CN103172657B - Containing the functionalized cage modle polyhedral polysilsesquioxane and preparation method thereof of alkynyl - Google Patents
Containing the functionalized cage modle polyhedral polysilsesquioxane and preparation method thereof of alkynyl Download PDFInfo
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Abstract
The invention discloses a kind of functionalized cage modle polyhedral polysilsesquioxane containing alkynyl, it is by reacting with containing the alkyl carboxylic acid of sulfydryl containing the cage modle polyhedral polysilsesquioxane of end thiazolinyl, gained containing the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or the reaction of alkynyl alcohol obtained.Its productive rate is high, and purity is high, and it is short that reaction process is easy to red-tape operati, reaction times.It can be widely used in the preparation of special construction cage modle polyhedral polysilsesquioxane, polymer modification, and can predict and develop on the functional materials such as medical, space.
Description
Technical field
The present invention relates to a kind of polyhedral oligomeric silsesquioxane (POSS) containing alkynyl and preparation method thereof.
Background technology
Polyhedral silsesquioxane (POSS) is chemical formula is [RSiO
1.5]
nmaterial general name, wherein n can be 6,8,10,12 etc., the most common with 6,8.The structure of common silsesquioxane comprises unformed, trapezoidal, cage modle and half cage modle.
Polyhedral silsesquioxane is as a kind of novel organic-inorganic matrix material grown up in recent years, not only there is low, the thermally-stabilised good advantage of organic materials density, have both good toughness and workability, also have high, the resistant to elevated temperatures traditional feature of inorganic materials intensity.
Owing to integrating multiple material performance, its research is also become to a focus in present material science.In recent years, more domestic scientific research institutions had also carried out the research work of this respect in succession.The synthesis of current POSS monomer mainly contains following three kinds of methods: hydrolytic condensation method, unfilled corner closed loop method, functional group's derivatization method is (see MikhailG.VoronkovandVladimirI.Lavrent ' yev.PolyhedralOligosilsesquioxanesandTheirHomoDerivative s.TopicsinCurrentChemistry, 1982,199.).
In addition, due to POSS unique texture and performance, POSS/ Nano-hybrid polymeric materials becomes a kind of high-performance organic/inorganic hybridization material that recent development is got up, but by the POSS based high molecular material property instability that physical blending process obtains, is easily separated.And pass through chemical process, can directly POSS be introduced in the middle of macromolecular scaffold, the high molecular nanometer hybrid material containing POSS is made to have organic and over-all properties that is inorganic materials, prepare thermoplasticity and thermoset macromolecule material, the second-order transition temperature of material, flame retardant properties, mechanical property, permeability are significantly improved.People by special for this class inorganic/organic Hybrid Materials is widely applied to polymer-based nano hybrid material field and other field.
But owing to needing reactive functionality support by chemical process hybridized polymer, so need not have the POSS of reactive behavior first to carry out functionalizedly obtaining suitable active function groups, more further with polymer reaction.So it is namely aobvious particularly important to carry out functionalized research to it, about containing the functionalized research of POSS, mainly contain aminofunctional " a kind of containing amino cage-type silsesquioxane and preparation method thereof " (Chinese Patent Application No. CN201010539696.7) at present, epoxy-functional " a kind of octa-epoxy cage type sesquialter siloxane and preparation method thereof " (Chinese Patent Application No. CN200910080803.1), azide-functionalized (LauraPetraruandWolfgangH.Binder.Azide/Alkyne-Functionali zedOligomericSilsesquioxanes.PolymerPreprints, 2005, 46 (2), 841.), hydroxy-functional " a kind of preparation method of poly-hydroxy silsesquioxane " (Chinese Patent Application No. CN03134129.2), halogen-functionalized (Liu Xueying, " synthesising process research of eight chloropropyl cage-type silsesquioxanes ", print during chemical industry, 2011, 25 (1), 22.) and other are functionalized as containing Maleic anhydride fimctionalized reaction etc.
