CN101117441A - Polyethylene silicon resin containing ethenyl cage model sesquialter siloxane and method for making same - Google Patents
Polyethylene silicon resin containing ethenyl cage model sesquialter siloxane and method for making same Download PDFInfo
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- CN101117441A CN101117441A CNA2007100985395A CN200710098539A CN101117441A CN 101117441 A CN101117441 A CN 101117441A CN A2007100985395 A CNA2007100985395 A CN A2007100985395A CN 200710098539 A CN200710098539 A CN 200710098539A CN 101117441 A CN101117441 A CN 101117441A
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Abstract
A polyvinyl silicone resin containing vinyl cage-like silsesquioxane and the method of preparation thereof belong to the organic-inorganic hybrid material technical field, in particular relates to a polyvinyl silicone resin containing vinyl cage-like silsesquioxane being in liquid state at normal temperature and the method of preparation thereof. The silicone resin which contains vinyl cage-like silsesquioxane and is in liquid state at normal temperature comprises liquid resin and vinyl cage-like silsesquioxane solid particle, wherein the molar percentage of the liquid resin in the whole system is 70 percent to 85 percent, while the molar percentage of the vinyl cage-like silsesquioxane is 15 percent and 30 percent. The method of preparation is as follows: vinyl trialkoxysilane which is adopted as raw material is hydrolyzed under acid-catalyzed condition and then is separated and purified to obtain the mixtures. The invention has the advantages that: with simple preparing process, short cycle and low cost, the resin does not contain solvent and possesses low viscosity at normal temperature; meanwhile, the invention overcomes the disadvantage of high content of silicone hydroxyl inside ordinary acid hydrolytic synthetic silicone resin.
Description
Technical field:
The invention belongs to the hybrid inorganic-organic materials technical field, polyethylene silicon resin that contains ethenyl cage model sesquialter siloxane (Vi-POSS) (PVSQ) that is in a liquid state under particularly a kind of normal temperature and preparation method thereof.
Background technology:
In recent years, (the Hybrid Plastics of U.S. hybrid material company, LLC, Fountain Valley, CA (US)) and domestic and international many research institutions all in the research of being devoted to based on the monomeric new chemical material of Vi-POSS, the patent No. is the United States Patent (USP) of US 6911518 B2, US6927270 B2, discloses synthetic, the structural parameter of the base POSS of functional group and the technology of application.The patent No. is that the Japanese Patent of JP 2007015991 discloses (the Tokyo University of Science of Tokyo University of Science and Technology, Japan) preparation method, this technology adopts the method for base catalysis to prepare Vi-POSS, at present, cage-type silsesquioxane (Vi-POSS) existing procucts (CAS[69655-76-1]) that contain vinyl.But because the synthesis technique complexity of functional group POSS (cage-type silsesquioxane) own, the production cycle is longer, and the cost height is poor with most resin mutual solubility, is difficult to practical application, does not appear in the newspapers especially for the hybrid resin that contains the POSS particulate that contains multifunctional group.
Summary of the invention:
The objective of the invention is to prepare a kind of vinyl and two kinds of active groups of alkoxyl group of containing, the uniform polyethylene silicon resin of vinyl POSS microparticulate, this product does not contain solvent, and can overcome the high shortcoming of silicon hydroxy radical content in the synthetic silicone resin of common acidic hydrolysis.A kind of reaction conditions milder, operation is easier, reaction time is shorter preparation method are provided simultaneously.
Particular content of the present invention is as follows:
Indication of the present invention contains polyethylene silicon resin (PVSQ) mixture of ethenyl cage model sesquialter siloxane (Vi-POSS), comprises liquid resin and Vi-POSS solid particulate, and wherein liquid resin structural formula (derivation result in theory) is:
Wherein: n is 2～4, and R is methyl, ethyl or ethanoyl;
The structural formula of Vi-POSS is:
The molar ratio of described liquid resin in whole system is 70%～85%, and the molar ratio in whole system of ethenyl cage model sesquialter siloxane is 15%～30%.
