CN101857607B - Tridecafluorooctyl propyl cage-shaped silsesquioxane and preparation method thereof - Google Patents
Tridecafluorooctyl propyl cage-shaped silsesquioxane and preparation method thereof Download PDFInfo
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- CN101857607B CN101857607B CN2010101979660A CN201010197966A CN101857607B CN 101857607 B CN101857607 B CN 101857607B CN 2010101979660 A CN2010101979660 A CN 2010101979660A CN 201010197966 A CN201010197966 A CN 201010197966A CN 101857607 B CN101857607 B CN 101857607B
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- propyl
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Abstract
The invention provides a tridecafluorooctyl propyl cage-shaped silsesquioxane and a preparation method thereof. The preparation method comprises the following steps: tridecafluorooctyl propyl polyhedral oligomeric silsesquioxane is dripped into an organic solvent; the tridecafluorooctyl propyl cage-shaped silsesquioxane and the organic solvent are evenly mixed in the presence of an acid catalyst; the mixture is heated to an organic solvent backflow temperature for reaction, and a standing reaction is carried out at room temperature; after a great quantity of white crystalline precipitates is produced in the solution, the mixture is pumped and filtered to obtain the white crystalline precipitates; then the obtained white crystalline precipitates are washed and dried in vacuum to obtain white tridecafluorooctyl propyl cage-shaped silsesquioxane. Filtrate obtained by pumping and filtering is heated and concentrated to 1/4 volume of the original filtrate volume; the organic solvent is recovered; then, the concentrated filtrate is added into water while stirred; then the obtained product is filtered, washed and dried in vacuum to obtain the white tridecafluorooctyl propyl cage-shaped silsesquioxane. The total recovery is 37-50%. The invention has simple and easy technology, low cost, high yield and high purity of product, the product has excellent hydrophobicity and oleophobic property and has excellent thermal stability and flame retardance and low dielectric constant.
Description
Technical field
The present invention relates to a kind of tridecafluorooctyl propyl cage-shaped silsesquioxane (ten trifluoro octyl group propyl group POSS), the invention still further relates to the preparation method of this tridecafluorooctyl propyl cage-shaped silsesquioxane.
Background technology
(Polydehral Oligomer Silsesquioxane, POSS) general molecular formula is (RSiO to cage-type silsesquioxane
1.5)
8The cage modle skeleton is made up of the SiO key, and the height of molecule on nanoscale is consistent, can be with molecule rank homodisperse in matrix; Can further optimize the interaction between material component; Effectively the advantage of good, low cost of kneading polymer materials processing technology and inorganic materials HS, stable performance gives material outstanding performance, has well solved traditional inorganic nano particle modified polymkeric substance and cann't be solved problem.The POSS cage skeleton that is made up of the silica element has good heatproof combustion resistance; (particle diameter is little for the POSS nanostructure; Specific surface area is big) have special effectses such as quantum size effect, special surface and interfacial effect, quantum tunneling effect; Can give the performance of the unique aspects such as sound, light, electricity, magnetic and catalysis of polymer materials, the polymer-modified important channel that has become preparation performance function material of POSS.
