CN103214509A - Cubic eight-methacryloyloxy silsesquioxane crystal and preparation method thereof - Google Patents
Cubic eight-methacryloyloxy silsesquioxane crystal and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 claims abstract description 41
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 20
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 239000012456 homogeneous solution Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
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- 238000013019 agitation Methods 0.000 claims description 6
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims description 6
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 abstract 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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- Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of organic-inorganic nanometer hybrid materials, and relates to a preparation method of cubic eight methacryloyloxy silsesquioxane crystal. The preparation method of the cubic eight-methacryloyloxy silsesquioxane crystal comprises the following steps: (1) preparation of gamma-methacryloxypropyl trimethoxy silane hydrolyzate, including mixing gamma-methylacryloxypropyl trimethoxy silane, a polar solvent, and a catalyst A, stirring with magnetic, removing the solvent, washing to be neutral, dewatering, and filtering; (2) preparation of a recondensation product of a gamma-methacryloxypropyl trimethoxy silane hydrolyzate, including dissolving the product in step (1), adding a catalyst B dropwisely, reacting in the presence of nitrogen, washing to be neutral, drying, filtering, and removing toluene; and (3) preparation of cubic eight-methacryloyloxy silsesquioxane crystal, including adding nuclei to the product of the step (2), precipitating and separating crystals to get the cubic eight-methacryloyloxy silsesquioxane crystal.
Description
Technical field
The invention belongs to the technical field of organosilicon/inorganic nano-hybrid material, be specifically related to a kind of cube of type prestox acryloxy silsesquioxane crystallization and preparation method thereof.
Background technology
Silsesquioxane generally is a kind of mixture that is obtained through hydrolytic condensation by T type chlorosilane or siloxanes, contains different structure siloxanes oligopolymers such as line style, ladder type, cage modle, net type; It is the general name that a class has the silsesquioxane of similar lantern structure that cage-type silsesquioxane (POSS) is called polyhedral oligomeric silsesquioxane again.Cube type silsesquioxane is a kind of of cage-type silsesquioxane, and its compound with regular structure, symmetry highly are T
8Structure.In a broad sense, except complete cagelike structure silsesquioxane, also the portion of comprising separates the cagelike structure silsesquioxane.From POSS found that time, the synthetic interest that has just attracted the scientific research personnel of this height symmetrical structure compound.In the POSS synthetic primary stage, generally be to use T type chlorosilane, the synthetic simple POSS monomer of siloxanes; Now, mainly be on POSS precursor basis, to introduce the functional group, utilize this functional group further to react the formation target product.The synthetic method of POSS mainly contains direct hydrolysis method, functional group's derivatization method, summit block method.Form the method (application number: just introduce the synthetic method with preparation of several POSS 00813875.3) of polyhedral oligomeric silsesquioxane in people's such as the J.D of U.S. Hybrid Plastics Inc. patent.
Comparatively speaking, because T
8Therefore the synthetic comparative maturity of type POSS concentrates on T
8The applied research of type POSS is maximum.The important feature that POSS is applied to nano composite material is its chemically modified characteristic, and it can form covalently bound by active group and body material, also can be applied to hybridized nano composite material with physical blending, improves material property.
Prestox acryloyl-oxy silsesquioxane (MA-POSS) can obtain by gamma-methyl allyl acyloxypropyl trimethoxysilane (MA) hydrolytic condensation under catalyst action.Yet actually rare about MA hydrolysis report under alkaline condition, bibliographical information MA is arranged in aqueous ethanolic solution, with the Tetramethylammonium hydroxide catalyzer, hydrolytic condensation is prepared the oligomer mixture of molecular-weight average about 5900Da.Though, the article of research MA hydrolysis is many, but real report does not but have by synthetic stricti jurise on cube type MA-POSS of hydrolytic condensation method, though Hybrid Plastics company brings sale with these two kinds of POSS, it still is oligomer mixture that but analytical results shows institute's product sold, and how preparing pure MA-POSS still is a great problem in the research field.Have the preparation method who has introduced the methacryloxypropyl silsesquioxane in the cage-type silsesquioxane resinoid of functional group and the manufacture method (application number 03154435.5) thereof in the grand patent of Japanese Nippon Steel Chemical Co., Ltd vegetarian rattan, its product that obtains is that structure is uncertain.Even if the manufacture method that is disclosed with reference to Japanese patent laid-open 11-29640 communique, execution has silsesquioxane resins synthetic of methylpropenyl, also be difficult to fully carry out the control of molecular weight distribution structure, cause and to produce the clear and definite silsesquioxane resins of molecular configuration as cube type structure with good yield.And most of document about the MA-POSS preparation is not all really isolated a cube type prestox acryloxy silsesquioxane crystallization, and the crystalline of discovery document is arranged, and the crystallization required time is long mostly again, and reaction conditions and separation method are badly in need of improving.Therefore, be necessary further to carry out the research for preparing cage-type silsesquioxane by the hydrolytic condensation method, research cube type prestox acryloxy silsesquioxane crystalline preparation method is for a cube type prestox acryloxy silsesquioxane crystalline application provides prerequisite.At present obtain a cube type prestox acryloxy silsesquioxane crystallization and yet there are no report about method by hydrolytic condensation.