Preparation process of mixture of the present invention comprises the steps:
(1) at 0～120 ℃, with 1 part of vinyl trialkyl oxysilane and 1～5 part of solvent, drip with the amount of vinyl trialkyl oxysilane than being 1～10 water and an acidic catalyst of 0.1～3wt%, hydrolysis 1～10 hour obtains the silane hydrolyzate prepolymer;
(2) improve 10～50 ℃ of Heating temperatures, separate, remove water purification, alcohols and an acidic catalyst, obtain the resin crude product with water trap;
(3) be equal to or higher than under the 0.05Mpa condition with vacuum tightness at 50～100 ℃, the solvent in the resin crude product is removed, re-use whizzer and separate, get the clarifying resin part in upper strata;
(4) be equal to or higher than under the 0.09Mpa condition with vacuum tightness at 100～150 ℃, behind the minimal residue solvent in the Ex-all clarification resin part, must contain the polyethylene silicon resin mixture of ethenyl cage model sesquialter siloxane.
Said solvent comprises toluene, tetrahydrofuran (THF), acetone, ethanol, alkane, hexanaphthene, ethyl acetate or methyl alcohol.These solvents all are this area usual vehicles commonly used, believe that those skilled in the art are appreciated that the using method of these solvents in conjunction with the embodiments.
Described an acidic catalyst is meant mineral acid and solution, acid organometallic compound and solution thereof, acid organic acid and solution thereof, preferred hydrochloric acid.
Beneficial effect of the present invention is: the synthetic mixture is a kind of liquid hybrid resin, and this resin not only contains vinyl and two kinds of active groups of alkoxyl group, and vinyl POSS microparticulate is even.This resin the fignal center of silicon hydroxyl do not occur by adopting Infrared spectroscopy and nuclear magnetic resonance spectroscopy, has proved not hydroxyl of whole product.Whole process of preparation reaction conditions gentleness, easy and simple to handle, be easy to control, and reaction time is short, toxicity is low.
Description of drawings:
Fig. 1 is the polyethylene silicon resin (PVSQ) that contains ethenyl cage model sesquialter siloxane (Vi-POSS), and as seen the result who utilizes phase microscope to observe under 150 times of conditions is evenly distributed with the cube solid particulate in synthetic resins.
Fig. 2 is the polyethylene silicon resin (PVSQ) that contains ethenyl cage model sesquialter siloxane (Vi-POSS), utilizes phase microscope to observe under 900 times of conditions and presents cuboidal Vi-POSS.
Fig. 3 carries out Fourier infrared spectrum FT-IR to synthetic product, and wherein (A) characterizes vinyltriethoxysilane, (B) characterizes vinyl polysiloxane PVSQ, (C) characterizes Vi-POSS.
Fig. 4 resolves flight time mass spectrum, MALID-TOF-MS to the laser of Vi-POSS.
Embodiment:
The example of enumerating below preferably draws for further specifying the present invention, should be not limited to these embodiment in actual applications.
Embodiment 1
In the 500ml round-bottomed flask, add 179g (1mol) vinyltriethoxysilane, 122g (1.45mol) hexanaphthene, 38.21g aqueous hydrochloric acid.Mix back flow reaction 7 hours.Under boiling state, adopt water trap,, hydrochloric acid, water and ethanol are separated 14 hours time length by utilizing solvent proportion difference.Under 82 ℃ and vacuum tightness=0.06Mpa condition, solvent in the resin crude product in the reaction flask is removed, re-using whizzer separates under 4000 rev/mins rotating speed and (believed and it will be appreciated by those skilled in the art that in 60 minutes, the isolating time of whizzer is according to centrifuge speed and wish how much deciding of acquisition product), get the clarifying resin part in upper strata; Under 120 ℃ and vacuum tightness=0.09Mpa condition, behind the minimal residue solvent in the Ex-all clarification resin part, must contain the polyethylene silicon resin mixture of ethenyl cage model sesquialter siloxane at last.Resin state is colourless translucent thick liquid.Calculate productive rate 98.2%.
According to " mensuration of tackiness agent non-volatile content " (GB/T 2793-1995), get the 2.000g sample, set test temperature at 150 ℃, time length 180min, the solid content that records this product is 99.32%.