The monomeric synthetic route of POSS mainly contains three kinds of hydrolytic condensation methods, unfilled corner closed loop method, functional group's derivatization method.The hydrolytic condensation method is RSiX
3Raw material direct hydrolysis condensation under certain catalyzer and solvent condition obtains POSS; Unfilled corner closed loop method is RSiX
3The incomplete hydrolytic condensation of raw material generates unfilled corner seven and gathers POSS, adds R ' SiX again
3The closed loop polycondensation generates R
7R ' Si
8O
12The POSS monomer of structure; Functional group's derivatization method is through the POSS organo-functional group generation chemical reaction POSS monomer of functional group of making new advances of deriving.Take all factors into consideration processing condition, yield, and the cost and the source of raw material, the most economical and convenient with the hydrolytic condensation method, reaction equation is following:
The POSS monomer of side group contain fluorine atoms generally has better hydrophobic can; This has relation with the low surface energy of fluorine atom; At present a lot of surface hydrophobicity materials, automatically cleaning material all are to use the organic fluorine material surface-treated to obtain; Lower surface energy is widely used in the material surface hydrophobically modified like tetrafluoroethylene, because also can be used as releasing agent and lubricant.Siliciumatom also has lower surface energy, is widely used as releasing agent and skimmer like silicone oil.See that from chemical constitution fluorine-containing POSS is not only fluorine-containing but also siliceous, have lower surface energy.Fluorine-containing POSS specific molecule structure makes its super-hydrophobic, ultra oleophobic performance more outstanding; Stretch out eight fluorine-containing organic side chains on the nanometer silica cage; Form rough surface microstructure on a kind of nanoscale, the microtexture of this special similar lotus leaf surface makes the hydrophobic oleophobic performance of fluorine-containing POSS obtain the raising of matter.Because fluorine atom is the nanometer unicellular structure of electronic cloud controllability and POSS efficiently, fluorine-containing POSS still is a kind of ultra-low dielectric constant material of excellence.
Just because of the excellent properties of fluorine-containing POSS has caused the very big concern of scientific circles.POSS synthesizes and applied research has obtained very big development in the nineties in last century, and various new POSS monomers constantly are synthesized and obtain, but the synthetic comparatively difficulty of fluorine-containing POSS, the synthetic difficulty of the fluorine-containing POSS of especially long carbon-chain structure is very big, and progress is slow.The fluorine-containing POSS monomer of the first short carbon chain was just arranged until 2005, and (the organic side chain structure is-CH
2CH
2CH
2CF
3) synthetic report (and see Macromolecules 2005,38,1264-1270), but the fluorine-containing density of long carbochain POSS is big, surface energy is little, hydrophobic oleophobic is effective, thus the fluorine-containing POSS of long carbochain synthetic be prepared into for the focus in studying.Joseph M.Mabry in 2008 etc. have delivered one piece at " AngewandteChemie " magazine and have been-CH with the synthetic organic side chain of NaOH base catalysis route
2CH
2(CF
2)
nCF
3The article of the fluorine-containing POSS of (n=3,5,7) it is reported that (the organic side chain structure is-CH the longest fluorine-containing POSS monomer of its synthetic carbochain
2CH
2(CF
2)
7CF
3) be the most hydrophobic crystalline substance (having ten carbon atoms on the single organic side chain) in the world, water contact angle up to 151 ° (see Angew.Chem.Int.Ed.2008,47,4137-4140); Anish Tuteja etc. publish an article on " Science " and have specialized in organic side chain and be-CH
2CH
2(CF
2)
7CF
3The super-hydrophobic oleophobic properties research of fluorine-containing POSS, and set forth fluorine-containing carbon chain lengths theoretically and the special 3-D nano, structure of POSS (is seen Science 2007,318,1618-1622) to the influence of fluorine-containing POSS surface energy and super-hydrophobic, ultra oleophobic interfacial property.
Seen that at present side chain is-CH
2CH
2(CF
2)
nCF
3(n=3,5,7) and-CH
2CH
2CH
2CF
3The fluorine-containing POSS monomer of straight chain synthetic bibliographical information, but synthetic precursor (fluorine-containing siloxanes raw material) dependence on import, raw materials cost is high, and generally adopts alkaline catalysts such as sodium hydroxide, reaction under heating condition.
The contriver applies for another patent of invention " ten difluoro heptyl propyl group silsesquioxanes and preparation method thereof " before this; Number of patent application 200910234995.7; Under 0～40 ℃ of condition; Just successfully synthesize Dodecafluoroheptyl-propyl polyhedral oligomeric silsesquioxane under room temperature or the low temperature, carbon-chain structure is (CF
3)
2CFCFHCF (CF
3) CH
2CH
2CH
2CH
2-, single organic side chain has 10 atomic structure of carbon and 12 fluorine atoms, but the reaction times is long, and need leave standstill just can have reasonable yield in 50～70 days, and the product yield also can only reach about 28%.
