CN103214509B - Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal and preparation method thereof - Google Patents
Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal and preparation method thereof Download PDFInfo
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000413 hydrolysate Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 41
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 36
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 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
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- -1 siloxanes Chemical class 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 12
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- 238000003756 stirring Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 10
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- 238000005119 centrifugation Methods 0.000 description 6
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention belongs to the technical field of organosilicon/inorganic nano-hybrid material, relate to a kind of preparation method of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.The preparation method of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal, comprise the following steps: the preparation of the hydrolysate of (1) gamma-methyl allyl acyloxypropyl trimethoxysilane: by gamma-methyl allyl acyloxypropyl trimethoxysilane, polar solvent, catalyst A mixing, magnetic agitation, except desolventizing, be washed till neutrality, dewater, filter; (2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: dissolved by the product of step (1), drips catalyst B, and nitrogen protection is reacted, and is washed till neutrality, dry, filters, except toluene; (3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: add nucleus in step (2) product, separate out, isolation of crystalline, obtains Cubic eight-methacryloyloxsilsesquioxane 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 Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal and preparation method thereof.
Background technology
Silsesquioxane is generally a kind of mixture obtained through hydrolytic condensation by T-shaped chlorosilane or siloxanes, containing different structure siloxane oligomers 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 also called polyhedral oligomeric silsesquioxane.Cubic silsesquioxane is the one of cage-type silsesquioxane, and its compound with regular structure, high degree of symmetry are T
8structure.In a broad sense, except complete cagelike structure silsesquioxane, also the portion of comprising separates cagelike structure silsesquioxane.From that time that POSS is found, the synthesis of this high degree of symmetry structural compounds has just attracted the interest of scientific research personnel.In the primary stage of POSS synthesis, be generally use T-shaped chlorosilane, siloxanes to synthesize simple POSS monomer; Now, mainly on POSS precursor basis, introduce functional group, utilize this functional group to react formation target product further.The synthetic method of POSS mainly contains direct hydrolysis method, functional group's derivatization method, summit block method.Method (the application number: the method just introducing several POSS synthesis and preparation 00813875.3) of polyhedral oligomeric silsesquioxane is formed in the patent of the people such as Hybrid Plastics Inc. of U.S. J.D.
Comparatively speaking, due to T
8the synthesis comparative maturity of type POSS, therefore 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 be formed covalently bound by active group and body material, also with physical blending, can be applied to hybridized nano composite material, improves material property.
Prestox acryloyl-oxy silsesquioxane (MA-POSS) can be obtained by gamma-methyl allyl acyloxypropyl trimethoxysilane (MA) hydrolytic condensation under catalyst action.But it is actually rare to be hydrolyzed report in the basic conditions about MA, having bibliographical information MA in aqueous ethanolic solution, take Tetramethylammonium hydroxide as catalyzer, and hydrolytic condensation prepares the oligomer mixture of molecular-weight average at about 5900Da.Although, the article of research MA hydrolysis is many, but real report is not but had by Cubic MA-POSS on hydrolytic condensation method synthesis stricti jurise, although these two kinds of POSS are brought sale by HybridPlastics company, but analytical results shows that institute's product sold is still oligomer mixture, how preparing pure MA-POSS is still a great problem in research field.Have the preparation method describing methacryloxypropyl silsesquioxane in the part of polyhedral oligomeric silsesquioxane resin of functional group and manufacture method (application number 03154435.5) thereof in the patent that nippon KCC vegetarian rattan is grand, its product obtained is that structure is uncertain.Even if with reference to the manufacture method that Japanese Patent Laid-Open 11-29640 publication discloses, implement the synthesis with the silsesquioxane resins of methylpropenyl, also be difficult to fully carry out the control of molecular weight distribution structure, cause to produce the clear and definite silsesquioxane resins of molecular configuration as constructed in Cubic with good yield.And the document that major part is prepared about MA-POSS does not all really isolate Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal, crystallization required time is long mostly again for the document being found crystallization, and reaction conditions and separation method are badly in need of improving.Therefore, be necessary to carry out the research being prepared cage-type silsesquioxane by hydrolytic condensation method further, the preparation method of research Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal, for the application of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal provides prerequisite.Obtain Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal about the method by hydrolytic condensation at present have not been reported.
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 the Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal (T of high yield pulp1 (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 the preparation method that above-mentioned Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal is provided.