Summary of the invention
In order to overcome the shortcoming and defect of prior art and method, primary and foremost purpose of the present invention prepares cube type prestox acryloxy silsesquioxane crystallization (T of high yield (reaching 90%) by the method for gamma-methyl allyl acyloxypropyl trimethoxysilane (MA) hydrolytic condensation
8The MA-POSS of structure).
Another object of the present invention is to provide above-mentioned cube of type prestox acryloxy silsesquioxane crystalline preparation method.
The objective of the invention is to be achieved through the following technical solutions:
The crystallization of a kind of cube of type prestox acryloxy silsesquioxane is the symmetric hexahedron T of a kind of compound with regular structure height
8Structure, its structural formula is:
Above-mentioned cube of type prestox acryloxy silsesquioxane crystalline preparation method may further comprise the steps:
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: 25g gamma-methyl allyl acyloxypropyl trimethoxysilane and 100mL polar solvent are mixed, add the 10mL catalyst A, magnetic agitation, vacuum rotary steam removes and desolvates, with the toluene dissolving, be washed till neutrality, dewater, filter, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane;
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: the hydrolysate of getting the gamma-methyl allyl acyloxypropyl trimethoxysilane of 20g step (1), be dissolved in the lower boiling non-polar solvent of 100mL, Dropwise 5 mL catalyst B, under the nitrogen protection, it is transparent and homogeneous solution that 100～110 ℃ of magnetic agitation are back to solution, be warming up to 115～125 ℃, back flow reaction 8h, take out product, be washed till neutrality, drying is filtered, remove toluene and obtain water white thick liquid, be gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again;
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: adding quality again in the condensation product to gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate that step (2) obtains is that 0.01～0.05% octaphenyl silsesquioxane of total mass is as nucleus, 50 ℃ of crystallization control temperature, separate out crystal in the viscous fluid, isolation of crystalline promptly obtains a cube type prestox acryloxy silsesquioxane crystallization.
The described polar solvent of step (1) is ethanol, Virahol, tetrahydrofuran (THF); The temperature of described magnetic agitation is 50～60 ℃, and the time is 10h; Described catalyst A is an acidic catalyst or basic catalyst; Wherein said an acidic catalyst A is formic acid or hydrochloric acid; Described basic catalyst A is Tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide or tetramethyl-oxyammonia.An acidic catalyst A that is more preferably is that concentration is 10% hydrochloric acid; The basic catalyst A that is more preferably is that concentration is 10% the aqueous sodium hydroxide solution or 10% the tetramethyl-oxyammonia aqueous solution.
The temperature of described vacuum rotary steam is 60 ℃; The described neutrality that is washed till is to be washed to neutrality with saturated common salt; Described dewatering is to carry out drying with anhydrous magnesium sulfate to dewater.
Catalyst system, temperature, solvent, system pH are the key factors that influences the first step hydrolysis reaction.The catalyst system of siloxanes hydrolysis has acidic catalyst system and basic catalyst system.The difference of catalyst system, its hydrolytic process and effect are also different.The solvent of hydrolysis reaction is generally chosen polar solvent, as ethanol, Virahol, tetrahydrofuran (THF) etc.Temperature of reaction also is the key factor of control reaction.Temperature is low excessively, and speed of response will be very slow, and hydrolization group will exist with unreacted state, and temperature is too high, reacts too high, and then carries out complicated condensation reaction.Hydrolysate is washed to neutrality with saturated common salt after removing solvent, and drying and dehydrating also is the key that the control hydrolysis product can not continue cross-linking reaction.