Synthetic product is carried out Fourier infrared spectrum characterize (see figure 3).FTIR (the cm of contrast raw material vinyltriethoxysilane
-1, KBr), synthetic product is at 1392cm
-1, 1446cm
-1And 1489cm
-1Place's characteristic peak disappears substantially.1602cm
-1And 1409cm
-1Be respectively the symmetric vibration of CH=CH and the absorption peak of plane scissors movement, 3026cm
-1And 3066cm
-1Be CH
2The symmetric vibration absorption peak C of the C-H of=CH-and the asymmetric vibration absorption peak of C-H illustrate that the ethene of synthetic product has neither part nor lot in reaction.Raw material is at 1080cm
-1Near sharp-pointed bimodal 1105cm
-1And 1081cm
-1In product, become the bimodal 1118cm of broad
-1And 1071cm
-1, illustrating that the Si-O key in the raw material has formed the Si-O-Si skeleton through hydrolytic condensation, a part has formed regular cagelike structure, and another part forms the structure silicone resin of irregularity.
Synthetic product is carried out nucleus magnetic resonance to be characterized.
1H NMR(600MHz，CDCl
3，300K，ppm)δ(-CH＝)＝5.89～5.95，δ(＝CH
2)＝6.02～6.12。
To synthetic product carry out gel permeation chromatography characterize (THF, 1mL/min, PS, 303K).Synthetic product has two components, Mn
1Be about 1900～2000, dispersion coefficient is about 1.59, and peak area is about 73.8%; Mn
2Be about 501, dispersion coefficient is about 1.12, and peak area is about 26.2%.
Embodiment 2
In the 500ml round-bottomed flask, add 148.2g (1mol) vinyltrimethoxy silane, 142g (1.45mol) toluene, the 38.21g organotin aqueous solution.Mix back flow reaction 7 hours.Under boiling state, adopt water trap,, water and ethanol are separated 12 hours time length by utilizing solvent proportion difference.Under 75 ℃ and vacuum tightness=0.06Mpa condition, the solvent in the resin crude product in the reaction flask is removed, re-use whizzer and under 4000 rev/mins rotating speed, separated 60 minutes, get the clarifying resin part in upper strata; Under 130 ℃ and vacuum tightness=0.09Mpa condition, behind the minimal residue solvent in the Ex-all clarification resin part, must contain the polyethylene silicon resin mixture of ethenyl cage model sesquialter siloxane at last.Resin state is colourless translucent thick liquid.Calculate productive rate 97.5%.
According to " mensuration of tackiness agent non-volatile content " (GB/T 2793-1995), get the 2.000g sample, set test temperature at 150 ℃, time length 180min, the solid content that records this product is 99.11%.
Synthetic product is carried out Fourier infrared spectrum to be characterized.FTIR (the cm of contrast raw material vinyltrimethoxy silane
-1, KBr).Synthetic product is 2820 and 1192cm
-1The Si-O-C at place stretches the shock absorbing peak and disappears substantially.1602cm
-1And 1409cm
-1Be respectively the symmetric vibration of CH=CH and the absorption peak of plane scissors movement, 3026cm
-1And 3066cm
-1Be CH
2The symmetric vibration absorption peak C of the C-H of=CH-and the asymmetric vibration absorption peak of C-H illustrate that the ethene of synthetic product has neither part nor lot in reaction.Raw material is at 1082cm
-1Near sharp-pointed bimodal 1103cm
-1And 1081cm
-1In product, become the bimodal 1120cm of broad
-1And 1078cm
-1, illustrating that the Si-O key in the raw material has formed the Si-O-Si skeleton through hydrolytic condensation, a part has formed regular cagelike structure, and another part forms the structure silicone resin of irregularity.
Synthetic product is carried out nucleus magnetic resonance to be characterized.
1H NMR(600MHz，CDCl
3，300K，ppm)δ(-CH＝)＝5.89～5.95，δ(＝CH
2)＝6.027～6.121。
Synthetic product is carried out gel permeation chromatography to be characterized.Synthetic product have two components (THF, 1mL/min, PS, 303K), Mn
1Be about 1900～2000, dispersion coefficient is about 1.47, and peak area is about 74.2%; Mn
1Be about 510, dispersion coefficient is about 1.14, and peak area is about 25.8%.
