CN103159795B - Monohydroxy modifies eight ethenyl cage model sesquialter siloxanes and preparation method thereof - Google Patents
Monohydroxy modifies eight ethenyl cage model sesquialter siloxanes and preparation method thereof Download PDFInfo
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- CN103159795B CN103159795B CN201310084358.2A CN201310084358A CN103159795B CN 103159795 B CN103159795 B CN 103159795B CN 201310084358 A CN201310084358 A CN 201310084358A CN 103159795 B CN103159795 B CN 103159795B
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- model sesquialter
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 siloxanes Chemical class 0.000 title claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 4
- 125000000524 functional group Chemical group 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of monohydroxy and modify eight ethenyl cage model sesquialter siloxanes and preparation method thereof.Cage-type silsesquioxane namely can as the presoma of organic-inorganic hybrid material, and also at liquid crystal material, fire retardant material, electroluminescent material has great application potential.And this wherein, cage-type silsesquioxane dispersiveness is in the base the key problem playing its performance.The functionalized cage-type silsesquioxane that can synthesize at present is single-activity, and also usually have process complexity, cost is higher, the inferior position that productive rate is low.The industrialized ethenyl cage model sesquialter siloxane of the present invention is raw material, body is modified for transition with trifluoromethanesulfonic acid base, obtain monohydroxy through hydrolysis and modify eight ethenyl cage model sesquialter siloxanes, the method cost is low, and process is simple, and productive rate is high, be applicable to large-scale industrial production, the simultaneously also functional group of grafting two kinds of reactive behavioies on POSS, greatly improves the range of choice of its graft modification, has good practical value.
Description
Technical field:
The present invention relates to the preparation method that monohydroxy modifies eight ethenyl cage model sesquialter siloxanes
Background technology:
Polyhedral oligomeric silsesquioxane (POSS) is that a class is containing (RSiO
1.5)
n, wherein n>=4, R is hydrogen, hydroxyl, epoxy group(ing), alkyl, the group etc. of thiazolinyl and their derivatives, and its primary structure comprises trapezoidal, half cage modle and cage modle etc., and this wherein, and the research of half cage modle and the cage-type silsesquioxane with symmetrical structure is many.
The organic substituent of cage-type silsesquioxane can be divided into two large classes according to activity: a class is inertia group, as alkyl, and alkylene, aryl, arylidene etc., can regulate the consistency of its nanostructure and polymkeric substance; Another kind of is active group, as hydrogen, chlorine, hydroxyl, carboxyl, aldehyde radical, epoxy group(ing) etc., can by further with polymer reaction, improve POSS dispersiveness in the base, thus play nano-meter characteristic and the potentiality of silica structure in thermal characteristics and flame retardant properties of POSS.Such as, Pan Jingbin etc. utilize eight anilino POSS and polyimide (PI) blended, test result show, modified PI improves a lot on dynamic modulus and resistance toheat.This also allows and it is found that the POSS preparing active group modification is the key point playing its characteristic.Wherein Xiao Jun equality people utilizes breach cagelike structure POSS, namely based on seven poly-(isobutyl-) silsesquioxanes three silanol (T7), adopts angle-sealing method, condensation method, the silsesquioxane of azide method synthesis single functionality.Wang Wen equality utilizes T7 sodium salt and trichlorosilane to prepare monochloro propyl group POSS equally, and replaces further with diethanolamine, the two hydroxyl cage-type silsesquioxane of preparation.
In sum, the many active POSS of preparation have great application prospect.But domestic too synthesis at present has POSS of two kinds of different activities and preparation method thereof and does not still report.The invention provides the preparation method that a kind of monohydroxy of preparation modifies eight ethenyl cage model sesquialter siloxanes.