Lower boiling non-polar solvent described in the step (2) is benzene, toluene or dimethylbenzene; Described catalyst B is an acidic catalyst B or basic catalyst B; Wherein, described an acidic catalyst B is that concentration is hydrochloric acid; Described basic catalyst B is aqueous sodium hydroxide solution or tetramethylammonium hydroxide aqueous solution.An acidic catalyst B that is more preferably is that concentration is 10% hydrochloric acid; The basic catalyst B that is more preferably is that concentration is 10～15% Tetramethylammonium hydroxide.
The described neutrality that is washed till is to be washed to neutrality with saturated common salt; Described drying is to carry out drying with anhydrous magnesium sulfate; The described toluene that removes is removed toluene with the method for 60 ℃ of vacuum rotary steams.
Gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate described in the step (3) quality of condensation product again is 18～18.4g; Described octaphenyl silsesquioxane quality is 0.00018～0.00093g; The purity of described octaphenyl silsesquioxane is 95%; The mode of described isolation of crystalline is suction filtration, and is centrifugal.
The present invention compared with prior art has following advantage:
(1) the present invention is in preparation cube type prestox acryloxy silsesquioxane crystalline two hydrolysis-condensation reactions, its reaction conditions bibliographical information before is gentle more, the choosing of catalytic reaction system determined after also having contrasted many different catalyst system catalytic effects, react more controlled, become the cage yield higher.
(2) utilization of the present invention's novelty when obtaining cube type prestox acryloxy silsesquioxane crystalline methods such as adding seed nucleus, Tc control realized T
8The crystallization of structure MA-POSS belongs to and obtains the clear and definite cube type prestox acryloxy silsesquioxane crystallization of structure first.
(3) the present invention also evaded in the general synthetic POSS experiment ambiguous, the uncertain deficiency of structure.Document about synthetic preparation MA-POSS is a lot, and what still most of document obtained all is the mixed system of one kind of multiple structures.The present invention successfully isolates a cube type prestox acryloxy silsesquioxane crystallization.
(4) of the present invention cube of type prestox acryloxy silsesquioxane crystalline preparation method, technology is comparatively simple, and selected raw material, reagent also all obtain than being easier to, the productive rate height of reaction.
Description of drawings
Fig. 1 (a) for the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate of embodiment 4 preparation again condensation product be the mass spectrum of water white transparency viscous liquid, Fig. 1 (b) is for separating out the mass spectrum of the upper strata viscous liquid after the crystallization among the embodiment 4;
Fig. 2 (a) is the DSC figure of the isolating crystalline that obtains cube type prestox acryloxy silsesquioxane among the effect embodiment 4, and Fig. 2 (b) is for isolating the DSC figure of viscous liquid after the crystallization among the effect embodiment 4.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: add 25g gamma-methyl allyl acyloxypropyl trimethoxysilane (MA) (Shanghai Aladdin reagent company limited) and the mixing of 100mL tetrahydrofuran (THF) in the there-necked flask, the 10%HCl that adds 10mL is as catalyzer, and there-necked flask stirs 10h as for 60 ℃ of lower magnetic forces.Take out the hydrolysis reaction mixing solutions, 60 ℃ of following vacuum rotary steam to tetrahydrofuran (THF)s are removed, with 150mL toluene dissolving hydrolysate, wash toluene solution until neutrality with saturated aqueous common salt solution, add the 15g anhydrous magnesium sulfate 0.5h that dewaters, filter out sal epsom, obtain the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate.
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: the hydrolysate that takes by weighing 20g step (1) preparation; be dissolved in the 100mL xylene solution; mixing solutions is moved in the 500mL there-necked flask; the 10%HCl of Dropwise 5 mL is a catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 110 ℃ of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, and rising temperature of reaction to 120 ℃ continues back flow reaction 8h.Take out condensation product, wash until neutrality with saturated aqueous common salt solution, add 15g anhydrous magnesium sulfate drying 0.5h, after filtering out anhydrous magnesium sulfate, 60 ℃ of backspins steam to be removed toluene solvant and obtains colorless transparent viscous liquid and be gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.0g again, productive rate 90%.
