CN101503420A - Octa-epoxy cage type sesquialter siloxane and preparation thereof - Google Patents
Octa-epoxy cage type sesquialter siloxane and preparation thereof Download PDFInfo
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Abstract
The invention relates to octa-epoxy group cage-like silsesquioxane and a preparation method thereof. At present, the preparation of the cage-like silsesquioxane is generally not functionalized, and has a plurality of synthesis steps, low yield and too high cost. The cage-like silsesquioxane with epoxy groups is most noticeable with unique performance, but the existing cage-like silsesquioxane prepared by taking vinyl trichlorosilane as a raw material through hydrolytic condensation and oxidation is not completely epoxidized, and most of final products are mixtures. The preparation method takes industrialized tetramethyl orthosilicate or tetraethyl orthosilicate as a primary raw material, firstly synthesizes hydrated octa cage-like silicate through hydrolytic condensation, and then prepares the octa-epoxy group cage-like silsesquioxane with flexible chains through hydrosilation reaction and hydrosilylation reaction. The invention is simple and feasible, has high yield and single product structure, and is suitable for industrialized production; and the octa-epoxy group cage-like silsesquioxane has high reactivity, and is easily modified by being compounded with resins such as epoxy resin, phenolic resin, nylon, and the like so as to prepare composite materials with high performance.
Description
Technical field:
The present invention relates to a kind of octa-epoxy cage type sesquialter siloxane and preparation method thereof.
Background technology:
Silsesquioxane (silsesquioxane) is that a class contains RSiO1.5 (O in the molecule: Si=1.5: the 1) material of structure, R substituting group are hydrogen, alkyl, thiazolinyl, aryl, arylidene, epoxy group(ing) and their derivatives group.Silsesquioxane can be used as presoma, functional polymer, liquid crystal material and the electroluminescent material etc. of hybrid inorganic-organic materials, and very application prospects is arranged.According to the structure difference, silsesquioxane can be divided into random structure, ladder structure, half cage structure and cage structure.Wherein the cagelike silsesquioxane performance is excellent in outstanding, has caused great interest of people and concern in recent years.
Polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane, POSS), because of its shape is called as cagelike silsesquioxane like cage.When n=8, the structure of cagelike silsesquioxane is a regular cube, and the Si atom is positioned at cubical 8 drift angles, and per two adjacent Si atoms connect (being called for short T8) by an O atom, and the size of cagelike structure is more than 1.5nm.Angle from molecular structure, POSS has realized that organic group combines with covalent linkage with inorganic group, so comparing with common inorganic nano-particle is a kind of novel nano particle, and the organic group that connects on its Si atom can design, therefore can obtain the POSS of different structure, the POSS of ligation functional group can with the polymer monomer copolymerization with the different polymkeric substance of processability/POSS nano-hybrid material; The POSS of functionalized modification, can be directly directly be scattered in the polymeric matrix in the mode of physical blending around inorganic core with organic group in addition, prepares polymkeric substance/POSS blend nano composite material.Because special construction and the performance of POSS make its novel nano particle that becomes the preparation Organic, thereby become one of focus of Materials science research.
Everybody is in the ascendant to the research of cage type sesquialter silane at present, and existing cagelike silsesquioxane drift angle is failed functionalized more, as phenyl cagelike silsesquioxane, normal-butyl cagelike silsesquioxane etc.Non-functionalized cage-type silsesquioxane is present in the hybrid material with crystalline form usually, and is easy to reunite.Have only the functionalized dispersion that could realize molecular level of cage-type silsesquioxane, could really embody the nano-meter characteristic of cage-type silsesquioxane.Pan Jingbin etc. utilize eight functionalized anilino cagelike silsesquioxane (OAPS) modified polyimides (PI), make the PI/POSS nano-hybrid material.The result shows that compare with pure polyimide, OAPS modification PI improves a lot in resistance toheat, dynamic modulus etc.Y.LLiu etc. show that with monoamine propyl group POSS modified epoxy, result having amino POSS and Resins, epoxy has good intermiscibility, is evenly distributed in epoxy matrix.The existence of Si-O skeleton effectively raises the thermal characteristics and the flame retardant properties of matrix material, has good application prospects.
In sum, how to prepare functionalized POSS and become restriction POSS key issue in application problem.Epoxide group has the reactive behavior height, can with multiple functional group reactions advantages such as (as Ammonia, anhydrides), therefore prepare and have the octa-epoxy cagelike silsesquioxane and have great potential application foreground.