Ten trifluoro octyl group propyl trimethoxy silicanes (trade(brand)name: be a kind of silane coupling agent of domestic suitability for industrialized production Actyflon-G602), be widely used in the modification of surface and interface hydrophobic oleophobic and other low-surface-energy material Application Areas, cheap and easy to get.If preparation becomes corresponding cage-type silsesquioxane; To give its better hydrophobic oleophobic interface performance because of the special 3-D nano, structure of POSS; But because carbon-chain structure is longer, number of fluorine atoms is many more; The hydrophobic oleophobic performance of fluorine-containing POSS and heat-proof combustion-resistant performance are also corresponding better, and synthetic difficulty is also corresponding bigger, does not also see the successfully relevant report of synthetic tridecafluorooctyl propyl cage-shaped silsesquioxane at present both at home and abroad.
Summary of the invention
For the carbon-chain structure that solves the prior art existence fluorine-containing POSS structural compounds long, that number of fluorine atoms is many is difficult for the synthetic problem; The invention provides a kind of tridecafluorooctyl propyl cage-shaped silsesquioxane and preparation method thereof; Have that preparation technology is easy, raw material is cheap and easy to get, the advantage that carbon-chain structure is long, number of fluorine atoms is many.
Technical scheme of the present invention is: the preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane; Ten trifluoro octyl group propyl trimethoxy silicanes are added dropwise in the organic solvent; In the presence of acid catalyst, mix, be heated under the organic solvent reflux temperature condition and react; Standing and reacting at ambient temperature again; After treating to generate a large amount of white crystalline precipitate in the solution, suction filtration obtains white crystalline precipitate, and the white crystalline precipitate washing, the vacuum-drying that obtain are obtained white tridecafluorooctyl propyl cage-shaped silsesquioxane.
Before the back flow reaction, can to add deionized water be cocatalyst in order to reach better effect.
The filtrating heating that suction filtration is obtained is concentrated into 1/4 of filtrating initial volume, reclaims organic solvent, and then, the filtrating after will concentrating while stirring adds in the entry, and filtration, washing, vacuum-drying obtain the tridecafluorooctyl propyl cage-shaped silsesquioxane of white.
Back flow reaction 12～48h, standing and reacting is 7～30 days under the room temperature condition.
Said organic solvent is any one or a few the mixture in ethanol, methyl alcohol, acetone, THF, propyl alcohol or the Virahol.
Said organic solvent is ethanol or methyl alcohol.
Said acid catalyst is any one or a few the mixture in hydrochloric acid, nitric acid, sulfuric acid, formic acid or the phosphoric acid.
Said acid catalyst is hydrochloric acid or nitric acid.
Use fresh solvent during washing, fresh solvent is any one or a few the mixture in methyl alcohol, ethanol, Virahol or the water.
The chemical molecular formula of tridecafluorooctyl propyl cage-shaped silsesquioxane is:
(CF
3(CF
2)
5CH
2CH(CH
3)CH
2CH
2CH
2)
8Si
8O
12
Chemical structural formula is:
Wherein, R is-CH
2CH
2CH
2(CH
3) CHCH
2(CF
2)
5CF
3
Beneficial effect:
1, the inventive method is simple for process, productive rate is higher, product purity is high, suitability for mass industrialized production.The tridecafluorooctyl propyl cage-shaped silsesquioxane product fusing point of preparation is 207 ℃; About 105 ℃ fusing point far above the fluorine-containing POSS of straight chain type of bibliographical information; 364 ℃ of temperature of initial decomposition, 800 ℃ of remaining rates of ablating are 43%, have excellent heat-proof combustion-resistant performance, hydrophobic oleophobic performance and low-k performance; And good consistency is arranged between the polymkeric substance, is a kind of polymkeric substance heat-proof combustion-resistant nano modifier of excellent property.Can be widely used in fields such as polymer modification, hydrophobic oleophobic boundary material, fire retardant, advanced low-k materials, trade sales coating, space material, medical material, luminescent material, liquid crystal material;
2, the present invention has improved the processing condition of the synthetic POSS of acid-catalyzed hydrolysis polycondensation method.Change reaction under general room temperature or the coldcondition under reflux condition hydrolysis condensation reaction, improved reactive behavior and speed of reaction, the reaction times was foreshortened to 7～30 days by 50～70 days, improved production efficiency and product yield simultaneously.