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: at 18g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again in the condensation product, octaphenyl-POSS (octaphenyl POSS quality be total mass 0.01%) (the Shanghai Aladdin reagent company limited that adds 0.00018g, purity 98.5%) as nucleus, 50 ℃ of crystallization control temperature have obtained T
8The MA-POSS crystallization of structure.Crystallization is separated out in the bottom enrichment, the transparent grain shape that is white in color, and a cube type prestox acryloxy silsesquioxane is after crystallization is separated out from highly viscous fluid, after not having crystallization to separate out, by suction filtration, the method for centrifugal (rotating speed 4000rpm, centrifugation time 30min) separation obtains crystalline T
8Structure MA-POSS.
With the T that obtains
8The MA-POSS crystal of structure by MALDI-TOF MS, DSC,
1H-NMR analysis and characterization, characterization result illustrative experiment successfully prepare and isolate a cube type prestox acryloxy silsesquioxane crystallization.
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: add 25gMA and 100mL alcohol mixed solution in the there-necked flask, add 10g deionized water and 1g sodium hydroxide, there-necked flask stirs 10h as for 60 ℃ of lower magnetic forces.Take out the hydrolysis reaction mixing solutions, 60 ℃ of following vacuum rotary steams desolvate to removing, with 150mL toluene dissolving hydrolysate.Until neutrality, add the 25g anhydrous magnesium sulfate 1h that dewaters with saturated aqueous common salt solution washing toluene solution, filter out sal epsom, obtain the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate.
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: take by weighing 20g hydrolysis head product; be dissolved in the 100mL benzole soln; mixing solutions is moved in the 500mL there-necked flask; Dropwise 5 mL15% tetramethylammonium hydroxide aqueous solution is a catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 110 ℃ of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, and rising temperature of reaction to 120 ℃ continues back flow reaction 8h.Take out condensation product, wash until neutrality with saturated aqueous common salt solution, add 25g anhydrous magnesium sulfate drying 1h, after filtering out anhydrous magnesium sulfate, 60 ℃ of backspins steam to be removed toluene solvant to obtain colorless transparent viscous liquid is gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.1g again, productive rate 90.5%.
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: at 18.1g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again in the condensation product, octaphenyl POSS (octaphenyl POSS quality be total mass 0.01%) (the Shanghai Aladdin reagent company limited that adds 0.000181g, purity 98.5%) as nucleus, 50 ℃ of crystallization control temperature have obtained T
8Structure MA-POSS crystallization.Crystallization is separated out in the bottom enrichment, the transparent grain shape that is white in color, a cube type prestox acryloxy silsesquioxane are after crystallization is separated out from highly viscous fluid, after not having crystallization to separate out, method separation by suction filtration, centrifugal (rotating speed 6000rpm, centrifugation time 20min) obtains crystalline T
8Structure MA-POSS.
With the T that obtains
8The MA-POSS crystal of structure by MALDI-TOF MS, DSC,
1H-NMR analysis and characterization, characterization result illustrative experiment successfully prepare and isolate a cube type prestox acryloxy silsesquioxane crystallization.
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: add 25gMA and 100mL alcohol mixed solution in the there-necked flask, add 10g deionized water and 1g sodium hydroxide, there-necked flask stirs 10h as for 55 ℃ of lower magnetic forces.Take out the hydrolysis reaction mixing solutions, 60 ℃ of following vacuum rotary steams desolvate to removing, with 150mL toluene dissolving hydrolysate.Until neutrality, add the 20g anhydrous magnesium sulfate 1h that dewaters with saturated aqueous common salt solution washing toluene solution, filter out sal epsom, obtain the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate.
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: take by weighing 20g hydrolysis head product; be dissolved in the 100mL toluene solution; mixing solutions is moved in the 500mL there-necked flask; Dropwise 5 mL15% tetramethylammonium hydroxide aqueous solution is a catalyzer, and there-necked flask loads additional units such as nitrogen protection, thermometer, water trap, prolong.110 ℃ of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, and rising temperature of reaction to 120 ℃ continues back flow reaction 8h.Take out condensation product, wash until neutrality with saturated aqueous common salt solution, add 20g anhydrous magnesium sulfate drying 1h, after filtering out anhydrous magnesium sulfate, 60 ℃ of backspins steam to be removed toluene solvant to obtain colorless transparent viscous liquid is gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.4g again, productive rate 92%.