Embodiment 3
In the 500ml round-bottomed flask, add 179g (1mol) vinyltriethoxysilane, 122g (1.45mol) hexanaphthene, aqueous hydrochloric acid (wherein institute's water consumption is respectively 2mol, 2.5mol, 3mol).Mix back flow reaction 7 hours.Under boiling state, adopt water trap,, water and ethanol are separated 14 hours time length by utilizing solvent proportion difference.Under 82 ℃ and vacuum tightness=0.06Mpa condition, the solvent in the resin crude product in the reaction flask is removed, re-use whizzer and under 4000 rev/mins rotating speed, separated 60 minutes, get the clarifying resin part in upper strata; Under 120 ℃ and vacuum tightness=0.09Mpa condition, behind the minimal residue solvent in the Ex-all clarification resin part, must contain the polyethylene silicon resin mixture of ethenyl cage model sesquialter siloxane at last.Resin state is colourless translucent thick liquid.
Three kinds of synthetic products are carried out Fourier infrared spectrum to be characterized.FTIR (the cm of contrast raw material vinyltriethoxysilane
-1, KBr), synthetic product is at 1392cm
-1, 1446cm
-1And 1489cm
-1Place's characteristic peak disappears substantially.1602cm
-1And 1409cm
-1Be respectively the symmetric vibration of CH=CH and the absorption peak of plane scissors movement, 3026cm
-1And 3066cm
-1Be CH
2The symmetric vibration absorption peak C of the C-H of=CH-and the asymmetric vibration absorption peak of C-H illustrate that the ethene of synthetic product has neither part nor lot in reaction.Raw material is at 1080cm
-1Near sharp-pointed bimodal 1105cm
-1And 1081cm
-1In three kinds of products, become the bimodal 1118cm of broad
-1And 1071cm
-1, illustrating that the Si-O key in the raw material has formed the Si-O-Si skeleton through hydrolytic condensation, a part has formed regular cagelike structure, and another part forms the structure silicone resin of irregularity.
According to " mensuration of tackiness agent non-volatile content " (GB/T 2793-1995), get the 2.000g sample, set test temperature at 150 ℃, time length 180min, the solid content that records this product is followed successively by 98.97%, 99.15% and 99.33%.
Synthetic product is carried out nucleus magnetic resonance to be characterized.
1H NMR (600MHz, CDCl
3, 300K, correlation data ppm) is as follows:
| Vinyl polysiloxane | Represent group | δ (chemical shift, ppm) | With respect to Si-CH=CH 2Molar fraction |
| Water consumption in the hydrolysis reaction (unit, mol) | |||
| 2 | -CH＝CH 2 | 5.89～6.11 | - |
| -CH 2-CH 3 | 3.79～3.84； 1.19～1.24 | 21.56％ | |
| -OH | - | ||
| 2.5 | -CH＝CH 2 | 5.89～6.11 | - |
| -CH 2-CH 3 | 3.81～3.84； 1.19～1.24 | 19.39 | |
| -OH | - | ||
| 3 | -CH＝CH 2 | 5.89～6.11 | - |
| -CH 2-CH 3 | 3.81～3.84； 1.19～1.24 | 17.06 | |
| -OH | - |
Three kinds of synthetic products are adopted the rotary viscosity method respectively, be controlled at 23 ℃ in test temperature, the viscosity that characterizes resin is as follows:
| Water consumption in the hydrolysis reaction (unit, mol) | Viscosity (unit, Pa.s) |
| 2 | 23.75 |
| 2.5 | 35.45 |
| 3 | 48.22 |
The supplementary notes example
Below from polyethylene silicon resin (PVSQ) resin that contains ethenyl cage model sesquialter siloxane (Vi-POSS), separate to purify with the explanation of example and obtain the concrete steps of ethenyl cage model sesquialter siloxane (Vi-POSS), and carry out concise and to the point structural characterization and performance test.
This illustrative examples is based on the preparation process of embodiment 1, and other each embodiment are similar with it.
By utilizing ethenyl cage model sesquialter siloxane (Vi-POSS) different with the solvent degree of polysilsesquioxane resins (PVSQ) in solvent, at ambient temperature, get resin 10g, add 100g methyl alcohol, being stirred to resin fully dissolves, use 4000 rev/mins in whizzer, 15 minutes, obtain white solid powder 1.82g.
The product that extraction is obtained carries out infrared spectra fourier sign.1602cm
-1And 1409cm
-1Be respectively the symmetric vibration of CH=CH and the absorption peak of plane scissors movement, 3026cm
-1And 3066cm
-1Be CH
2The symmetric vibration absorption peak C of the C-H of=CH-and the asymmetric vibration absorption peak of C-H illustrate that the ethene of synthetic product has neither part nor lot in reaction.1112cm
-1Very big unimodal of intensity appears in the place.This is the charateristic avsorption band of Si-O-Si key in the cage type POSS structure.Si-O-Si is absorbed as unimodal phase in the cage type POSS structure, and is consistent with cage structure.