The object of the invention is to be achieved through the following technical solutions:
A kind of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal is a kind of hexahedron T of compound with regular structure high degree of symmetry
8structure, its structural formula is:
The preparation method of above-mentioned Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal, comprises the following steps:
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: by 25g gamma-methyl allyl acyloxypropyl trimethoxysilane and the mixing of 100mL polar solvent, add 10mL catalyst A, magnetic agitation, vacuum rotary steam is except desolventizing, dissolve with toluene, be washed till neutrality, dewater, filter, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane;
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: the hydrolysate getting the gamma-methyl allyl acyloxypropyl trimethoxysilane of 20g step (1), be dissolved in the lower boiling non-polar solvent of 100mL, drip 5mL catalyst B, under nitrogen protection, it is transparent and homogeneous solution that 100 ~ 110 DEG C of magnetic agitation are back to solution, be warming up to 115 ~ 125 DEG C, back flow reaction 8h, take out product, be washed till neutrality, dry, filter, except toluene obtains water white thick liquid, be gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again,
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: it is that the octaphenyl silsesquioxane of 0.01 ~ 0.05% of total mass is as nucleus that the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate obtained to step (2) adds quality in condensation product again, crystallization control temperature 50 C, crystallize out in viscous fluid, isolation of crystalline, namely obtains Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
Polar solvent described in step (1) is ethanol, Virahol, tetrahydrofuran (THF); The temperature of described magnetic agitation is 50 ~ 60 DEG C, 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 be more preferably to be concentration be 10% hydrochloric acid; The basic catalyst A be more preferably is concentration is the aqueous sodium hydroxide solution of 10% or the tetramethyl-aqueous ammonium hydroxide of 10%.
The temperature of described vacuum rotary steam is 60 DEG C; The described neutrality that is washed till is washed to neutrality with saturated common salt; Described dewatering carries out drying with anhydrous magnesium sulfate to dewater.
Catalyst system, temperature, solvent, system pH are the key factors affecting 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 generally chooses polar solvent, as ethanol, Virahol, tetrahydrofuran (THF) etc.Temperature of reaction is also the key factor controlling reaction.Temperature is too low, 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.After hydrolysate removes solvent, being washed to neutrality with saturated common salt, drying and dehydrating, is also the key that controlled hydrolysis product can not continue cross-linking reaction.
Lower boiling non-polar solvent described in 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 concentration is hydrochloric acid; Described basic catalyst B is aqueous sodium hydroxide solution or tetramethylammonium hydroxide aqueous solution.An acidic catalyst B be more preferably to be concentration be 10% hydrochloric acid; The basic catalyst B be more preferably to be concentration be 10 ~ 15% Tetramethylammonium hydroxide.
The described neutrality that is washed till is washed to neutrality with saturated common salt; Described drying carries out drying with anhydrous magnesium sulfate; The described method removing toluene removing toluene 60 DEG C of vacuum rotary steams.
The quality of the condensation product again of the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate described in step (3) 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, centrifugal.
Compared with prior art, tool has the following advantages in the present invention:
(1) the present invention is in two hydrolysis-condensation reactions of preparation Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal, its reaction conditions comparatively before bibliographical information gentleer, determine after the choosing of catalytic reaction system also compared for many different catalyst system catalytic effects, react more controlled, become cage yield higher.
(2) the present invention's make use of of novelty when obtaining Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal adds the method such as seed crystal nuclei, Tc control and achieves T
8the crystallization of structure MA-POSS, belongs to and obtains the clear and definite Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal of structure first.
(3) the present invention also evaded general synthesis POSS test in ambiguous, structure uncertain deficiency.Document about synthesis preparation MA-POSS is a lot, but most of document obtains is all the mixed system of one kind of multiple structures.The present invention successfully isolates Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
(4) preparation method of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal of the present invention, technique is comparatively simple, selected raw material, and reagent also all obtains than being easier to, and the productive rate of reaction is high.