3, the present invention will be concentrated into half recrystallize, filtering technology changes into and is concentrated into 1/4 volume; Can reclaim organic solvent simultaneously like this; And need not further processing treatment, recovered solvent can directly put into production again as reaction solvent; Realize solvent recycling, reduced the quantity discharged of organic solvent; With water is that precipitation agent has good separating effect; Because product is water insoluble; Liquid starting material, acid catalyst, organic solvent and part intermediate product have then been stayed aqueous phase; This method separation efficiency is high, effective, and the product yield can be increased to 37%～50% by 28%, effectively reduces production cost.When may there be emulsion in water consumption more after a little while, can add the salt breakdown of emulsion at this moment, separate out deposition and improve yield.
4, product solvability of the present invention is good, can be dissolved in common solvents such as acetone, THF, and the fluorine-containing POSS monomer of long carbochain of existing report need be dissolved in the specific organic fluorine solvent, and price is high, toxicity is big;
5, the present invention is a raw material with the coupling agent ten trifluoro octyl group propyl trimethoxy silicanes (G-602) of domestic suitability for industrialized production first, the fluorine-containing POSS of synthetic long carbochain, and preparation technology is easy, and raw material is cheap and easy to get, greatly reduces synthetic cost;
6, the present invention is catalyzer with strong acid, can accelerate the hydrolysis condensation reaction process, promotes the formation of silsesquioxane cage type structure; Polar organic solvent can promote the formation of silsesquioxane cage modle structure, plays the effect of structure control;
7, the tridecafluorooctyl propyl cage-shaped silsesquioxane that makes of the present invention, single organic side chain structure is CF
3(CF
2)
5CH
2CH (CH
3) CH
2CH
2CH
2-, have 12 carbon atoms and 18 fluorine atoms, carbon chain length and have the cladodification structure, than in the bibliographical information the most fluorine-containing POSS of long carbon-chain structure (the organic side chain structure is CF
3(CF
2)
7CH
2CH
2-) more than two carbon atoms; Thereby the density of the outer fluorine atom of POSS monomer is bigger; Have lower surface energy, the special silica cagelike structure of ten trifluoro octyl group propyl group POSS will be given its excellent hydrophobic oleophobic performance, stretch out eight fluorine-containing organic side chains on the nanometer silica cage; Form rough surface microstructure on a kind of nanoscale, the microtexture of this special similar lotus leaf surface makes the hydrophobic oleophobic performance of ten trifluoro octyl group propyl group POSS get a qualitative improvement.
Description of drawings
The FTIR spectrogram of the tridecafluorooctyl propyl cage-shaped silsesquioxane that Fig. 1 makes for the embodiment of the invention 1.
The ten trifluoro octyl group propyl group that Fig. 2 makes for the embodiment of the invention 1 are the XRD figure spectrum of siloxanes by every means.
The ten trifluoro octyl group propyl group that Fig. 3 makes for the embodiment of the invention 1 are the TGA-DSC collection of illustrative plates of siloxanes by every means.
Embodiment
Through the mode of embodiment, technical scheme of the present invention is elaborated below, but protection scope of the present invention is not limited to said embodiment.
The preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane provided by the invention, concrete steps are:
Step 1,1mol ten trifluoro octyl group propyl trimethoxy silicanes are added dropwise in 250～10000ml organic solvent; Drip the acid catalyst of 0.5～1.5mol again, deionized water 0～250ml, restir is even after dropwising; Be heated to the reflux temperature of organic solvent; Reflux conditions is reaction 12～24h down, leaves standstill at ambient temperature 7～30 days again, treats to generate in the solution a large amount of white crystalline precipitate; When obtaining better reaction effect, can add some deionized waters.