Synthetic product is carried out nucleus magnetic resonance to be characterized.
1H NMR(600MHz，CDCl
3，300K，ppm)δ(-CH＝)＝5.895～5.954，δ(＝CH
2)＝6.027～6.121。
13C NMR(600MHz，CDCl
3，300K，ppm)δ(-CH＝)＝128.21～129.20，δ(＝CH
2)＝136.74～136.97。
29Si NMR(600MHz，CDCl
3，300K，ppm)δ＝80.23。
29Si is the characteristic peak of typical cagelike structure.
Synthetic product measured (laser is resolved flight time mass spectrum, MALID-TOF-MS).In the mass-spectrometric data shown in Figure 4, two peaks that between m/z=400～1000Da, only occur, m/z (M+Na
+)=656.5, m/z (M+K
+)=672.4.According to inferring the molecular weight (Vi-POSS+Na that structural formula calculated that
+, Vi-POSS+K
+) with to record data in full accord.Know easily that by simple computation the molecular weight of synthetic product (Vi-POSS) is 633.0, is T
8Structure.
Claims (6)
1. a polyethylene silicon resin mixture that contains ethenyl cage model sesquialter siloxane comprises liquid resin and ethenyl cage model sesquialter siloxane solid particulate, and wherein the structural formula of liquid resin is:
Wherein: n is 2～4, and R is methyl, ethyl or ethanoyl;
The structural formula of ethenyl cage model sesquialter siloxane is:
2. the polyethylene silicon resin mixture that contains ethenyl cage model sesquialter siloxane according to claim 1, it is characterized in that: the molar ratio of described liquid resin in whole system is 70%～85%, and the molar ratio of ethenyl cage model sesquialter siloxane in whole system is 15%～30%.
3. according to the described preparation process of mixture of claim 1, comprise the steps:
(1) at 0～120 ℃, with 1 part of vinyl trialkyl oxysilane and 1～5 part of solvent, drip with the amount of vinyl trialkyl oxysilane than being 1～10 water and an acidic catalyst of 0.1～3wt%, hydrolysis 1～10 hour obtains the silane hydrolyzate prepolymer;
(2) improve 10～50 ℃ of Heating temperatures, separate, remove water purification, alcohols and an acidic catalyst, obtain the resin crude product with water trap;
(3) be equal to or higher than under the 0.05Mpa condition with vacuum tightness at 50～100 ℃, the solvent in the resin crude product is removed, re-use whizzer and separate, get the clarifying resin part in upper strata;
(4) be equal to or higher than under the 0.09Mpa condition with vacuum tightness at 100～150 ℃, behind the minimal residue solvent in the Ex-all clarification resin part, must contain the polyethylene silicon resin mixture of ethenyl cage model sesquialter siloxane.
4. preparation method according to claim 3 is characterized in that: described solvent is meant toluene, tetrahydrofuran (THF), acetone, ethanol, alkane, hexanaphthene, ethyl acetate or methyl alcohol.
5. according to the arbitrary described preparation method of claim 3 to 4, it is characterized in that: described an acidic catalyst is meant mineral acid and solution, acid organometallic compound and solution thereof, acid organic acid and solution thereof.
6. according to the described method of claim 5, it is characterized in that: described an acidic catalyst is a hydrochloric acid.
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| US6911518B2 (en) * | 1999-12-23 | 2005-06-28 | Hybrid Plastics, Llc | Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities |
| KR20000063142A (en) * | 2000-02-17 | 2000-11-06 | 이응찬 | Starting materials for manufacturing polyorganosilsesquioxanes, polyorganosilsesquioxanes and method for manufacturing polyorganosilsesquioxanes |
| WO2003064490A2 (en) * | 2001-06-27 | 2003-08-07 | Hybrid Plastics Llp | Process for the functionalization of polyhedral oligomeric silsesquioxanes |
| CN100412077C (en) * | 2006-05-19 | 2008-08-20 | 北京化工大学 | Process for preparing amino phenyl silsesquioxane |
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