In numerous functionalized POSS, the advantage that the POSS containing end alkynyl radical has other POSS incomparable, such as excellent reactive behavior, has more the molecular designing (nitrine-alkynyl click chemistry reaction, monomer polyaddition reaction etc.) etc. of prospect.2010, AxelH.E.M ü ller reports and has synthesized single-ended alkynyl POSS (see A " ClickChemistry " ApproachtoLinearandStar-ShapedTelechelicPOSS-ContainingH ybridPolymers by three-step reaction route, Macromolecules, 2010,43,3148-3152).But according to its bibliographical information, the alkynyl-functional POSS comprehensive yied obtained by this method is only 59.1%, and link alkylyl side chain is comparatively tediously long.In addition, so far in the open and article delivered or patent, report prepared by many alkynyl-functional POSS is not had.
Summary of the invention
Contriver is through studying discovery with keen determination, by mercapto-olefin addition reaction, the cage modle polyhedral polysilsesquioxane of end thiazolinyl and the carboxylic acid reaction containing sulfydryl will be contained, obtain the cage modle polyhedral polysilsesquioxane containing end carboxyl, by itself and alkynylamine or alkynyl alcohol carries out amidation or esterification is reacted, obtain the cage modle polyhedral polysilsesquioxane containing alkynyl, thus complete the present invention.
The object of the present invention is to provide the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl, it is obtained by the method comprised the following steps:
(1) under initiator exists, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is carried out with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or the reaction of alkynyl alcohol, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
Another object of the present invention is to the preparation method providing a kind of functionalized cage modle polyhedral polysilsesquioxane containing alkynyl, the method comprises the following steps:
(1) under initiator exists, containing cage modle polyhedral polysilsesquioxane and the alkyl carboxylic acid containing sulfydryl of end thiazolinyl, the cage modle polyhedral polysilsesquioxane containing end carboxyl is obtained;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or the reaction of alkynyl alcohol, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
According to the present invention, reaction process is easy to control, operate, reaction times is short, the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl can be obtained with high yield, high purity, it can be widely used in the preparation of special construction cage modle polyhedral polysilsesquioxane, polymer modification and can predict and develop on the functional materials such as medical, space, of many uses.
Accompanying drawing explanation
Fig. 1 to illustrate in POSS, embodiment 1 obtain the infrared spectrum of mono-carboxy-functionalized POSS and single alkynyl-functional POSS.
Fig. 2 to illustrate in POSS, embodiment 1 obtain the nmr spectrum of mono-carboxy-functionalized POSS and single alkynyl-functional POSS.
Fig. 3 to illustrate in POSS, embodiment 5 obtain the infrared spectrum of mono-carboxy-functionalized POSS and single alkynyl-functional POSS.
Fig. 4 to illustrate in POSS, embodiment 5 obtain the nmr spectrum of mono-carboxy-functionalized POSS and single alkynyl-functional POSS.
Fig. 5 to illustrate in POSS, embodiment 7 obtain the infrared spectrum of the functionalized POSS of tricarboxylic base and three alkynyl-functional POSS.
Fig. 6 to illustrate in POSS, embodiment 8 obtain the infrared spectrum of five carboxy-functionalized POSS and five alkynyl-functional POSS.
Fig. 7 to illustrate in POSS, embodiment 9 obtain the nmr spectrum of eight carboxy-functionalized POSS and eight alkynyl-functional POSS.
Embodiment
Below by way of embodiment, the present invention is described in detail, and illustrated by these, the features and advantages of the invention will become clearly, clearly.
On the one hand, the invention provides the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl, it is obtained by the method comprised the following steps:
(1) under initiator exists, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or the reaction of alkynyl alcohol, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
As the cage modle polyhedral polysilsesquioxane containing end thiazolinyl, referring to as shown in the formula the silsesquioxane shown in I containing in the functionalized cage modle polyhedral polysilsesquioxane of alkynyl according to of the present invention,
Wherein, R can be hydrogen, alkyl, aryl, alicyclic radical or other organic groups (as alkyl silyl, itrile group etc.) independently of one another,
R ' can be alkyl, aryl, alicyclic radical or other organic groups (as alkyl siloxy, itrile group, thioether etc.);
Or by eight vinyl silsesquioxanes shown in Formula Il
In a preferred embodiment, in formula I, R can be hydrogen, ethyl, propyl group, isobutyl-, iso-octyl, cyclopentyl, cyclohexyl or phenyl etc. independently of one another,
R ' is ethyl, propyl group, butyl or phenyl.