The epoxidised cage-type silsesquioxane of synthetic part is starting raw material with the vinyl trichloro silane at present, through 1～2 all hydrolytic condensations, prepares eight vinyl cagelike silsesquioxanes earlier.Make part epoxy group(ing) cage type sesquialter silane through oxidation then.Epoxy group(ing) cagelike silsesquioxane through the preparation of this kind method, average each cagelike silsesquioxane can only have 3～4 epoxy group(ing), and the relative position of epoxy group(ing) is unfixing, and what obtain is the cagelike silsesquioxane mixture that has different numbers and different positions epoxy group(ing).And the epoxy group(ing) that this kind method obtains directly is connected on the skeleton Si of cagelike silsesquioxane, because steric hindrance is bigger, reactive behavior reduces greatly, has influenced the dispersion of epoxy group(ing) cagelike silsesquioxane in other resin, and then influences its use properties.
And be not reported at present about octa-epoxy cage type sesquialter siloxane of having the certain-length flexible chain and preparation method thereof.The invention provides a kind of octa-epoxy cagelike silsesquioxane preparation method who has soft segment of preparation.
Summary of the invention:
The invention provides a kind of octa-epoxy cage type sesquialter siloxane and preparation method thereof, with industrialized positive tetraethyl orthosilicate or positive quanmethyl silicate is the synthetic cage-type silsesquioxane silicate of primary raw materials, utilize the preparation of cagelike silsesquioxane silicate to have eight poly-(dimethylsilyl bis) silsesquioxanes of Si-H active function groups then, utilize Si-H and glycidyl allyl ether that two key addition reactions take place again, make the octa-epoxy cagelike silsesquioxane.
A kind of octa-epoxy cage type sesquialter siloxane, its structural formula is as follows:
The preparation method of above-mentioned octa-epoxy cage type sesquialter siloxane comprises synthetic, the preparation of eight poly-(dimethylsilyl bis) silsesquioxanes of the poly-clathrasil hydrochlorates of hydration eight, three steps of preparation of octa-epoxy silsesquioxane, and is specific as follows:
(1) under the room temperature, one of tetraethoxysilane or tetramethoxy-silicane are added drop-wise in one of the aqueous solution of Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide, the mass percent concentration of tetraethoxysilane or tetramethoxy-silicane is 15～20wt%, is warming up to 50～60 ℃ of reaction 10～15h after stirring and obtains reaction solution; With rotatory evaporator reaction solution is concentrated 8～10 times, place refrigerator and cooled to freeze and make its crystallization, crystal is through washing with acetone, and vacuum-drying gets white hydration eight poly-clathrasil hydrochlorates;
(2) will join normal hexane: N in the dimethylchlorosilane, the dinethylformamide volume ratio is in 1: 1～3: 1 the mixed solvent, and the frozen water cooling obtains reaction system; Wherein the volume ratio of dimethylchlorosilane and mixed solvent is 1: 6～1: 4;
And then the hydration eight poly-cage modle silicate that step (1) is obtained join in the above-mentioned reaction system, behind stirring at room 2～3h, add volume ratio with mixed solvent and be 2: 1 frozen water; Tell organic layer with separating funnel, after wash with water to neutrality; To be washed to the neutral organic layer with rotatory evaporator and concentrate 10 times, the volume ratio of adding and mixed solvent is 1: 2～1: 1 a dehydrated alcohol then, be cooled to separate out until a large amount of crystal below 5 ℃, after filtration, vacuum-drying gets eight poly-(dimethylsilyl bis) silsesquioxane crystal;
(3) eight poly-(dimethylsilyl bis) silsesquioxane crystal and the catalyzer 1 that step (2) obtained, 3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) joins in the exsiccant toluene; The consumption of toluene makes the mass concentration of eight poly-(dimethylsilyl bis) silsesquioxanes maintain 10%～20%, and the add-on of catalyzer and eight poly-(dimethylsilyl bis) silsesquioxane crystalline mol ratios are 0.5～2%; Reaction system is reflux under nitrogen protection, drips glycidyl allyl ether in system, and allyl group base glycidyl ether mole dosage is 9.6～12 times of eight poly-(dimethylsilyl bis) silsesquioxane mole dosage, dropwises afterreaction 10～15h; Unnecessary solvent and unreacted glycidyl allyl ether are removed in underpressure distillation, finally obtain thick octa-epoxy cage type sesquialter siloxane, productive rate 〉=96%.