Accompanying drawing explanation
The mass spectrum of the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate that Fig. 1 (a) is prepared for embodiment 4 condensation product and water white transparency viscous liquid again, Fig. 1 (b) is the mass spectrum of the upper strata viscous liquid after crystallization in embodiment 4;
Fig. 2 (a) is that the DSC figure of the Cubic prestox acryloxy silsesquioxane of the crystallization obtained be separated in effect example 4, Fig. 2 (b) are for isolating the DSC figure of viscous liquid after crystallization in effect example 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 there-necked flask, add the 10%HCl of 10mL as catalyzer, there-necked flask stirs 10h as 60 DEG C of lower magnetic forces.Take out hydrolysis reaction mixing solutions, at 60 DEG C, vacuum rotary steam removes to tetrahydrofuran (THF), with 150mL toluene dissolved water hydrolysis products, with saturated aqueous common salt solution washing toluene solution until neutrality, add 15g anhydrous magnesium sulfate to dewater 0.5h, filter out magnesium sulfate, obtain gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate.
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: take hydrolysate prepared by 20g step (1); be dissolved in 100mL xylene solution; mixing solutions is moved in 500mL there-necked flask; the 10%HCl dripping 5mL is catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 110 DEG C of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, raise temperature of reaction to 120 DEG C, continue back flow reaction 8h.Take out condensation product, with the washing of saturated aqueous common salt solution until neutral, add 15g anhydrous magnesium sulfate drying 0.5h, after filtering out anhydrous magnesium sulfate, 60 DEG C of backspin steaming removing toluene solvants obtain colorless transparent viscous liquid and are gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.0g again, productive rate 90%.
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: in 18g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again condensation product, add octaphenyl-POSS (octaphenyl POSS quality is 0.01% of total mass) (the Shanghai Aladdin reagent company limited of 0.00018g, purity 98.5%) as nucleus, crystallization control temperature 50 C, obtains T
8the MA-POSS crystallization of structure.Crystallization is in bottom enrichment, and in white clear particulate state, Cubic prestox acryloxy silsesquioxane is from highly viscous fluid after crystallization, after there is no crystallization, by suction filtration, the method for centrifugal (rotating speed 4000rpm, centrifugation time 30min) is separated the T obtaining crystallization
8structure MA-POSS.
By the T obtained
8the MA-POSS crystal of structure by MALDI-TOFMS, DSC,
1h-NMR analysis and characterization, characterization result illustrative experiment is successfully prepared and is isolated Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
Embodiment 2
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: add 25gMA and 100mL alcohol mixed solution in there-necked flask, adds 10g deionized water and 1g sodium hydroxide, and there-necked flask stirs 10h as 60 DEG C of lower magnetic forces.Take out hydrolysis reaction mixing solutions, at 60 DEG C, vacuum rotary steam is to except desolventizing, with 150mL toluene dissolved water hydrolysis products.With saturated aqueous common salt solution washing toluene solution until neutrality, add 25g anhydrous magnesium sulfate and to dewater 1h, filter out magnesium sulfate, obtain gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate.
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: take 20g and be hydrolyzed head product; be dissolved in 100mL benzole soln; mixing solutions is moved in 500mL there-necked flask; dripping 5mL15% tetramethylammonium hydroxide aqueous solution is catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 110 DEG C of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, raise temperature of reaction to 120 DEG C, continue back flow reaction 8h.Take out condensation product, with the washing of saturated aqueous common salt solution until neutral, add 25g anhydrous magnesium sulfate drying 1h, after filtering out anhydrous magnesium sulfate, 60 DEG C of backspins steam removing toluene solvant and obtain colorless transparent viscous liquid and gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.1g again, productive rate 90.5%.
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: in 18.1g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again condensation product, add octaphenyl POSS (octaphenyl POSS quality is 0.01% of total mass) (the Shanghai Aladdin reagent company limited of 0.000181g, purity 98.5%) as nucleus, crystallization control temperature 50 C, obtains T
8structure MA-POSS crystallization.Crystallization is in bottom enrichment, in white clear particulate state, Cubic prestox acryloxy silsesquioxane from highly viscous fluid after crystallization, after there is no crystallization, the T obtaining crystallization is separated by the method for suction filtration, centrifugal (rotating speed 6000rpm, centrifugation time 20min)
8structure MA-POSS.