As the specific examples of the cage modle polyhedral polysilsesquioxane containing end thiazolinyl, mention following material: seven isobutyl-allyl group silsesquioxanes, seven isobutyl vinyl ether-glycidyl silsesquioxanes, seven phenyl allyl silsesquioxanes, seven phenyl vinyl silsesquioxanes, seven allyl ethyl silsesquioxanes, seven ethyl vinyl silsesquioxanes, seven cyclopentyl allyl group silsesquioxanes, seven cyclopentylethylene base silsesquioxanes, seven cyclohexyl allyl group silsesquioxanes, seven cyclohexylvinyl silsesquioxane eight vinyl silsesquioxanes and eight allyl group silsesquioxanes etc.。
Containing in the functionalized cage modle polyhedral polysilsesquioxane of alkynyl according to of the present invention, the described cage modle polyhedral polysilsesquioxane containing end thiazolinyl contains 1-8 end thiazolinyl, when using containing 1 end thiazolinyl cage modle polyhedral polysilsesquioxane, obtain the functionalized cage modle polyhedral polysilsesquioxane with an alkynyl, when using containing 8 end thiazolinyl cage modle polyhedral polysilsesquioxane, according to the alkynyl number that the product expected has, control the ratio of the molar weight of reaction raw materials, can obtain that there is the functionalized cage modle polyhedral polysilsesquioxane expecting number alkynyl.
The described cage modle polyhedral polysilsesquioxane containing end thiazolinyl can be commercially available, also can synthesize (see DavidB.Cordes according to currently known methods, PaulD.Lickiss, andFranckRataboul.RecentDevelopmentsintheChemistryofCubi cPolyhedralOligosilsesquioxanes.Chem.Rev.2010,110,2081-2173.).
In the present invention, be not particularly limited as the alkyl carboxylic acid containing sulfydryl, be preferably the alkyl carboxylic acid containing end sulfydryl, be more preferably formula HS-(CH
2)
nend mercaptoalkyl carboxylic acid shown in-COOH, wherein n=1-12.
As the specific examples of the alkyl carboxylic acid containing sulfydryl, described Thiovanic acid can be commercially available, or according to currently known methods synthesis (see such as " China Chemical Industry product is complete works of, upper volume ", Da197 Thiovanic acid, 537 pages).
In the present invention, initiator used can be photosensitizers or thermal initiator, they, under UV-irradiation or under heating state, can produce free radical, thus the cage modle polyhedral polysilsesquioxane caused containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl.
In the present invention, as photosensitizers, be not particularly limited, as long as it can produce radical initiation reaction under UV-irradiation, specifically mention 2-hydroxy-2-methyl-1-phenyl-acetone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, etc. benzoin methyl ether etc.
In the present invention, can be used alone any one that be selected from above-mentioned photosensitizers, or arbitrary combination to use wherein multiple.
When using photosensitizers, need to use UV-irradiation, make photosensitizers to produce free radical, preferably, the wavelength of irradiation UV-light is within the scope of 250 ~ 400nm.
According to the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl of the present invention, in a preferred embodiment, above-mentioned steps (1) is: under photosensitizers exists, under UV-irradiation, cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl.
In the present invention, as thermal initiator, be not particularly limited, as long as it can produce radical initiation reaction under heating state, specifically mention Diisopropyl azodicarboxylate (AIBN).
In the present invention, can be used alone any one that be selected from above-mentioned thermal initiator, or arbitrary combination to use wherein multiple.
When using thermal initiator, needing heating, making thermal initiator to produce free radical, Heating temperature need reach or higher than decomposing the temperature of thermal initiator used.
According to the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl of the present invention, in a preferred embodiment, above-mentioned steps (1) is: under thermal initiator exists, under heating state, cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl.
According to the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl of the present invention, in step (1), after the functionalized cage modle polyhedral polysilsesquioxane containing end carboxyl is obtained by reacting the cage modle polyhedral polysilsesquioxane containing end carboxyl with the alkyl carboxylic acid containing sulfydryl, the cage modle polyhedral polysilsesquioxane containing end carboxyl that can be separating obtained.Such as, reaction solution is precipitated in acetonitrile, filter the cage modle polyhedral polysilsesquioxane obtained containing end carboxyl.