The preparation method's of octa-epoxy cage type sesquialter siloxane of the present invention synthetic route is as follows:
Wherein Pt (dvs) is 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0)
The present invention compares the unusual effect that has with background technology:
Success of the present invention cagelike silsesquioxane is carried out functional modification, the epoxide group of being introduced has the reactive behavior height, can with the advantage of multiple functional group reactionses such as amino, hydroxyl.And each cagelike silsesquioxane is introduced 8 epoxide groups, compare with background technology, improved the functionality of single cagelike silsesquioxane greatly, can effectively improve its reactive behavior, and then raising intermiscibility, reach Nano grade and disperse, a kind of inorganic precursor of excellent property is provided for preparation organic-inorganic nano material.
In addition, synthetic method of the present invention is starting raw material, the extensive and low price of raw material sources because of using industrialized positive tetraethyl orthosilicate or positive quanmethyl silicate.And the preparation process that present method is related, post-treating method is simple, is suitable for suitability for industrialized production.The method of the invention also has high yield characteristics, usually greater than 85%.
Embodiment:
Example 1
(1) the poly-clathrasil hydrochlorates of hydration eight (Tetramethylammonium silicate " Octanion ') is synthetic.
Under the room temperature, the 104.0g tetraethoxysilane is added drop-wise in the 590g10wt% tetramethylammonium hydroxide aqueous solution, is warming up to 50 ℃ after stirring, reaction 15h obtains reaction solution under this temperature.With rotatory evaporator reaction solution is concentrated 10 times, place refrigerator and cooled to freeze and make its crystallization, crystal is washed through acetone, and vacuum-drying gets white hydration eight poly-clathrasil hydrochlorate 106.1g, productive rate 95%.Its nucleus magnetic resonance and infrared absorption analysis characterization data are:
29Si-NMR (119MHz, CD
3OD, 300K, ppm)-99.1;
13C-NMR (159MHz, CD
3OD, 300K, ppm) 15.10;
1H-NMR (600MHz, CD
3OD, 300K, ppm) 3.19; FTIR (cm
-1, KBr) 3393,1643 (v
N-O), 1489 (v
As C-N), 1116 (v
Si-O-Si).
(2) contain 60ml normal hexane, 60ml N with once joining in the 20ml dimethylchlorosilane, in the mixed solvent of dinethylformamide, the frozen water cooling.And then the hydration cage modle silicate 2.85g that step (1) obtains joined in the above-mentioned reaction system of reaction, behind the stirring at room 2h, add the 240ml frozen water.Tell organic layer with separating funnel, after wash with water to neutrality.With rotatory evaporator organic layer is concentrated, add the 80ml dehydrated alcohol then, put into refrigerator cooling 2h, have crystal to separate out, after filtration, vacuum-drying gets crystal 1.54g.Its nucleus magnetic resonance and infrared absorption analysis characterization data are:
29Si-NMR (119MHz, CD
3OD, 300K, ppm)-108.5,12.5; FTIR (cm
-1, KBr) 2967 (v
As C-H), 2145 (v
Si-H), 1259 (v
C-N), 1097 (v
Si-O-Si).
(3) 1 of eight poly-(dimethylsilyl bis) silsesquioxane 2.04g that step (2) obtained and 1.4g1wt%; 3-divinyl-1; 1; 3; 3-tetramethyl disiloxane platinum (0) (Pt (dvs)) joins in the 18.36g exsiccant toluene; reflux under nitrogen protection drips glycidyl allyl ether in reaction system, reacted 10 hours.Unnecessary solvent and unreacted glycidyl allyl ether are removed in pressure distillation, obtain heavy-gravity octa-epoxy cage type sesquialter siloxane 3.78g, productive rate 98%.Its nucleus magnetic resonance and infrared absorption analysis characterization data are:
29Si?NMR(119MHz，CD
3OD，300K，ppm)-107.0，15.3；FTIR(cm
-1，KBr)2967(v
as?C-H)，1259(v
as?C-N)，1097(v
Si-O-Si)。
Example 2
(1) the poly-clathrasil hydrochlorates of hydration eight (Tetramethylammonium silicate " Octanion ') is synthetic.
Under the room temperature, the 104.0g tetraethoxysilane is added drop-wise in the 936g10wt% tetramethylammonium hydroxide aqueous solution, is warming up to 60 ℃ after stirring, continue reaction 10h and obtain reaction solution.With rotatory evaporator reaction solution is concentrated into 8 times, places refrigerator and cooled to freeze and make its crystallization, crystal is washed through acetone, and vacuum-drying gets white hydration eight poly-clathrasil hydrochlorate 108.3g, productive rate 97%.Its nucleus magnetic resonance and infrared absorption analysis characterization data are:
29Si-NMR (119MHz, CD
3OD, 300K, ppm)-99.1;
13C-NMR (159MHz, CD
3OD, 300K, ppm) 15.10;
1H-NMR (600MHz, CD
3OD, 300K, ppm) 3.19; FTIR (cm
-1, KBr) 3393,1643 (v
N-O), 1489 (v
AsC-N), 1116 (v
Si-O-Si).