Summary of the invention:
The invention provides a kind of monohydroxy eight ethenyl cage model sesquialter siloxane and preparation method thereof, modify through trifluoromethanesulfonic acid and be hydrolyzed for primary raw materials in anhydrous solvent with industrialized eight ethenyl cage model sesquialter siloxanes and prepare monohydroxy eight ethenyl cage model sesquialter siloxane.
A kind of monohydroxy eight ethenyl cage model sesquialter siloxane, its structural formula is as follows:
Concrete steps are as follows:
(1), under room temperature, be dissolved in by octavinyl-POSS in anhydrous methylene chloride or anhydrous trichloromethane, concentration range is the colourless solution of 20mg/mL-100mg/mL; Dropwise adding with octavinyl-POSS mol ratio is the trifluoromethanesulfonic acid of 1:0.95-1:1.05, and logical nitrogen, stirs 4-8 hour, and control temperature of reaction within the scope of 0 DEG C-25 DEG C by water bath with thermostatic control, solution is faint yellow; Gained solution obtains solid by rotary evaporation, and preserve under nitrogen atmosphere, solid transfers baby pink to by white.
(2) by step (1) gained dissolution of solid in the mixed solvent of acetone and water, the volume ratio of acetone and water is 2:1-8:1, forms colourless solution, at 0 DEG C-20 DEG C, stirs more than 4h, obtains white solid by rotary evaporation.And utilizing silicagel column, vacuum-drying obtains final monohydroxy and modifies eight ethenyl cage model sesquialter siloxanes.
The chemical equation of the preparation method of monohydroxy eight ethenyl cage model sesquialter siloxane of the present invention is as follows:
The present invention, compared with background technology, has following advantage:
1. the present invention prepares a kind of cage-type silsesquioxane with two kinds of active function groups.
2. the present invention uses industrialization eight ethenyl cage model sesquialter siloxane to be raw material, and raw material sources are extensive, low price.
3. the method for the invention has the higher feature of productive rate, is usually greater than 60%
Embodiment:
Example 1
(1) join in 50ml eggplant type flask by 1g octavinyl-POSS, 10ml anhydrous methylene chloride, stirred at ambient temperature, makes to mix.In water bath with thermostatic control, temperature control is 0 DEG C and dropwise adds 1.58mmol trifluoromethanesulfonic acid, stirs 4h, and return to room temperature gradually under nitrogen atmosphere.Gained soln using saturated sodium carbonate solution washs more than 3 times, and solution is become colorless by yellow, separatory, utilizes rotary evaporation to obtain white powder.
(2) powder obtained in (1) is directly added 20ml to wet (V in acetone
acetone: V
water=4:1), stirred at ambient temperature 24h, obtains white solution, utilizes anhydrous magnesium sulfate drying, utilizes rotary evaporation, and ambient temperature in vacuum drying obtains product.
Structural characterization is as follows:
.
1HNMR(500MHz,CDCl
3,25℃):δ6.15-5.90(m,21H),3.85(t,J7.2Hz,2H,CH
2OH),1.18(t,J7.2Hz,
2H,SiCH
2).
13C{1H}NMR(125MHz,CDCl
3,25℃):δ137.07,137.05,136.95(rel.int.3:3:1forCH
2),128.58,128.56(rel.int.4:3forCH),58.48(CH
2OH),17.28(SiCH
2).
29Si{
1H}NMR(99MHz,CDCl
3,25℃):δ-68.00,δ-80.16,δ-80.36(rel.int.1:3:4).EI(70eV,200℃)
Example 2
(1) under room temperature, 0.5g octavinyl-POSS is dissolved in the anhydrous trichloromethane solvent of 10ml, form homogeneous solution, at room temperature dropwise add 0.79mmol trifluoromethanesulfonic acid, solution is light yellow, stirs 8h under nitrogen atmosphere, gained soln using saturated sodium carbonate solution washs more than 3 times, solution is become colorless by yellow, separatory, utilizes rotary evaporation to obtain white powder.
