CN1291991C - Preparation method of multihydroxy sesqui siloxane - Google Patents
Preparation method of multihydroxy sesqui siloxane Download PDFInfo
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- CN1291991C CN1291991C CN 03134129 CN03134129A CN1291991C CN 1291991 C CN1291991 C CN 1291991C CN 03134129 CN03134129 CN 03134129 CN 03134129 A CN03134129 A CN 03134129A CN 1291991 C CN1291991 C CN 1291991C
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Abstract
The present invention relates to a preparation method for multi-hydroxy sequin-siloxane. The prepared multi-hydroxy sequin-siloxane can be used as an intermediate body for preparing various organic-inorganic hybridized nanostructure materials. The multi-hydroxy sequin-siloxane is prepared according to the following proportion of catalysts and the method: 1. under the condition of vacuum, triethoxysilane and phenylate react according to a molar ratio of 1:2, the reaction temperature is 30 to 70 DEG C., the reaction time is 20 to 30 hours, and the reaction product is a silicane monomer; 2. the silicane monomer prepared by step 1 is dissolved in tetrahydrofuran according to a ratio of 1:1 to 2, water is added according to a ratio of 1 part of H2O to 6 parts of Si, and acid or base catalysts are added according to ratios of 0.4 part of NaOH to 0.6 part of Si, 1 part of CHOOH to 6 parts of Si and 0.01 part of NaOH to 0.1 part of Si; a hydrolytic condensation reaction is carried out at 30 to 70 DEG C. for 20 to 30 hours, and three kinds of multi-hydroxy sequin-siloxane are respectively obtained. Each multi-hydroxy sequin-siloxane has 18 active hydroxy groups which can further assemble and synthesize the prospective organic-inorganic hybridized functional materials. Because nanometer particles are evenly bonded in an organic main body, the defects of an agglomeration phenomenon of the nanometer particles and a poor dispersion degree of traditional composite materials are overcome, and the present invention is easily popularized.
Description
Technical field: the present invention relates to a kind of poly-hydroxy silsesquioxane preparation method, the poly-hydroxy silsesquioxane of preparation can be used as the intermediate (nano particle or structural unit) for preparing all kinds of inorganic-organic hybridization nano structured materials, belongs to chemical field.
Background technology: in recent years, the organic-inorganic hybridized nano structured material has become the advanced subject of domestic and international matrix material research field, and this material is called the leading material of a new generation abroad.The process of traditional preparation process nano composite material is as follows: at first utilize sol-gel processing to prepare the nanogel particle, then with gel drying, sintering, pulverize, use the method for machinery or physics that nano particle (powder) is blended in the body at last, form composite nano materials.This synthesis technique is the process complexity not only, and nano particle has agglomeration, the relatively poor deficiency that waits of dispersity in system.
Summary of the invention: the intermediate-poly-hydroxy silsesquioxane that the objective of the invention is to prepare a kind of inorganic-organic hybridization nano structured material.This intermediate can further be assembled the hybrid inorganic-organic functional materials of synthetic expection.This intermediate not only synthesis technique is simply effective, and nano particle is bonded in organic body equably, and it is relatively poor etc. not enough to have overcome in the conventional composite materials nanoparticle agglomerates phenomenon and dispersity, is easy to promote.The preparation method of poly-hydroxy silsesquioxane is summarized as follows: the first step is the preparation silane monomer.Under vacuum condition, make (3-aminopropyl) triethoxyl silane and (2, the 3-epoxypropyl) phenylate reacts according to 1: 2 molar ratio, temperature of reaction is 30～70 ℃, reaction times is 20～30 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-aminopropyl triethoxysilane, and the developed by molecule formula of this reaction product is R
2N (CH
2)
3Si (OC
2H
5)
3, R=(C wherein
6H
5) OCH
2CH (OH) CH
2Second step was a preparation poly-hydroxy silsesquioxane, silane monomer was dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1～2, and press H
2The usage ratio of O: Si=1～6 adds entry, temperature is under 30～70 ℃ of conditions, hydrolysis-condensation reaction is 20～30 hours, this step is when beginning, add different ratios acid or alkaline catalysts respectively, can prepare the different poly-hydroxy silsesquioxane of three classes respectively: when (1) pressed the usage ratio adding sodium hydroxide of NaOH: Si=0.4～0.6, product was single poly-hydroxy organic-inorganic nano structural unit T
8(OH)
2(the poly-hydroxy silsesquioxane of single form), T=R in this structural unit
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2, this intermediate can carry out chaining and the bridging assembling between unit and the unit, is assembled into the material with specific function; (2) press CHOOH: when the usage ratio of Si=1～6 added formic acid, the product main component was polymorphic poly-hydroxy silsesquioxane intermediate T
8～T
10, T=R wherein
2N (CH
2)
3SiO
1.5,, R=(C
6H
5) OCH
2CH (OH) CH
2This intermediate can be used for stronger function film of processability or block materials; (3) press NaOH: when the usage ratio of Si=0.01～0.1 added sodium hydroxide, product was the lower polymorphic poly-hydroxy silsesquioxane intermediate T of the polymerization degree
5～T
10, T=R wherein
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2This intermediate can be used for stronger film of processability or block materials.