Said organic solvent is selected any one or a few the mixture in ethanol, methyl alcohol, acetone, THF, propyl alcohol or the Virahol usually for use, is preferably methyl alcohol or ethanol; Said acid catalyst is any one or a few the mixture in hydrochloric acid, nitric acid, sulfuric acid, formic acid or the phosphoric acid, is preferably hydrochloric acid or nitric acid.
Step 2 obtains white solid with the reaction mixture suction filtration, and with the fresh solvent washing, vacuum-drying obtains white depositions; Get 1/4 volume that the filtrating heating is concentrated into the filtrating initial volume, reclaim organic solvent, agitation condition adds in certain water gaging down, and the volume ratio that concentrates rear filtrate and water is 1: 2～10, and filtration, washing, vacuum-drying obtain white depositions; The merging of two portions white depositions is obtained the title product tridecafluorooctyl propyl cage-shaped silsesquioxane.
Said washing uses fresh solvent as any one or a few the mixture in methyl alcohol, ethanol, Virahol or the water, is preferably methyl alcohol, ethanol or water.
Reaction formula of the present invention is:
R＝-CH
2CH
2CH
2(CH
3)CHCH
2(CF
3)
5CF
3
Another object of the present invention is achieved in that tridecafluorooctyl propyl cage-shaped silsesquioxane (ten trifluoro octyl group propyl group POSS), and its chemical molecular formula is: (CF
3(CF
2)
5CH
2CH (CH
3) CH
2CH
2CH
2)
8Si
8O
12
Its chemical structural formula is:
Wherein, R is-CH
2CH
2CH
2(CH
3) CHCH
2(CF
2)
5CF
3
Embodiment 1
With 52.4g ten trifluoro octyl group propyl trimethoxy silicane (trade(brand)name: Actyflon-G602, molecular formula: C
6F
13CH
2CH (CH
3) C
3H
6Si (OCH
3)
3) 0.1mol is added dropwise to 8000ml ethanol, adds catalyzer concentrated hydrochloric acid 100ml (concentration 37.5%), water 10ml again, it is even to dropwise the back restir, is heated to 75 ℃ of back flow reaction 29h, and standing and reacting is 27 days again, generates a large amount of white crystal shapes depositions in the solution.
2) the reaction mixture filtration is obtained white crystal, use methanol wash, drying obtains portioned product.Get the filtrating heating and be concentrated into 2000ml, reclaim organic solvent, agitation condition adds (concentrating rear filtrate and water volume ratio is 1: 7) in the 14000ml water, filtration, washing, vacuum-drying down.The two merging obtains product 21.4g, yield about 47% altogether.
Product tridecafluorooctyl propyl cage-shaped silsesquioxane of the present invention (ten trifluoro octyl group propyl group POSS), its chemical molecular formula is: (CF
3(CF
2)
5CH
2CH (CH
3) CH
2CH
2CH
2)
8Si
8O
12
Its chemical structural formula is:
Wherein, R is-CH
2CH
2CH
2(CH
3) CHCH
2(CF
2)
5CF
3
Product is characterized: as shown in Figure 1, each organic group charateristic avsorption band of side chain is complete in the FTIR spectrogram, wherein 2500-3000
-1The broad peak at place is the absorbed oscillation peak of C-F and C-H, 1086cm
-1A strong and sharp-pointed absorption peak occurred, the absorbed oscillation peak of corresponding single cage modle silica structure, and the disappearance of the absorbed oscillation peak of Si-O-C and Si-O-H explain that reaction is complete, and product is target compound.As shown in Figure 2,7.48 ° of characteristic peaks appear in the XRD spectra, show to have generated complete cage modle eight polysilsesquioxane structures.As shown in Figure 2,207 ℃ endotherm(ic)peak corresponds to the fusing point of product in the DSC spectrogram, and the product temperature of initial decomposition is 364 ℃ in the TGA spectrogram, and 800 ℃ of remaining rates of ablating are 43%, and tridecafluorooctyl propyl cage-shaped silsesquioxane has good heat-proof combustion-resistant performance.