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: at 18.4g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again in the condensation product, octaphenyl POSS (octaphenyl POSS quality be total mass 0.025%) (the Shanghai Aladdin reagent company limited that adds 0.00046g, purity 98.5%) as nucleus, 50 ℃ of crystallization control temperature have obtained T
8Structure MA-POSS crystallization.Crystallization is separated out in the bottom enrichment, the transparent grain shape that is white in color is at a cube type prestox acryloxy silsesquioxane after crystallization is separated out from highly viscous fluid, after not having crystallization to separate out, method separation by suction filtration, centrifugal (rotating speed 5000rpm, centrifugation time 25min) obtains crystalline T
8Structure MA-POSS.
With the T that obtains
8The MA-POSS crystal of structure by MALDI-TOF MS, DSC,
1H-NMR analysis and characterization, characterization result illustrative experiment successfully prepare and isolate a cube type prestox acryloxy silsesquioxane crystallization.
Embodiment 4
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: add 25gMA and 100mL isopropyl alcohol mixture in the there-necked flask, add 10g deionized water and 1g Tetramethylammonium hydroxide, there-necked flask stirs 10h as for 50 ℃ of lower magnetic forces.Take out the hydrolysis reaction mixing solutions, 50 ℃ of following vacuum rotary steam to solvents are removed, with 150mL toluene dissolving hydrolysate., add the 20g anhydrous magnesium sulfate and dewater until neutrality with saturated aqueous common salt solution washing toluene solution, filter out sal epsom, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane.
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: take by weighing the 20g hydrolysate; be dissolved in the 100mL toluene solution; mixing solutions is moved in the 500mL there-necked flask; Dropwise 5 mL15% Tetramethylammonium hydroxide is a catalyzer, and there-necked flask loads additional units such as nitrogen protection, thermometer, water trap, prolong.110 ℃ of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, and rising temperature of reaction to 120 ℃ continues back flow reaction 8h.Take out condensation product, wash until neutrality with saturated aqueous common salt solution, add 20g anhydrous magnesium sulfate drying 0.5h, after filtering out anhydrous magnesium sulfate, 60 ℃ of backspins steam to be removed toluene solvant to obtain colorless transparent viscous liquid is gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.5g again, productive rate 92.5%.
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: at 18.4g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again in the condensation product, octaphenyl POSS (octaphenyl POSS quality be total mass 0.025%) (the Shanghai Aladdin reagent company limited that adds 0.00046g, purity 98.5%) as nucleus, the method that the crystallization control temperature is 50 ℃ has obtained the MA-POSS crystallization.Crystallization is separated out in the bottom enrichment, the transparent grain shape that is white in color is not after having crystallization to separate out, at a cube type prestox acryloxy silsesquioxane after crystallization is separated out from highly viscous fluid, method separation by suction filtration, centrifugal (rotating speed 4000rpm, centrifugation time 30min) obtains crystalline T
8Structure MA-POSS.Can analyze by MS and confirm that cube type prestox acryloxy silsesquioxane crystalline generates.As accompanying drawing 1,1 (a) is the mass spectrum of the colorless transparent viscous liquid of embodiment 4 steps (2) preparations, 1455, (1746,1814), (2105,2173) are respectively T
8, T
10, T
12The molecule peak of MA-POSS; 1 (b) is for separating out the mass spectrum of upper strata viscous liquid after the crystallization in embodiment four steps (3), and (1746,1814,1831), (2105,2173) are respectively T
10, T
12The molecule peak of MA-POSS, the disappearance at 1455 molecule peaks shows T
8Type MA-POSS separates out with the crystalline form.
Crystalline separates and can be analyzed by DSC.See the DSC figure of accompanying drawing 2,2 (a), visible T for the isolating cube type prestox acryloxy silsesquioxane that obtains in embodiment four steps (3)
8Type MA-POSS crystallization melting peak is sharp-pointed, and melting enthalpy is big, shows that its purity is higher; 2 (b) are for isolating the DSC figure of upper strata viscous liquid after the crystallization, its no crystallization fusion absorption peak in embodiment four steps (3).