More than three class poly-hydroxy silsesquioxanes be thick liquid state, this product also can be after repeatedly molten water be purified, and 80～110 ℃ of heating 20～30 hours down, grind to form white powder then.
Characteristics of the present invention are: (1) synthesis technique is simply effective, and industrialization can get final product with existing generalization construction equipment; (2) can carry out the molecule assembling, thereby can prepare desired material by controlling the size that synthesis condition is controlled with special macro property; (3) in Zhi Bei the material, inorganic nanoparticles can be bonded in organic body equably, makes its macro property be better than two-phase mixing compound nano material greatly.
Specific embodiment:
Embodiment 1:
The first step is the preparation silane monomer.Under vacuum condition, make (3-aminopropyl) triethoxyl silane and (2, the 3-epoxypropyl) phenylate is according to the reaction of 1: 2 molar ratio, be reflected under 50 ℃ of temperature condition, carried out 24 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-amine propyl-triethoxysilicane, and the developed by molecule formula of this product is R
2N (CH
2)
3Si (OC
2H
5)
3, R=(C wherein
6H
5) OCH
2CH (OH) CH
29Second step was a preparation poly-hydroxy silsesquioxane.The product of the first step is dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1.5, and press H
2The usage ratio of O: Si=3 adds entry, press NaOH: the usage ratio of Si=0.5 adds sodium hydroxide (catalyzer), under 50 ℃ temperature condition, hydrolysis-condensation reaction 24 hours is silsesquioxane (poly-hydroxy organic-inorganic nano structural unit) T thick, single form
8(OH)
2, T=R in this structural unit
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2Product can heat 24 hours down at 95 ℃ after repeatedly molten water is purified, and ground to form white powder then.This product can be used as structure assembling intermediate (nano particle or structural unit); carry out chaining between unit and the unit and bridging assembling, the inorganic-organic hybridization nano structured material of functions such as that the assembling preparation has is high temperature resistant, high strength, super transparent, low-k.
Embodiment 2:
The first step is the preparation silane monomer.Under vacuum condition, make (3-aminopropyl) triethoxyl silane and of the molar ratio reaction of (2, the 3-epoxypropyl) phenylate, be reflected under 50 ℃ of temperature condition according to 1: 2, carried out 24 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-amine propyl-triethoxysilicane; Second step was a preparation poly-hydroxy silsesquioxane.The product of the first step is dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1.5, and press H
2The usage ratio of O: Si=3 adds entry, presses CHOOH: the usage ratio of Si=3 adds formic acid (catalyzer), and under 50 ℃ temperature condition, hydrolysis-condensation reaction 24 hours, product are thick, polymorphic poly-hydroxy silsesquioxane intermediate T
8～T
10This product heated 24 hours down at 95 ℃ after repeatedly molten water is purified, and can grind to form white powder.This intermediate can be used for preparing the inorganic-organic hybridization nano functional materials with performances such as stronger thermodynamics, mechanics, electricity, optics, and cost is lower.