Embodiment 2～6
The preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane, its concrete steps be with embodiment 1, preparation technology parameter, raw materials used and specifically with scale 1:
Preparation technology parameter, raw materials used and concrete consumption among table 1 embodiment 2～6
Claims (8)
1. the preparation method of a tridecafluorooctyl propyl cage-shaped silsesquioxane, it is characterized in that: ten trifluoro octyl group propyl trimethoxy silicanes are added dropwise in the organic solvent, and the molecular formula of described ten trifluoro octyl group propyl trimethoxy silicanes is: C
6F
13CH
2CH (CH
3) C
3H
6Si (OCH
3)
3In the presence of acid catalyst, mix, be heated to reaction under the organic solvent reflux conditions; Standing and reacting at ambient temperature again; After treating to generate a large amount of white crystalline precipitate in the solution, suction filtration obtains white crystalline precipitate, and the white crystalline precipitate washing, the vacuum-drying that obtain are obtained white tridecafluorooctyl propyl cage-shaped silsesquioxane;
Said organic solvent is any one or a few the mixture in ethanol, methyl alcohol, acetone, THF, propyl alcohol or the Virahol;
Said acid catalyst is any one or a few the mixture in hydrochloric acid, nitric acid, sulfuric acid, formic acid or the phosphoric acid.
2. the preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane as claimed in claim 1, it is characterized in that: before the back flow reaction, the adding deionized water is a cocatalyst.
3. the preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane as claimed in claim 1; It is characterized in that: the filtrating heating that suction filtration is obtained is concentrated into 1/4 of filtrating initial volume; Reclaim organic solvent; Then, the filtrating after will concentrating while stirring adds in the entry, and filtration, washing, vacuum-drying obtain the tridecafluorooctyl propyl cage-shaped silsesquioxane of white.
4. the preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane as claimed in claim 1, it is characterized in that: back flow reaction 12～48h, standing and reacting is 7～30 days under the room temperature condition.
5. the preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane as claimed in claim 1, it is characterized in that: said organic solvent is ethanol or methyl alcohol.
6. the preparation method of tridecafluorooctyl propyl cage-shaped silsesquioxane as claimed in claim 1, it is characterized in that: said acid catalyst is hydrochloric acid or nitric acid.
7. like the preparation method of claim 1 or 3 described tridecafluorooctyl propyl cage-shaped silsesquioxanes, it is characterized in that: using fresh solvent, fresh solvent during washing is any one or a few the mixture in methyl alcohol, ethanol, Virahol or the water.
8. the tridecafluorooctyl propyl cage-shaped silsesquioxane of the preparation method of the described tridecafluorooctyl propyl cage-shaped silsesquioxane of claim 1 preparation, it is characterized in that: chemical molecular formula is: (CF
3(CF
2)
5CH
2CH (CH
3) CH
2CH
2CH
2)
8Si
8O
12
Chemical structural formula is:
Wherein, R is-CH
2CH
2CH
2(CH
3) CHCH
2(CF
2)
5CF
3
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| CN105666610A (en) * | 2016-02-22 | 2016-06-15 | 泗洪新创源木业有限公司 | Preparation method of high-hydrophobicity and self-cleaning wood |
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Non-Patent Citations (3)
| Title |
|---|
| Joseph M.Mabry et al..Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS).《Angew.Chem.Int.Ed.》.2008,第47卷(第22期),4137-4140. * |
| Scott T.Iacono et al..Facile synthesis of hydrophobic fluoroalkyl functionalized silsesquioxane nanostructures.《Chem.Commun.》.2007,(第47期),4992-4994. * |
| 曾科.含氟丙基笼状倍半硅氧烷（POSS）的两亲性嵌段共聚物合成、表征及其自组装行为的研究.《中国博士学位论文全文数据库 工程科技Ⅰ辑》.2009,(第12期),B014-26. * |
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