Embodiment 5
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: add 25gMA and 100mL isopropyl alcohol mixture in the there-necked flask, add 10g deionized water and 1g Tetramethylammonium hydroxide, there-necked flask stirs 10h as for 50 ℃ of lower magnetic forces.Take out the hydrolysis reaction mixing solutions, 50 ℃ of following vacuum rotary steams remove and desolvate, with 150mL toluene dissolving hydrolysate.Until neutrality, add the 15g anhydrous magnesium sulfate 2h that dewaters with saturated aqueous common salt solution washing toluene solution, filter out sal epsom, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane.
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: take by weighing the 20g hydrolysate; be dissolved in the 100mL toluene solution; mixing solutions is moved in the 500mL there-necked flask; Dropwise 5 mL12.5% tetramethylammonium hydroxide aqueous solution is a catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 105 ℃ of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, and rising temperature of reaction to 125 ℃ continues back flow reaction 8h.Take out condensation product, wash until neutrality with saturated aqueous common salt solution, add 15g anhydrous magnesium sulfate drying 2h, after filtering out anhydrous magnesium sulfate, 60 ℃ of backspins steam to be removed toluene solvant to obtain colorless transparent viscous liquid is gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.3g again, productive rate 91.5%.
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: at 18.3g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again in the condensation product, octaphenyl POSS (octaphenyl POSS quality be total mass 0.05%) (the Shanghai Aladdin reagent company limited that adds 0.00093g, purity 98.5%) as nucleus, the method that the crystallization control temperature is 50 ℃ has obtained T
8Structure MA-POSS crystallization.Crystallization is separated out in the bottom enrichment, the transparent grain shape that is white in color, a cube type prestox acryloxy silsesquioxane are after crystallization is separated out from highly viscous fluid, after not having crystallization to separate out, method separation by suction filtration, centrifugal (rotating speed 4000rpm, centrifugation time 30min) obtains crystalline T
8Structure MA-POSS.
With the T that obtains
8The MA-POSS crystal of structure by MALDI-TOF MS, DSC,
1H-NMR analysis and characterization, characterization result illustrative experiment successfully prepare and isolate a cube type prestox acryloxy silsesquioxane crystallization.
Embodiment 6
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: add 25gMA and 100mL isopropyl alcohol mixture in the there-necked flask, add 10g deionized water and 1g Tetramethylammonium hydroxide, there-necked flask stirs 10h as for 50 ℃ of lower magnetic forces.Take out the hydrolysis reaction mixing solutions, 50 ℃ of following vacuum rotary steams remove and desolvate, with 150mL toluene dissolving hydrolysate.Until neutrality, add the 15g anhydrous magnesium sulfate 0.5h that dewaters with saturated aqueous common salt solution washing toluene solution, filter out sal epsom, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane.
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: take by weighing 20g hydrolysis head product; be dissolved in the 100mL toluene solution; mixing solutions is moved in the 500mL there-necked flask; Dropwise 5 mL10% tetramethylammonium hydroxide aqueous solution is a catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 100 ℃ of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, and rising temperature of reaction to 115 ℃ continues back flow reaction 8h.Take out condensation product, wash until neutrality with saturated aqueous common salt solution, add 15g anhydrous magnesium sulfate drying 0.5h, after filtering out anhydrous magnesium sulfate, 60 ℃ of backspins steam to be removed toluene solvant to obtain colorless transparent viscous liquid is gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.2g again, productive rate 91%.
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: at 18.2g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again in the condensation product, octaphenyl POSS (octaphenyl POSS quality be total mass 0.05%) (the Shanghai Aladdin reagent company limited that adds 0.00091g, purity 98.5%) as nucleus, the method that the crystallization control temperature is 50 ℃ has obtained T
8Structure MA-POSS crystallization.Crystallization is separated out in the bottom enrichment, the transparent grain shape that is white in color, a cube type prestox acryloxy silsesquioxane are after crystallization is separated out from highly viscous fluid, after not having crystallization to separate out, method separation by suction filtration, centrifugal (rotating speed 4000rpm, centrifugation time 30min) obtains crystalline T
8Structure MA-POSS.