Containing in the functionalized cage modle polyhedral polysilsesquioxane of alkynyl according to of the present invention, in step (2), tiing up under aqua and catalyst action, carry out condensation reaction containing the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or alkynyl alcohol, obtain the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
In the present invention, in step (2), aqua of tiing up used, also referred to as dewatering agent, contributes to sloughing water molecules, thus promote to carry out condensation reaction, as amidation or esterification containing between the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or alkynyl alcohol.
In the present invention, for tiing up aqua not special requirement, the common amidation in this area or esterification can be used with tiing up aqua.But, found by great many of experiments, tie up aqua and be preferably such as dicyclohexylcarbodiimide (DCC) and analogue thereof, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) etc.
In the present invention, in step (2), used catalyst can for conventional acylation catalyst.But, found by great many of experiments, catalyzer is preferably such as DMAP (DMAP) and analogue thereof, I-hydroxybenzotriazole (HOBT) and analogue etc. thereof.
In the present invention, in step (2), do not specially require for temperature of reaction, reaction can be carried out at normal temperatures.
In the present invention, in step (2), containing after carrying out condensation reaction between the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or alkynyl alcohol, the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl can be isolated.Such as, precipitation, washing etc.
On the other hand, the invention provides a kind of preparation method of the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl, the method comprises the following steps:
(1) under initiator exists, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and alkynylamine or the reaction of alkynyl alcohol, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
Wherein, for explanation and the optimization of step, condition, raw material etc., and above about functionalized cage modle polyhedral polysilsesquioxane identical containing alkynyl, do not repeat at this.
embodiment
Below by way of exemplary embodiment, the present invention is described further, but these embodiments are only exemplary, should not be construed as limitation of the scope of the invention.
Embodiment 1
Step 1: 5g seven isobutyl-allyl group POSS (5.8mmol) and 0.4ml Thiovanic acid (7.2mmol) are dissolved completely in 20ml tetrahydrofuran (THF), then 0.05g thermal initiator AIBN (0.3mmol) is added, constant temperature oil bath reaction system being placed in 80 DEG C refluxes 5h, carries out thermal booster reaction.After reaction terminates, reaction drop is carried out precipitate, drying, obtain the cage modle polyhedral polysilsesquioxane of end carboxyl, productive rate is 98%.
Step 2: by the cage modle polyhedral polysilsesquioxane 2g (2.1mmol) of gained end carboxyl in step 1, propargyl amine 173 μ l (2.5mmol) dissolves completely in 20ml methylene dichloride, then add 0.41g and tie up aqua 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl, 2.1mmol) with 0.05g catalyzer DMAP (DMAP, 0.4mmol), by reaction system at 35 DEG C of stirring reaction 12h, after reaction terminates, reaction solution is washed, extraction, volatile dry obtains single alkynyl-functional's cage modle polyhedral polysilsesquioxane, productive rate is 87%.
In above-mentioned steps 1 gained containing gained list alkynyl-functional cage modle polyhedral polysilsesquioxane in the cage modle polyhedral polysilsesquioxane of end carboxyl and step 2 carry out respectively infrared (IR), nuclear-magnetism test (
1hNMR), to characterize product structure.
In step 1 and 2, the IR spectrogram of products therefrom is shown in Fig. 1, its
1hNMR spectrogram is shown in Fig. 2.By Fig. 1 and Fig. 2, the change of related functional group can be found out: at 1640cm
-1allylic double bond peak complete reaction, simultaneously at 1710cm
-1occur the characteristic peak of C=O, contrast contains the cage modle polyhedral polysilsesquioxane of end carboxyl and single alkynyl-functional's cage modle polyhedral polysilsesquioxane, finds 1710cm
-1c=O characteristic peak in place disappears, at 3312cm
-1there is the peak position of alkynyl H in place, 1652cm
-1there is the characteristic peak of primary amide carbon, 1537cm
-1for CNH angle vibration be coupled with C-N stretching vibration, division place spectral line, confirm reaction.From Fig. 2, see the remaining peak of the alkynyl hydrogen can seen at δ=2.27ppm, in addition, δ=4.10,4.12ppm is respectively the CH connected with NH
2absorption peak, be the CH that both sides are respectively S and N element at δ=3.25ppm
2absorption peak, present one unimodal, confirm product structure equally.