(2) contain 90ml normal hexane, 30ml N with once joining in the 30ml dimethylchlorosilane, in the mixed solvent of dinethylformamide, the frozen water cooling.And then the hydration cage modle silicate 2.85g that step (1) obtains joined in the above-mentioned reaction system of reaction, behind the stirring at room 3h, add the 240ml frozen water.Tell organic layer with separating funnel, after wash with water to neutrality.With rotatory evaporator organic layer is concentrated, add the 80ml dehydrated alcohol then, put into refrigerator cooling 3h, have crystal to separate out, after filtration, vacuum-drying gets crystal 1.54g, productive rate 95%.Its nucleus magnetic resonance and infrared absorption analysis characterization data are:
29Si-NMR (119MHz, CD
3OD, 300K, ppm)-108.5,12.5; FTIR (cm
-1, KBr) 2967 (v
As C-H), 2145 (v
Si-H), 1259 (v
C-N), 1097 (v
Si-O-Si).
(3) eight poly-(dimethylsilyl bis) silsesquioxane 2.04g that step (2) obtained add 1 of 0.35g1wt%; 3-divinyl-1; 1; 3; 3-tetramethyl disiloxane platinum (0) (Pt (dvS)) joins in the 8.12g exsiccant toluene; reflux under nitrogen protection drips glycidyl allyl ether in reaction system, reacted 15 hours.Unnecessary solvent and unreacted glycidyl allyl ether are removed in pressure distillation, obtain heavy-gravity octa-epoxy cage type sesquialter siloxane 3.78g, productive rate 98%.Its nucleus magnetic resonance and infrared absorption analysis characterization data are:
29Si?NMR(119MHz，CD
3OD，300K，ppm)-107.0，15.3；FTIR(cm
-1，KBr)2967(v
as?C-H)，1259(v
as?C-N)，1097(v
si-o-si)
Claims (2)
1. octa-epoxy cage type sesquialter siloxane, its structural formula is as follows:
2. the preparation method of an octa-epoxy cage type sesquialter siloxane is characterized in that, may further comprise the steps:
(1) under the room temperature, one of tetraethoxysilane or tetramethoxy-silicane are added drop-wise in one of the aqueous solution of Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide, the mass percent concentration of tetraethoxysilane or tetramethoxy-silicane is 15～20wt%, is warming up to 50～60 ℃ of reaction 10～15h after stirring and obtains reaction solution; With rotatory evaporator reaction solution is concentrated 8～10 times, place refrigerator and cooled to freeze and make its crystallization, crystal is through washing with acetone, and vacuum-drying gets white hydration eight poly-clathrasil hydrochlorates;
(2) will join normal hexane: N in the dimethylchlorosilane, the dinethylformamide volume ratio is in the mixed solvent of 1:1～3:1, and the frozen water cooling obtains reaction system; Wherein the volume ratio of dimethylchlorosilane and mixed solvent is 1:6～1:4;
And then the hydration eight poly-cage modle silicate that step (1) is obtained join in the above-mentioned reaction system, and behind stirring at room 2～3h, the volume ratio that adds with mixed solvent is the frozen water of 2:1; Tell organic layer with separating funnel, after wash with water to neutrality; To be washed to the neutral organic layer with rotatory evaporator and concentrate 10 times, adding is the dehydrated alcohol of 1:2～1:1 with the volume ratio of mixed solvent then, be cooled to separate out until a large amount of crystal below 5 ℃, after filtration, vacuum-drying gets eight poly-(dimethylsilyl bis) silsesquioxane crystal;
(3) eight poly-(dimethylsilyl bis) silsesquioxane crystal and the catalyzer 1 that step (2) obtained, 3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) joins in the exsiccant toluene; The consumption of toluene makes the mass concentration of eight poly-(dimethylsilyl bis) silsesquioxanes maintain 10%～20%, and the add-on of catalyzer and eight poly-(dimethylsilyl bis) silsesquioxane crystalline mol ratios are 0.5～2%; Reaction system is reflux under nitrogen protection, drips glycidyl allyl ether in system, and allyl group base glycidyl ether mole dosage is 9.6～12 times of eight poly-(dimethylsilyl bis) silsesquioxane mole dosage, dropwises afterreaction 10～15h; Unnecessary solvent and unreacted glycidyl allyl ether are removed in underpressure distillation.
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