(2) powder obtained in (1) is directly added 12ml to wet (V in acetone
acetone: V
water=3:1), stirred at ambient temperature 18h, obtains white solution, utilizes anhydrous magnesium sulfate drying, utilizes rotary evaporation, and ambient temperature in vacuum drying obtains product.Product structure characterizes with example 1.
Claims (1)
1. monohydroxy modifies a preparation method for eight ethenyl cage model sesquialter siloxanes, and it is as follows that described monohydroxy modifies eight ethenyl cage model sesquialter siloxane structural formulas:
It is characterized in that, comprise step as follows:
(1), under room temperature, be dissolved in by octavinyl-POSS in anhydrous methylene chloride or anhydrous trichloromethane, concentration range is the colourless solution of 20mg/mL-100mg/mL; Dropwise adding with octavinyl-POSS mol ratio is the trifluoromethanesulfonic acid of 1:0.95-1:1.05, and logical nitrogen, stirs 4-8 hour, and control temperature of reaction within the scope of 0 DEG C-25 DEG C by water bath with thermostatic control, solution is faint yellow; Gained solution obtains solid by rotary evaporation, and preserve under nitrogen atmosphere, solid transfers baby pink to by white;
(2) by step (1) gained dissolution of solid in the mixed solvent of acetone and water, the volume ratio of acetone and water is 2:1-8:1, forms colourless solution, at 0 DEG C-20 DEG C, stirs more than 4h, obtains white solid by rotary evaporation; And utilizing silicagel column, vacuum-drying obtains final monohydroxy and modifies eight ethenyl cage model sesquialter siloxanes.
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| CN106751863A (en) * | 2016-12-26 | 2017-05-31 | 沈阳化工大学 | A kind of silicon rubber radiation hardness auxiliary agent and preparation method thereof |
| CN109942620A (en) * | 2019-04-29 | 2019-06-28 | 哈尔滨工业大学 | A kind of polyhydroxy modifies the preparation method of eight ethenyl cage model sesquialter siloxanes |
| CN110423501B (en) * | 2019-06-19 | 2021-07-09 | 永康市嘉禧厨具有限公司 | Antibacterial non-stick pan coating, preparation method and non-stick pan |
| CN110669198A (en) * | 2019-10-15 | 2020-01-10 | 浙江禾欣科技有限公司 | Solvent-free polyurethane resin for POSS (polyhedral oligomeric silsesquioxane) -based automobile leather and preparation method thereof |
| CN111944150A (en) * | 2020-08-19 | 2020-11-17 | 五邑大学 | Preparation method of fluorine-containing semi-cage silsesquioxane |
| CN113913997A (en) * | 2021-08-25 | 2022-01-11 | 厦门求特新材料有限公司 | Four-in-one-step formed flame-retardant woven tape product and processing technology |
| CN114191853A (en) * | 2021-12-29 | 2022-03-18 | 杭州撒拉弗科技有限公司 | Preparation method of modified silane papermaking wastewater defoaming agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100417A (en) * | 1999-08-31 | 2000-08-08 | The United States Of America As Represented By The Secretary Of The Air Force | Functionalizing olefin bearing silsesquioxanes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100417A (en) * | 1999-08-31 | 2000-08-08 | The United States Of America As Represented By The Secretary Of The Air Force | Functionalizing olefin bearing silsesquioxanes |
Non-Patent Citations (2)
| Title |
|---|
| Breaking Symmetry toward Nonspherical Janus Particles Based on Polyhedral Oligomeric Silsesquioxanes: Molecular Design, "Click" Synthesis, and Hierarchical Structure;Yiwen Li et al.;《Journal of the American Chemical Society》;20110616;第133卷;第10713页图1反应条件ii，Supporting Information * |
| Methods for effecting monofunctionalization of (CH2NCH)8Si8O12;Frank J. Feher et al.;《Chemical Communications》;19991231;第1289页图1,第1290页左栏倒数1-2段 * |
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