Embodiment 2
Step 1: 5g seven isobutyl-allyl group POSS (5.8mmol) and 0.4ml Thiovanic acid (7.2mmol) are dissolved completely in 20ml tetrahydrofuran (THF), add 0.05g light trigger benzophenone (BP afterwards, 0.3mmol), under 365nm ultraviolet lamp, Photoinitiated reactions is carried out.Whole reaction system is at room temperature at the uniform velocity stirring reaction 12h.After reaction terminates, reaction drop is carried out precipitate, drying, obtain the cage modle polyhedral polysilsesquioxane of end carboxyl, productive rate is 97%.
Step 2: identical with the step 2 in embodiment 1, obtains single alkynyl-functional's cage modle polyhedral polysilsesquioxane.
Embodiment 3
Step 1: similar to the step 1 of embodiment 2, obtains the cage modle polyhedral polysilsesquioxane of end carboxyl, and its difference is that the light trigger used is benzoin methyl ether (DMPA).
Step 2: identical with the step 2 of embodiment 2, obtains single alkynyl-functional's cage modle polyhedral polysilsesquioxane.
Embodiment 4
Step 1: identical with the step 1 of embodiment 1, obtains the cage modle polyhedral polysilsesquioxane of end carboxyl.
Step 2: similar to the step 2 of embodiment, obtain single alkynyl-functional's cage modle polyhedral polysilsesquioxane, its difference is to use 0.43g to tie up aqua dicyclohexylcarbodiimide (DCC, 2.1mmol), use 0.05g catalyzer DMAP (DMAP, 0.4mmol), productive rate is 85%.
Embodiment 5
Step 1: identical with the step 1 of embodiment 1, obtains the cage modle polyhedral polysilsesquioxane of end carboxyl.
Step 2: similar to the step 2 of embodiment 1, obtains single alkynyl-functional's cage modle polyhedral polysilsesquioxane, and its difference is that use 146 μ l propargyl ethanol (2.5mmol) replaces propargyl, and productive rate is 89%.
Single alkynyl cage modle polyhedral polysilsesquioxane of gained in step 2 is carried out infrared and nuclear-magnetism test, gained IR spectrogram is shown in Fig. 3,
1hNMR spectrogram is shown in Fig. 4.The change of related functional group can be found out: at 1640cm by Fig. 3 and Fig. 4
-1allylic double bond peak complete reaction, simultaneously at 1710cm
-1occur the characteristic peak of C=O, contrast contains the cage modle polyhedral polysilsesquioxane of end carboxyl and single alkynyl-functional's cage modle polyhedral polysilsesquioxane, finds 1710cm
-1c=O characteristic peak in place disappears, at 3309cm
-1there is the peak position of alkynyl H in place, 1744cm
-1there is ester carbonyl group characteristic peak, confirm product structure.Find out that the remaining peak of the alkynyl of alkynyl H appears in δ=2.51ppm place in fig. 2, δ=4.75,4.76ppm is the CH connected with O
2absorption peak, be the CH that both sides are respectively S and O element at δ=3.25ppm
2absorption peak, confirms product structure equally.
Embodiment 6
Step 1: identical with the step 1 of embodiment 5, obtains the cage modle polyhedral polysilsesquioxane of end carboxyl.
Step 2: similar to the step 2 of embodiment 5, obtain single alkynyl-functional's cage modle polyhedral polysilsesquioxane, its difference is to use 0.43g to tie up aqua dicyclohexylcarbodiimide (DCC, 2.1mmol) replace EDC.HCl, and use 0.05g catalyzer DMAP (DMAP, 0.4mmol), productive rate is 86%.
Embodiment 7
Step 1: 2g octavinyl-POSS (3.16mmol) and 0.656ml Thiovanic acid (9.5mmol) are dissolved completely in 20ml tetrahydrofuran (THF), then 0.03g thermal initiator Diisopropyl azodicarboxylate (AIBN is added, 0.18mmol), constant temperature oil bath reaction system being placed in 80 DEG C refluxes 5h, carries out thermal booster reaction.After reaction terminates, precipitated by reaction solution, drying obtains three carboxy-functionalized cage modle polyhedral polysilsesquioxane, and productive rate is 98%.