With the T that obtains
8The MA-POSS crystal of structure by MALDI-TOF MS, DSC,
1H-NMR analysis and characterization, characterization result illustrative experiment successfully prepare and isolate a cube type prestox acryloxy silsesquioxane crystallization.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. one kind of cube of type prestox acryloxy silsesquioxane crystallization, it is characterized in that: its structural formula is:
2. a kind of cube of type prestox acryloxy silsesquioxane crystalline preparation method according to claim 1 is characterized in that: may further comprise the steps:
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: 25g gamma-methyl allyl acyloxypropyl trimethoxysilane and polar solvent are mixed, add the 10mL catalyst A, magnetic agitation, vacuum rotary steam to polarity solvent is removed, with the toluene dissolving, be washed till neutrality, dewater, filter, obtain the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate;
(2) the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate preparation of condensation product again: the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate of getting 20g step (1), be dissolved in the lower boiling non-polar solvent, Dropwise 5 mL catalyst B, under the nitrogen protection, it is transparent and homogeneous solution that 100～110 ℃ of magnetic agitation are back to solution, be warming up to 115～125 ℃, back flow reaction 8h, take out product, be washed till neutrality, drying, filter, remove lower boiling non-polar solvent, obtain water white thick liquid, be gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again;
(3) cube type prestox acryloxy silsesquioxane crystalline preparation: adding quality again in the condensation product to gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate that step (2) obtains is that 0.01～0.05% octaphenyl silsesquioxane of total mass is as nucleus, 50 ℃ of crystallization control temperature, separate out crystal in the viscous fluid, isolation of crystalline promptly obtains a cube type prestox acryloxy silsesquioxane crystallization.
3. preparation method according to claim 2 is characterized in that: the described polar solvent of step (1) is ethanol, Virahol, tetrahydrofuran (THF); Described catalyst A is an acidic catalyst A or basic catalyst A; The temperature of described magnetic agitation is 50～60 ℃, and the time is 10h; The temperature of described vacuum rotary steam is 60 ℃; The described neutrality that is washed till is to be washed to neutrality with saturated common salt; Described dewatering is to dewater with anhydrous magnesium sulfate.
4. preparation method according to claim 2 is characterized in that: the lower boiling non-polar solvent described in the step (2) is benzene, toluene or dimethylbenzene; Described catalyst B is an acidic catalyst B or basic catalyst B; The described neutrality that is washed till is to be washed to neutrality with saturated common salt; Described drying is to use anhydrous magnesium sulfate drying; The described toluene that removes is removed toluene with the method for 60 ℃ of vacuum rotary steams.
5. preparation method according to claim 2 is characterized in that: the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate described in the step (3) quality of condensation product again is 18～18.4g; Described octaphenyl silsesquioxane quality is 0.00018～0.00093g; The purity of described octaphenyl silsesquioxane is 95%; The mode of described isolation of crystalline is suction filtration, and is centrifugal.
6. preparation method according to claim 3 is characterized in that: described an acidic catalyst A is formic acid or hydrochloric acid; Described basic catalyst A is Tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide or tetramethyl-oxyammonia; The consumption that described anhydrous magnesium sulfate dewaters is 15～25g, and the time is 0.5～2h.
7. preparation method according to claim 4 is characterized in that: described an acidic catalyst B is a hydrochloric acid; Described basic catalyst B is aqueous sodium hydroxide solution or tetramethylammonium hydroxide aqueous solution; The consumption of described anhydrous magnesium sulfate drying is 15～25g, and the time is 0.5～2h.
8. preparation method according to claim 5 is characterized in that: described centrifugal rotation speed is 4000rpm, and the time is 30min.
9. preparation method according to claim 6 is characterized in that: described an acidic catalyst A is that concentration is 10% hydrochloric acid; Described basic catalyst A is that concentration is 10% the aqueous sodium hydroxide solution or 10% the tetramethyl-oxyammonia aqueous solution.
10. according to the described preparation method of claim 7, it is characterized in that: described an acidic catalyst B is that concentration is 10% hydrochloric acid; Described basic catalyst B is that concentration is 10～15% tetramethylammonium hydroxide aqueous solution.
