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CN101117441B - A kind of polyvinyl silicone resin containing vinyl cage silsesquioxane and preparation method thereof - Google Patents

A kind of polyvinyl silicone resin containing vinyl cage silsesquioxane and preparation method thereof Download PDF

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CN101117441B
CN101117441B CN2007100985395A CN200710098539A CN101117441B CN 101117441 B CN101117441 B CN 101117441B CN 2007100985395 A CN2007100985395 A CN 2007100985395A CN 200710098539 A CN200710098539 A CN 200710098539A CN 101117441 B CN101117441 B CN 101117441B
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cage silsesquioxane
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silicone resin
vinyl cage
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CN101117441A (en
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张军营
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韩雁明
谷晓昱
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Beijing University of Chemical Technology
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Abstract

一种含乙烯基笼型倍半硅氧烷的聚乙烯基硅树脂及其制备方法，属于有机-无机杂化材料技术领域，特别涉及一种常温下呈液态的含乙烯基笼型倍半硅氧烷的聚乙烯基硅树脂及其制备方法。该树脂为一种常温下呈液态的含乙烯基笼型倍半硅氧烷的硅树脂，包含液体树脂和乙烯基笼型倍半硅氧烷固体颗粒，其中液体树脂在整个体系中的摩尔比例为70％～85％，乙烯基笼型倍半硅氧烷的摩尔比例为15％～30％；其制备方法为：以乙烯基三烷氧基硅烷为原料，在酸性催化条件下水解，再分离提纯得到该混合物。制备过程简单，周期短，成本低廉，树脂本身不含溶剂，常温下黏度低，并且克服了普通酸性水解合成硅树脂中硅羟基含量高的缺点。

Figure 200710098539

A polyvinyl silicone resin containing vinyl cage silsesquioxane and a preparation method thereof, belonging to the technical field of organic-inorganic hybrid materials, in particular to a vinyl cage silsesquioxane that is liquid at room temperature Polyvinyl silicone resins of oxanes and methods for their preparation. The resin is a silicone resin containing vinyl cage silsesquioxane that is liquid at room temperature, and contains liquid resin and solid particles of vinyl cage silsesquioxane. The molar ratio of the liquid resin in the entire system is The molar ratio of vinyl cage silsesquioxane is 15% to 30%; its preparation method is: use vinyl trialkoxysilane as raw material, hydrolyze under acidic catalytic conditions, and then The mixture was obtained by separation and purification. The preparation process is simple, the cycle is short, the cost is low, the resin itself does not contain solvent, the viscosity is low at normal temperature, and it overcomes the shortcoming of high silanol content in ordinary acid hydrolysis synthetic silicone resin.

Figure 200710098539

Description

A kind of polyethylene silicon resin that contains ethenyl cage model sesquialter siloxane and preparation method thereof
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 US6911518B2, US6927270B2, 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 JP2007015991 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:
Figure S07198539520070508D000021
Wherein: n is 2～4, and R is methyl, ethyl or ethanoyl;
The structural formula of Vi-POSS is:
Figure S07198539520070508D000022
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/T2793-1995), 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 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/T2793-1995), 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 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 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/T2793-1995), 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. 1HNMR (600MHz, CDCl 3, 300K, correlation data ppm) is as follows:
Figure S07198539520070508D000061
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)

1.一种含乙烯基笼型倍半硅氧烷的聚乙烯基硅树脂混合物，包含液体树脂1. A polyvinyl silicone resin mixture containing vinyl cage silsesquioxane, comprising a liquid resin 和乙烯基笼型倍半硅氧烷固体颗粒，其中液体树脂的结构式为：and vinyl cage silsesquioxane solid particles, wherein the structural formula of the liquid resin is:
Figure DEST_PATH_FA20186595200710098539501C00011
Figure DEST_PATH_FA20186595200710098539501C00011
 其中：n为2～4；Among them: n is 2 to 4; 乙烯基笼型倍半硅氧烷的结构式为：The structural formula of vinyl cage silsesquioxane is:
Figure DEST_PATH_FA20186595200710098539501C00012
Figure DEST_PATH_FA20186595200710098539501C00012
 2.根据权利要求1所述的含乙烯基笼型倍半硅氧烷的聚乙烯基硅树脂混合物，其特征在于：所述液体树脂在整个体系中的摩尔比例为70％～85％，乙烯基笼型倍半硅氧烷在整个体系中的摩尔比例为15％～30％。2. The polyvinyl silicone resin mixture containing vinyl cage silsesquioxane according to claim 1, characterized in that: the molar ratio of the liquid resin in the whole system is 70% to 85%. The molar ratio of cage-type silsesquioxane in the whole system is 15%-30%. 3.根据权利要求1所述混合物的制备方法，包括如下步骤：3. the preparation method of mixture according to claim 1, comprises the steps: (1)在0～120℃，将1份乙烯基三乙氧基硅烷和1～5份溶剂混合，滴加与乙烯基三乙氧基硅烷的物质量比为1～10的水，和0.1～3wt％的酸性催化剂，水解1～10小时，得到硅烷水解预聚物；(1) Mix 1 part of vinyltriethoxysilane with 1 to 5 parts of solvent at 0 to 120°C, add dropwise water with a mass ratio of 1 to 10 to vinyltriethoxysilane, and 0.1 ～3wt% acidic catalyst, hydrolysis for 1～10 hours to obtain silane hydrolysis prepolymer; (2)提高加热温度10～50℃，用分水器分离，除净水、醇类和酸性催化剂，得到树脂粗产物；(2) Increase the heating temperature by 10-50°C, separate with a water separator, remove clean water, alcohols and acidic catalysts, and obtain a crude resin product; (3)在50～100℃和真空度等于或高于0.05Mpa条件下，将树脂粗产物中的溶剂除去，再使用离心机分离，取上层澄清的树脂部分；(3) Remove the solvent in the crude resin product at 50-100°C and a vacuum degree equal to or higher than 0.05Mpa, then use a centrifuge to separate, and take the upper clarified resin part; (4)在100～150℃和真空度等于或高于0.09Mpa条件下，除净澄清树脂部分中的微量残留溶剂后，得含乙烯基笼型倍半硅氧烷的聚乙烯基硅树脂混合物。(4) Under the conditions of 100-150°C and a vacuum degree equal to or higher than 0.09Mpa, after removing a small amount of residual solvent in the clear resin part, a polyvinyl silicone resin mixture containing vinyl cage silsesquioxane is obtained . 4.根据权利要求3所述的制备方法，其特征在于：所述溶剂是指甲苯、四氢呋喃、丙酮、乙醇、烷烃、环己烷、乙酸乙酯或甲醇。4. The preparation method according to claim 3, characterized in that: the solvent is toluene, tetrahydrofuran, acetone, ethanol, alkane, cyclohexane, ethyl acetate or methanol. 5.根据权利要求3至4任一所述的制备方法，其特征在于：所述酸性催化剂是指无机酸及其溶液、酸性有机金属化合物及其溶液、酸性有机酸及其溶液。5. The preparation method according to any one of claims 3 to 4, characterized in that: the acidic catalyst refers to inorganic acids and solutions thereof, acidic organic metal compounds and solutions thereof, acidic organic acids and solutions thereof. 6.根据权利要求5所述方法，其特征在于：所述酸性催化剂是盐酸。6. The method according to claim 5, characterized in that: the acidic catalyst is hydrochloric acid.
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