Embodiment 3:
The first step is the preparation silane monomer.Under vacuum condition, make (3-aminopropyl) triethoxyl silane and of the molar ratio reaction of (2, the 3-epoxypropyl) phenylate, be reflected under 50 ℃ of temperature condition according to 1: 2, carried out 24 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-amine propyl-triethoxysilicane; Second step was a preparation poly-hydroxy silsesquioxane intermediate.The product of the first step is dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1.5, and press H
2The usage ratio of O: Si=3 adds entry, press NaOH: the usage ratio of Si=0.05 adds sodium hydroxide (catalyzer), under 50 ℃ temperature condition, hydrolysis-condensation reaction 24 hours, product are lower thick, the polymorphic poly-hydroxy silsesquioxane intermediate T of the polymerization degree
5～T
10This product heated 24 hours down at 95 ℃ after repeatedly molten water is purified, and can grind to form white powder.This intermediate can be used for preparing film or the block materials with performances such as stronger thermodynamics, mechanics, electricity, optics, and cost is lower.
Claims (5)
1. the preparation method of a poly-hydroxy silsesquioxane, it is characterized in that: this poly-hydroxy silsesquioxane is to make according to ratio and the different technology conditions of controlling acid or alkaline catalysts: the first step is the preparation silane monomer, under vacuum condition, make (3-aminopropyl) triethoxyl silane and (2, the 3-epoxypropyl) phenylate reacts according to 1: 2 molar ratio, temperature of reaction is 30～70 ℃, reaction times is 20～30 hours, reaction product is a N-[(2-dihydroxypropyl phenylate)]-the 3-aminopropyl triethoxysilane, the developed by molecule formula of this product is R
2N (CH
2)
3Si (OC
2H
5)
3, R=(C wherein
6H
5) OCH
2CH (OH) CH
2Second step was a preparation poly-hydroxy silsesquioxane, silane monomer was dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1～2, and press H
2The ratio of O: Si=1～6 adds entry, and temperature is under 30～70 ℃ of conditions, and hydrolysis-condensation reaction is 20～30 hours, and this step adds different ratios acid or alkaline catalysts respectively when beginning, and can prepare the different poly-hydroxy silsesquioxane of three classes respectively:
(1) press NaOH: when the usage ratio of Si=0.4～0.6 added sodium hydroxide, product was single poly-hydroxy organic-inorganic nano structural unit T8 (OH) 2, T=R in this structural unit
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2
(2) press CHOOH: when the usage ratio of Si=1～6 added formic acid, the product main component was polymorphic poly-hydroxy silsesquioxane intermediate T
8～T
10, T=R wherein
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2
(3) press NaOH: when the usage ratio of Si=0.01～0.1 added sodium hydroxide, product was the lower polymorphic poly-hydroxy silsesquioxane intermediate T of the polymerization degree
5～T
10, T=R wherein
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2
2. the preparation method of a kind of poly-hydroxy silsesquioxane according to claim 1, it is characterized in that described three class poly-hydroxy silsesquioxanes are thick liquid state, this product also can be after repeatedly molten water be purified, heated 20～30 hours down at 80～110 ℃, grind the white powder state that is prepared into then.
3. the preparation method of a kind of poly-hydroxy silsesquioxane according to claim 1, it is characterized in that controlling in the preparation process ratio and the processing condition difference of acid or alkaline catalysts, the first step is the preparation silane monomer, under vacuum condition, make (3-aminopropyl) triethoxyl silane and (2, the 3-epoxypropyl) phenylate is according to the reaction of 1: 2 molar ratio, be reflected under 50 ℃ of temperature condition, carried out 24 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-amine propyl-triethoxysilicane, and the developed by molecule formula of this product is R
2N (CH
2)
3Si (OC
2H
5)
3, R=(C wherein
6H
5) OCH
2CH (OH) CH
2Second step was a preparation poly-hydroxy silsesquioxane, the product of the first step was dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1.5, and press H