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| PCT/CN2014/073921 WO2014154116A1 (en) | 2013-03-25 | 2014-03-24 | Cubic octamethyl acryloyloxy silsesquioxane crystal and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014154116A1 (en) * | 2013-03-25 | 2014-10-02 | 中科院广州化学有限公司 | Cubic octamethyl acryloyloxy silsesquioxane crystal and preparation method thereof |
| CN104226275A (en) * | 2014-08-21 | 2014-12-24 | 中科院广州化学有限公司 | Hollow microsphere based on methacrylic acyloxy cage-like silsesquioxane and preparation method and application thereof |
| CN107082882A (en) * | 2017-05-27 | 2017-08-22 | 安徽硅宝有机硅新材料有限公司 | A kind of preparation method of methacryloxypropyl silane polymer |
| CN109053795A (en) * | 2018-08-15 | 2018-12-21 | 哈尔滨工业大学 | A kind of preparation method of more methacryloxy sesquialter silane |
| CN109776802A (en) * | 2019-01-11 | 2019-05-21 | 广州艾科普新材料有限公司 | A kind of preparation method of methacryloxypropyl tri-alkoxy polysilsesquioxane |
| CN110483780A (en) * | 2019-08-23 | 2019-11-22 | 哈尔滨工业大学 | A kind of process for separation and purification of the polyhedral oligomeric silsesquioxane containing methacryloxy |
| CN113773499A (en) * | 2021-09-29 | 2021-12-10 | 安徽硅宝有机硅新材料有限公司 | Functional silane macromolecular polymer, preparation method, additive and application |
| CN115275520A (en) * | 2022-08-29 | 2022-11-01 | 江苏欧力特能源科技有限公司 | Composite diaphragm for lithium battery and preparation method thereof |
| CN116063981A (en) * | 2022-12-29 | 2023-05-05 | 中科院广州化学有限公司 | High-temperature-resistant anaerobic adhesive with functional cage-type silsesquioxane structure, and preparation method and application thereof |
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| WO2014154116A1 (en) * | 2013-03-25 | 2014-10-02 | 中科院广州化学有限公司 | Cubic octamethyl acryloyloxy silsesquioxane crystal and preparation method thereof |
| CN104226275A (en) * | 2014-08-21 | 2014-12-24 | 中科院广州化学有限公司 | Hollow microsphere based on methacrylic acyloxy cage-like silsesquioxane and preparation method and application thereof |
| CN104226275B (en) * | 2014-08-21 | 2016-08-24 | 中科院广州化学有限公司 | Hollow microsphere based on methacryloxy cage-type silsesquioxane and its preparation method and application |
| CN107082882A (en) * | 2017-05-27 | 2017-08-22 | 安徽硅宝有机硅新材料有限公司 | A kind of preparation method of methacryloxypropyl silane polymer |
| CN109053795A (en) * | 2018-08-15 | 2018-12-21 | 哈尔滨工业大学 | A kind of preparation method of more methacryloxy sesquialter silane |
| CN109776802A (en) * | 2019-01-11 | 2019-05-21 | 广州艾科普新材料有限公司 | A kind of preparation method of methacryloxypropyl tri-alkoxy polysilsesquioxane |
| CN109776802B (en) * | 2019-01-11 | 2022-01-14 | 广州艾科普新材料有限公司 | Preparation method of methacryloxypropyl trialkoxy polysilsesquioxane |
| CN110483780A (en) * | 2019-08-23 | 2019-11-22 | 哈尔滨工业大学 | A kind of process for separation and purification of the polyhedral oligomeric silsesquioxane containing methacryloxy |
| CN113773499A (en) * | 2021-09-29 | 2021-12-10 | 安徽硅宝有机硅新材料有限公司 | Functional silane macromolecular polymer, preparation method, additive and application |
| CN115275520A (en) * | 2022-08-29 | 2022-11-01 | 江苏欧力特能源科技有限公司 | Composite diaphragm for lithium battery and preparation method thereof |
| CN115275520B (en) * | 2022-08-29 | 2023-07-07 | 江苏欧力特能源科技有限公司 | Composite diaphragm for lithium battery and preparation method thereof |
| CN116063981A (en) * | 2022-12-29 | 2023-05-05 | 中科院广州化学有限公司 | High-temperature-resistant anaerobic adhesive with functional cage-type silsesquioxane structure, and preparation method and application thereof |
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