By the T obtained
8the MA-POSS crystal of structure by MALDI-TOFMS, DSC,
1h-NMR analysis and characterization, characterization result illustrative experiment is successfully prepared and is isolated Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
Embodiment 3
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: add 25gMA and 100mL alcohol mixed solution in there-necked flask, adds 10g deionized water and 1g sodium hydroxide, and there-necked flask stirs 10h as 55 DEG C of lower magnetic forces.Take out hydrolysis reaction mixing solutions, at 60 DEG C, vacuum rotary steam is to except desolventizing, with 150mL toluene dissolved water hydrolysis products.With saturated aqueous common salt solution washing toluene solution until neutrality, add 20g anhydrous magnesium sulfate and to dewater 1h, filter out magnesium sulfate, obtain gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate.
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: take 20g and be hydrolyzed head product; be dissolved in 100mL toluene solution; mixing solutions is moved in 500mL there-necked flask; dripping 5mL15% tetramethylammonium hydroxide aqueous solution is catalyzer, and there-necked flask loads the additional units such as nitrogen protection, thermometer, water trap, prolong.110 DEG C of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, raise temperature of reaction to 120 DEG C, continue back flow reaction 8h.Take out condensation product, with the washing of saturated aqueous common salt solution until neutral, add 20g anhydrous magnesium sulfate drying 1h, after filtering out anhydrous magnesium sulfate, 60 DEG C of backspins steam removing toluene solvant and obtain colorless transparent viscous liquid and gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.4g again, productive rate 92%.
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: in 18.4g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again condensation product, add octaphenyl POSS (octaphenyl POSS quality is 0.025% of total mass) (the Shanghai Aladdin reagent company limited of 0.00046g, purity 98.5%) as nucleus, crystallization control temperature 50 C, obtains T
8structure MA-POSS crystallization.Crystallization is in bottom enrichment, in white clear particulate state, at Cubic prestox acryloxy silsesquioxane from highly viscous fluid after crystallization, after there is no crystallization, the T obtaining crystallization is separated by the method for suction filtration, centrifugal (rotating speed 5000rpm, centrifugation time 25min)
8structure MA-POSS.
By the T obtained
8the MA-POSS crystal of structure by MALDI-TOFMS, DSC,
1h-NMR analysis and characterization, characterization result illustrative experiment is successfully prepared and is isolated Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
Embodiment 4
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: add 25gMA and 100mL isopropyl alcohol mixture in there-necked flask, add 10g deionized water and 1g Tetramethylammonium hydroxide, there-necked flask stirs 10h as 50 DEG C of lower magnetic forces.Take out hydrolysis reaction mixing solutions, at 50 DEG C, vacuum rotary steam removes to solvent, with 150mL toluene dissolved water hydrolysis products.With saturated aqueous common salt solution washing toluene solution until neutrality, add 20g anhydrous magnesium sulfate and dewater, filter out magnesium sulfate, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane.
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: take 20g hydrolysate; be dissolved in 100mL toluene solution; mixing solutions is moved in 500mL there-necked flask; dripping 5mL15% Tetramethylammonium hydroxide is catalyzer, and there-necked flask loads the additional units such as nitrogen protection, thermometer, water trap, prolong.110 DEG C of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, raise temperature of reaction to 120 DEG C, continue back flow reaction 8h.Take out condensation product, with the washing of saturated aqueous common salt solution until neutral, add 20g anhydrous magnesium sulfate drying 0.5h, after filtering out anhydrous magnesium sulfate, 60 DEG C of backspins steam removing toluene solvant and obtain colorless transparent viscous liquid and gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.5g again, productive rate 92.5%.
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: in 18.4g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again condensation product, add octaphenyl POSS (octaphenyl POSS quality is 0.025% of total mass) (the Shanghai Aladdin reagent company limited of 0.00046g, purity 98.5%) as nucleus, the method for crystallization control temperature 50 C obtains MA-POSS crystallization.Crystallization is in bottom enrichment, in white clear particulate state, after there is no crystallization, at Cubic prestox acryloxy silsesquioxane from highly viscous fluid after crystallization, the T obtaining crystallization is separated by the method for suction filtration, centrifugal (rotating speed 4000rpm, centrifugation time 30min)
8structure MA-POSS.The generation confirming Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal can be analyzed by MS.As accompanying drawing 1, the mass spectrum of the colorless transparent viscous liquid that 1 (a) is prepared for embodiment 4 step (2), 1455, (1746,1814), (2105,2173) are respectively T
8, T
10, T
12the molecule peak of MA-POSS; 1 (b) is the mass spectrum of upper strata viscous liquid after crystallization in embodiment four step (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 form of crystallization.