2O: the Si=3 usage ratio adds entry, press NaOH: the usage ratio of Si=0.5 adds sodium hydroxide, under 50 ℃ temperature condition, hydrolysis-condensation reaction 24 hours, product is after repeatedly molten water is purified, heated 24 hours down at 95 ℃, grind to form white powder then, be poly-hydroxy organic-inorganic nano structural unit T
8(OH)
2, T=R in this structural unit
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2
4. the preparation method of a kind of poly-hydroxy silsesquioxane according to claim 1, it is characterized in that, the ratio and the processing condition difference of control acid or alkaline catalysts in the preparation process, the first step is the preparation silane monomer, under vacuum condition, makes (3-aminopropyl) triethoxyl silane and (2, the 3-epoxypropyl) phenylate is according to the reaction of 1: 2 molar ratio, be reflected under 50 ℃ of temperature condition, carried out 24 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-amine propyl-triethoxysilicane; Second step was a preparation poly-hydroxy silsesquioxane, the product of the first step was dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1.5, and press H
2The usage ratio of O: Si=3 adds entry, presses CHOOH: the usage ratio of Si=3 adds formic acid, under 50 ℃ temperature condition, and hydrolysis-condensation reaction 24 hours, the main component of product is polymorphic poly-hydroxy silsesquioxane intermediate T
8～T
10, T=R wherein
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2
5. the preparation method of a kind of poly-hydroxy silsesquioxane according to claim 1, it is characterized in that, the ratio and the processing condition difference of control acid or alkaline catalysts in the preparation process, the first step is the preparation silane monomer, under vacuum condition, makes (3-aminopropyl) triethoxyl silane and (2, the 3-epoxypropyl) phenylate is according to the reaction of 1: 2 molar ratio, be reflected under 50 ℃ of temperature condition, carried out 24 hours, reaction product is N-(2-dihydroxypropyl phenylate)-3-amine propyl-triethoxysilicane; Second step was a preparation poly-hydroxy silsesquioxane intermediate, the product of the first step was dissolved in tetrahydrofuran (THF), silane monomer: tetrahydrofuran (THF)=1: 1.5, and press H
2The usage ratio of O: Si=3 adds entry, presses NaOH: the usage ratio of Si=0.05 adds sodium hydroxide, and under 50 ℃ temperature condition, hydrolysis-condensation reaction 24 hours, product are the lower polymorphic poly-hydroxy silsesquioxane intermediate T of the polymerization degree
5～T
10, T=R wherein
2N (CH
2)
3SiO
1.5, R=(C
6H
5) OCH
2CH (OH) CH
2
Priority Applications (1)
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|---|---|---|---|
| CN 03134129 CN1291991C (en) | 2003-08-20 | 2003-08-20 | Preparation method of multihydroxy sesqui siloxane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03134129 CN1291991C (en) | 2003-08-20 | 2003-08-20 | Preparation method of multihydroxy sesqui siloxane |
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|---|---|
| CN1513858A CN1513858A (en) | 2004-07-21 |
| CN1291991C true CN1291991C (en) | 2006-12-27 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331870C (en) * | 2004-10-27 | 2007-08-15 | 西北工业大学 | Epoxy-silsesquioxanes preparation method |
| DE602005008100D1 (en) * | 2004-12-17 | 2008-08-21 | Dow Corning | METHOD FOR FORMING AN ANTI-REFLECTION COATING |
| CN100351314C (en) * | 2005-04-28 | 2007-11-28 | 陈俊光 | Water-proofing agent of water based type organic silicon resin and preparation process thereof |
| KR101226888B1 (en) * | 2007-11-23 | 2013-01-28 | 제일모직주식회사 | Silicone Bead with Excellent Hydrophobic and Alkaliproof Properties, Method for Preparing the Same and Coating Composition Using the Same |
| CN104263022B (en) * | 2014-10-23 | 2017-04-12 | 国网辽宁省电力有限公司营口供电公司 | Potassium silicate paint added with hydroxyl silsesquioxane and preparation method thereof |
| JP6894150B2 (en) * | 2017-04-20 | 2021-06-23 | 国立研究開発法人産業技術総合研究所 | Silanol compound and method for producing silanol compound |
| CN108948073B (en) * | 2018-08-15 | 2020-07-28 | 哈尔滨工业大学 | A kind of preparation method of polyhydroxysilsesquioxane |
| CN109053795B (en) * | 2018-08-15 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of polymethacryloxy silsesquioxane |
| JP7338681B2 (en) * | 2019-05-22 | 2023-09-05 | 信越化学工業株式会社 | Fiber treatment agent |
| CN110483777B (en) * | 2019-09-10 | 2022-02-08 | 哈尔滨工业大学 | Synthesis method of poly-silicon hydroxyl POSS |
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