Step 2: obtain in step 1 three carboxy-functionalized cage modle polyhedral polysilsesquioxane 1g (1.1mmol), propargyl amine 330 μ l (4.8mmol) are dissolved in 20ml methylene dichloride, then add 0.66g and tie up aqua EDC.HCl (3.3mmol) and 0.026g catalyzer DMAP (0.2mmol), by reaction system at 35 DEG C of stirring reaction 12h, after reaction terminates, reaction solution washing, extraction, volatilization and drying are obtained three alkynyl-functional's cage modle polyhedral polysilsesquioxane, and productive rate is 82%.
Infrared (IR) spectrogram of products therefrom is shown in Fig. 5.As can be seen from Figure 5, contrast octavinyl-POSS and step 1 product, at 1715cm
-1there is the characteristic peak of obvious C=O, in the product of step 2, at 3302cm
-1there is the peak position of alkynyl H in place, 1768cm
-1there is ester carbonyl group characteristic peak, confirm product structure.
Embodiment 8
Step 1: similar to the step 1 of embodiment 7, its difference is that Thiovanic acid consumption is 1.09ml (15.8mmol), and finally obtain five carboxy-functionalized cage modle polyhedral polysilsesquioxane, productive rate is 95%.
Step 2: similar to the step 2 of embodiment 7, its difference is, five carboxy-functionalized cage modle polyhedral polysilsesquioxane 1g (0.9mmol) and propargyl amine 469 μ l (6.8mmol) are dissolved in 20ml methylene dichloride, then add 0.87g and tie up aqua EDC.HCl (4.6mmol) and 0.03g catalyzer DMAP (0.25mmol), finally obtain five alkynyl-functional's cage modle polyhedral polysilsesquioxane, productive rate is 81%.
Infrared (IR) spectrogram of products therefrom is shown in Fig. 6.As can be seen from Figure 6, contrast octavinyl-POSS and step 1 product, at 1711cm
-1there is the characteristic peak of obvious C=O, in the product of step 2, at 3305cm
-1there is the peak position of alkynyl H in place, 1759cm
-1there is ester carbonyl group characteristic peak, confirm product structure.
Embodiment 9
Step 1: similar to the step 1 of embodiment 7, its difference is that Thiovanic acid consumption is 1.75ml (25.3mmol), and finally obtain eight carboxy-functionalized cage modle polyhedral polysilsesquioxane, productive rate is 95%.
Step 2: similar to the step 2 of embodiment 7, its difference is, eight carboxy-functionalized cage modle polyhedral polysilsesquioxane 1g (0.73mmol) and propargyl amine 602 μ l (8.76mmol) are dissolved in 20ml methylene dichloride, then 1.12g catalyzer EDC.HCl (5.84mmol) and 0.04g catalyzer DMAP (0.3mmol) is added, finally obtain eight alkynyl-functional's cage modle polyhedral polysilsesquioxane, productive rate is 85%.
Products therefrom
1hNMR spectrogram is shown in Fig. 5.Find out from spectrogram, the remaining peak completely dissolve of the vinyl of product at δ=5.5-6.5ppm place in step 1 and step 2, and there is the broad peak of typical carboxyl functional group at δ=8.5-10ppm place, there is the remaining peak of the alkynyl of ≡ H in δ=2.25ppm place, confirm product structure.
test example
Experimental example 1: infrared (IR) tests
Adopt Nicolet company of U.S. Nexsus670-FTIR, KBr film, sweep limit: 4000cm
-1-400cm
-1.
Experiment 2: nuclear-magnetism (
1hNMR) test
Adopt BrukerAvance400MHz Liquid NMR spectrometer, deuterochloroform is solvent, tests under room temperature.
Below describe the present invention through the specific embodiment and the embodiment, but these illustrate just illustrative, and should not be construed as limiting the scope of the invention.When not departing from the present invention's spirit and protection domain, those skilled in the art can carry out multiple improvement, modification or equivalencing to technical solutions and their implementation methods of the present invention, and these all should fall within the scope of protection of the present invention.
The all documents mentioned in literary composition, introduce in full at this, as a reference.