The separation of crystallization can be analyzed by DSC.See accompanying drawing 2, the DSC figure that 2 (a) is the Cubic prestox acryloxy silsesquioxane obtained of separation in embodiment four step (3), visible T
8type MA-POSS crystalline melting peak is sharp-pointed, and melting enthalpy is large, shows that its purity is higher; 2 (b) is for isolating the DSC figure of upper strata viscous liquid after crystallization, its nodeless mesh melting absorption peak in embodiment four step (3).
Embodiment 5
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: add 25gMA and 100mL isopropyl alcohol mixture in there-necked flask, add 10g deionized water and 1g Tetramethylammonium hydroxide, there-necked flask stirs 10h as 50 DEG C of lower magnetic forces.Take out hydrolysis reaction mixing solutions, at 50 DEG C, vacuum rotary steam is except desolventizing, with 150mL toluene dissolved water hydrolysis products.With saturated aqueous common salt solution washing toluene solution until neutrality, add 15g anhydrous magnesium sulfate and to dewater 2h, filter out magnesium sulfate, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane.
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: take 20g hydrolysate; be dissolved in 100mL toluene solution; mixing solutions is moved in 500mL there-necked flask; dripping 5mL12.5% tetramethylammonium hydroxide aqueous solution is catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 105 DEG C of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, raise temperature of reaction to 125 DEG C, continue back flow reaction 8h.Take out condensation product, with the washing of saturated aqueous common salt solution until neutral, add 15g anhydrous magnesium sulfate drying 2h, after filtering out anhydrous magnesium sulfate, 60 DEG C of backspins steam removing toluene solvant and obtain colorless transparent viscous liquid and gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.3g again, productive rate 91.5%.
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: in 18.3g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again condensation product, add octaphenyl POSS (octaphenyl POSS quality is 0.05% of total mass) (the Shanghai Aladdin reagent company limited of 0.00093g, purity 98.5%) as nucleus, the method for crystallization control temperature 50 C obtains T
8structure MA-POSS crystallization.Crystallization is in bottom enrichment, in white clear particulate state, Cubic prestox acryloxy silsesquioxane from highly viscous fluid after crystallization, after there is no crystallization, the T obtaining crystallization is separated by the method for suction filtration, centrifugal (rotating speed 4000rpm, centrifugation time 30min)
8structure MA-POSS.
By the T obtained
8the MA-POSS crystal of structure by MALDI-TOFMS, DSC,
1h-NMR analysis and characterization, characterization result illustrative experiment is successfully prepared and is isolated Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
Embodiment 6
(1) preparation of the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane: add 25gMA and 100mL isopropyl alcohol mixture in there-necked flask, add 10g deionized water and 1g Tetramethylammonium hydroxide, there-necked flask stirs 10h as 50 DEG C of lower magnetic forces.Take out hydrolysis reaction mixing solutions, at 50 DEG C, vacuum rotary steam is except desolventizing, with 150mL toluene dissolved water hydrolysis products.With saturated aqueous common salt solution washing toluene solution until neutrality, add 15g anhydrous magnesium sulfate and to dewater 0.5h, filter out magnesium sulfate, obtain the hydrolysate of gamma-methyl allyl acyloxypropyl trimethoxysilane.
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: take 20g and be hydrolyzed head product; be dissolved in 100mL toluene solution; mixing solutions is moved in 500mL there-necked flask; dripping 5mL10% tetramethylammonium hydroxide aqueous solution is catalyzer; there-necked flask loads nitrogen protection, thermometer, water trap, prolong; 100 DEG C of lower magnetic force stirring and refluxing to solution are transparent and homogeneous solution, raise temperature of reaction to 115 DEG C, continue back flow reaction 8h.Take out condensation product, with the washing of saturated aqueous common salt solution until neutral, add 15g anhydrous magnesium sulfate drying 0.5h, after filtering out anhydrous magnesium sulfate, 60 DEG C of backspins steam removing toluene solvant and obtain colorless transparent viscous liquid and gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product 18.2g again, productive rate 91%.
