoxy base functionalization, it is characterized in that described mixed solvent is that water and benzene or water and toluene are 4 by volume: mixture (1-2).
6. the preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization according to claim 1; It is characterized in that step (2) specifically may further comprise the steps: with mol ratio is 10-20: a 12-30 dry pyridine and a hydrogen dimethylamino base chlorosilane or vinyl-dimethyl base chlorosilane or chloropropyl dimethylchlorosilane join in exsiccant toluene or the benzene solvent together; Stirring at room 5-20 minute; Add hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt again, the mol ratio of above-mentioned chlorosilane and hexaphenyl ring six sodium silanolates/nickel salt or pregnancy basic ring six sodium silanolates/nickel salt is 50-100: 1, at room temperature reaction 1-3 days; Remove by filter deposition; Filtrate water is washed till neutrality, uses anhydrous magnesium sulfate drying, revolves to steam to remove toluene or benzene and obtain transparent oily matter and get final product.
7. the preparation method of the big annular oligomeric silsesquioxanes of a kind of novel epoxy base functionalization according to claim 1; It is characterized in that step (3) specifically may further comprise the steps: with the mol ratio of hexaphenyl six silicon hydrogen, six siloxanes or hexamethyl six silicon hydrogen, six siloxanes and glycidyl allyl ether is 1: 2-5 joins in exsiccant toluene or the benzene, under the nitrogen protection condition; Add the Karstedt catalyzer; Under 70-90 ℃ of condition, reacted 15-30 hour, remove excessive solvent and reactant; After the vacuum-drying, the thickness oily matter that obtains is product and contains annular ten binary oligomeric silsesquioxanes.
8. according to the preparation method of claim 1 or the big annular oligomeric silsesquioxanes of 7 described a kind of novel epoxy base functionalization; It is characterized in that described product is six epoxy group(ing) annular, ten binary oligomeric silsesquioxanes, contains six vinyl annular ten binary oligomeric silsesquioxanes or contain chlordene propyl group annular ten binary oligomeric silsesquioxanes.
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Cited By (5)
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| CN104610546A (en) * | 2013-11-04 | 2015-05-13 | 上海华明高技术（集团）有限公司 | Preparation method of annular reticular silicon resin |
| CN105294750A (en) * | 2015-11-11 | 2016-02-03 | 上海交通大学 | Synthetic method of hexamine phenyl large ring oligomerization silsesquioxane |
| CN109023225A (en) * | 2018-10-11 | 2018-12-18 | 含山县林头宝兴铸造厂 | A kind of corrosion-resistant lathe gear |
| CN114570422A (en) * | 2021-10-12 | 2022-06-03 | 浙江衢州硅宝化工有限公司 | Catalyst filler for producing ketoxime silane and preparation method thereof |
| CN117069945B (en) * | 2023-08-21 | 2024-06-07 | 广州白云科技股份有限公司 | Organic silicon resin toughening agent, single-component high-strength epoxy structural adhesive and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610546A (en) * | 2013-11-04 | 2015-05-13 | 上海华明高技术（集团）有限公司 | Preparation method of annular reticular silicon resin |
| CN105294750A (en) * | 2015-11-11 | 2016-02-03 | 上海交通大学 | Synthetic method of hexamine phenyl large ring oligomerization silsesquioxane |
| CN105294750B (en) * | 2015-11-11 | 2018-09-11 | 上海交通大学 | The synthetic method of hexamine phenyl macrocyclic oligomer silsesquioxane |
| CN109023225A (en) * | 2018-10-11 | 2018-12-18 | 含山县林头宝兴铸造厂 | A kind of corrosion-resistant lathe gear |
| CN114570422A (en) * | 2021-10-12 | 2022-06-03 | 浙江衢州硅宝化工有限公司 | Catalyst filler for producing ketoxime silane and preparation method thereof |
| CN114570422B (en) * | 2021-10-12 | 2024-03-29 | 浙江衢州硅宝化工有限公司 | Catalyst filler for producing ketoxime silane and preparation method thereof |
| CN117069945B (en) * | 2023-08-21 | 2024-06-07 | 广州白云科技股份有限公司 | Organic silicon resin toughening agent, single-component high-strength epoxy structural adhesive and preparation method thereof |
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