Claims (7)
1., containing a functionalized cage modle polyhedral polysilsesquioxane for alkynyl, it is obtained by the method comprised the following steps:
(1) under initiator exists, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and propargyl amine or propargyl ethanol reaction, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl;
Wherein, containing holding the cage modle polyhedral polysilsesquioxane of thiazolinyl by shown in following formula I
Wherein, R is hydrogen, ethyl, propyl group, isobutyl-, iso-octyl, cyclopentyl, cyclohexyl or phenyl independently of one another, and R ' is ethyl, propyl group, butyl or phenyl;
Or containing holding the cage modle polyhedral polysilsesquioxane of thiazolinyl by shown in Formula Il
Or, be seven isobutyl vinyl ether-glycidyl silsesquioxanes, seven phenyl vinyl silsesquioxanes, seven ethyl vinyl silsesquioxanes, seven cyclohexylvinyl silsesquioxanes containing the cage modle polyhedral polysilsesquioxane of end thiazolinyl;
The described alkyl carboxylic acid containing sulfydryl is formula HS-(CH
2)
nmercaptoalkyl carboxylic acid shown in-COOH, wherein n=1-12.
2., containing a functionalized cage modle polyhedral polysilsesquioxane for alkynyl, it is obtained by the method comprised the following steps:
(1) under initiator exists, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and propargyl amine or propargyl ethanol reaction, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl;
Wherein, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is seven isobutyl-allyl group silsesquioxanes, seven phenyl allyl silsesquioxanes, seven allyl ethyl silsesquioxanes, seven cyclopentyl allyl group silsesquioxanes and seven cyclohexyl allyl group silsesquioxanes;
The described alkyl carboxylic acid containing sulfydryl is formula HS-(CH
2)
nmercaptoalkyl carboxylic acid shown in-COOH, wherein n=1-12.
3., containing a preparation method for the functionalized cage modle polyhedral polysilsesquioxane of alkynyl, the method comprises the following steps:
(1) under initiator exists, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtains the cage modle polyhedral polysilsesquioxane containing end carboxyl;
(2) tiing up under aqua and catalyzer exist, gained, containing the cage modle polyhedral polysilsesquioxane of end carboxyl and propargyl amine or propargyl ethanol reaction, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
4. according to the preparation method of the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl described in claim 3, wherein, step (1) is: under photosensitizers exists, under UV-irradiation, cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, obtain the cage modle polyhedral polysilsesquioxane containing end carboxyl, described photosensitizers is selected from 2-hydroxy-2-methyl-1-phenyl-acetone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzoin methyl ether, or
Under thermal initiator exists, under heating state, the cage modle polyhedral polysilsesquioxane containing end thiazolinyl is reacted with the alkyl carboxylic acid containing sulfydryl, and obtain the cage modle polyhedral polysilsesquioxane containing end carboxyl, thermal initiator is selected from Diisopropyl azodicarboxylate.
5. according to the preparation method of the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl described in claim 3 or 4, wherein, in step (2), tie up aqua and be selected from dicyclohexylcarbodiimide and 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
6., according to the preparation method of the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl described in claim 3 or 4, wherein, in step (2), catalyzer is selected from DMAP and I-hydroxybenzotriazole.
7. the preparation method of the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl according to claim 3, comprises the following steps:
(1) by containing after the cage modle polyhedral polysilsesquioxane of terminal olefine and mercaptoalkyl acid dissolve, add initiator, carry out mercapto-olefin addition reaction, after reaction terminates, reaction solution is precipitated in acetonitrile, filters the cage modle polyhedral polysilsesquioxane obtained containing end carboxyl;
(2) by after dissolving containing the cage modle polyhedral polysilsesquioxane of end carboxyl, propargyl amine or propargyl ethanol, add and tie up aqua and catalyzer, at room temperature react, reaction terminates rear washing, precipitation, obtains the functionalized cage modle polyhedral polysilsesquioxane containing alkynyl.
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| CN106279246B (en) * | 2015-05-21 | 2018-12-18 | 北京化工大学 | Furans is functionalized double tower type polyhedral oligomeric silsesquioxane and preparation method thereof |
| CN105418670B (en) * | 2015-12-11 | 2018-02-09 | 华东理工大学 | Poly- (acetenyl dimethyl silica) silsesquioxane of cage modle eight and its synthetic method |
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| CN110511383B (en) * | 2019-08-29 | 2020-10-23 | 北京理工大学 | Zinc-containing polyhedral oligomeric silsesquioxane coordination polymer and preparation method and application thereof |
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