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: in 18.2g gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate again condensation product, add octaphenyl POSS (octaphenyl POSS quality is 0.05% of total mass) (the Shanghai Aladdin reagent company limited of 0.00091g, purity 98.5%) as nucleus, the method for crystallization control temperature 50 C obtains T
8structure MA-POSS crystallization.Crystallization is in bottom enrichment, in white clear particulate state, Cubic prestox acryloxy silsesquioxane from highly viscous fluid after crystallization, after there is no crystallization, the T obtaining crystallization is separated by the method for suction filtration, centrifugal (rotating speed 4000rpm, centrifugation time 30min)
8structure MA-POSS.
By the T obtained
8the MA-POSS crystal of structure by MALDI-TOFMS, DSC,
1h-NMR analysis and characterization, characterization result illustrative experiment is successfully prepared and is isolated Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a preparation method for Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal, is characterized in that: comprise the following steps:
(1) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate: by 25g gamma-methyl allyl acyloxypropyl trimethoxysilane and polar solvent mixing, add 10mL catalyst A, magnetic agitation, vacuum rotary steam removes to polar solvent, dissolve with toluene, be washed till neutrality, dewater, filter, obtain gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate; The temperature of described magnetic agitation is 50 ~ 60 DEG C; Described catalyst A is an acidic catalyst A or basic catalyst A, and 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;
(2) preparation of gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again: the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate getting 20g step (1), be dissolved in lower boiling non-polar solvent, drip 5mL catalyst B, under nitrogen protection, it is transparent and homogeneous solution that 100 ~ 110 DEG C of magnetic agitation are back to solution, be warming up to 115 ~ 125 DEG C, back flow reaction 8h, take out product, be washed till neutrality, dry, filter, except lower boiling non-polar solvent, obtain water white thick liquid, be gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate condensation product again, described catalyst B is an acidic catalyst B or basic catalyst B, and described an acidic catalyst B is hydrochloric acid, described basic catalyst B is aqueous sodium hydroxide solution or tetramethylammonium hydroxide aqueous solution,
(3) preparation of Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal: it is that the octaphenyl silsesquioxane of 0.01 ~ 0.05% of total mass is as nucleus that the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate obtained to step (2) adds quality in condensation product again, crystallization control temperature 50 C, crystallize out in viscous fluid, isolation of crystalline, namely obtains Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal.
2. preparation method according to claim 1, is characterized in that: the polar solvent described in step (1) is ethanol, Virahol, tetrahydrofuran (THF); The time of described magnetic agitation is 10h; The temperature of described vacuum rotary steam is 60 DEG C; The described neutrality that is washed till is washed to neutrality with saturated common salt; Described dewatering dewaters with anhydrous magnesium sulfate.
3. preparation method according to claim 1, is characterized in that: the lower boiling non-polar solvent described in step (2) is benzene, toluene or dimethylbenzene; The described neutrality that is washed till is washed to neutrality with saturated common salt; Described drying is with anhydrous magnesium sulfate drying; The described method removing toluene removing toluene 60 DEG C of vacuum rotary steams.
4. preparation method according to claim 1, is characterized in that: the quality of the condensation product again of the gamma-methyl allyl acyloxypropyl trimethoxysilane hydrolysate described in step (3) 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, centrifugal.
5. preparation method according to claim 2, is characterized in that: the consumption that described anhydrous magnesium sulfate carries out dewatering is 15 ~ 25g, and the time is 0.5 ~ 2h.
6. preparation method according to claim 3, is characterized in that: the consumption of described anhydrous magnesium sulfate drying is 15 ~ 25g, and the time is 0.5 ~ 2h.
7. preparation method according to claim 4, is characterized in that: described centrifugal rotating speed is 4000rpm, and the time is 30min.
8. preparation method according to claim 1, is characterized in that: described an acidic catalyst A to be concentration be 10% hydrochloric acid; Described basic catalyst A is concentration is the aqueous sodium hydroxide solution of 10% or the tetramethyl-aqueous ammonium hydroxide of 10%.
9. preparation method according to claim 1, is characterized in that: described an acidic catalyst B to be concentration be 10% hydrochloric acid; Described basic catalyst B to be concentration be 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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| 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 |
| CN109053795B (en) * | 2018-08-15 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of polymethacryloxy silsesquioxane |
| 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 |
| CN110483780B (en) * | 2019-08-23 | 2022-05-24 | 哈尔滨工业大学 | Separation and purification method of 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 |
| 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 |
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| US20040163570A1 (en) * | 2003-02-26 | 2004-08-26 | Luc Vanmaele | Radiation curable ink compositions suitable for ink-jet printing |
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