CN1235170A - Synthesis of vinyl organic/inorganic nano-size hybridized material - Google Patents
Synthesis of vinyl organic/inorganic nano-size hybridized material Download PDFInfo
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- CN1235170A CN1235170A CN 98108617 CN98108617A CN1235170A CN 1235170 A CN1235170 A CN 1235170A CN 98108617 CN98108617 CN 98108617 CN 98108617 A CN98108617 A CN 98108617A CN 1235170 A CN1235170 A CN 1235170A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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Abstract
A process for preparing nm-class ethylene-based organic-inorganic hybridized material features that it is use of traditional Sol-Gel method, and includes such steps as hydrolyzing the ethyl n-silicate that is the Sol-Gel precursor of inorganic component under the catatlysis of hydrochloric acid to obtain sol, addition of ethyl monomer to form sol, and radiating the ethyl monomer with alpha rays in in-situ polymerized sol. The principle of polymerization is free radical polymerization. With the process, high-inorganic (SiO2)-content hydridized material can be made up with short period and simple method.
Description
The invention belongs to the synthetic method of vinyl organic/inorganic nano hybrid material.
Preparing optically transparent organic/inorganic hybridization material by colloidal sol-gel (Sol-Gel) method is that recent two decades comes one of research focus in the international material.The Sol-Gel method be a kind of based on inorganic polymeric prepare glass or the pottery method, its distinctive chilling process for the preparation organic/inorganic hybridization material provide may.At present, organic/inorganic hybridization material mostly is nano hybridization, and promptly the disperse phase yardstick is in nanometer scale, and this just makes it compare with conventional composite materials to have more excellent comprehensive performance.As: the hydridization of nanometer level makes material have optical transparence, and organic introduction makes material itself have more toughness, has increased the energy-to-break of material greatly.
The preparation of organic/inorganic hybridization material can have several different methods, and modal is that soluble high-molecular is incorporated in the inorganic network, or inorganic Sol-Gel precursor is introduced in the macromolecule matrix.Original position (In-Situ) polymerization process receives increasing concern in recent years, and the Sol-Gel precursor that is about to polymerizable organic monomer and inorganic component is molten altogether, adopts corresponding polymerization means according to different monomers, and then in-situ polymerization forms hybrid material.Wherein, adopting cosolvent is that the method for polymerisable monomer is prepared into small size and shrinks that even not shrink sample more noticeable.From bibliographical information, at the nineties initial stage, Bruce M.Novac etc. has reported preparation (1. Macromolecules, 1991 of non-contraction organic/inorganic hybridization material, 24,5481,2. Adv.Mater., 1993,5,422), they adopt UV-light and free radical polymerization, and C.L.Jacson etc. have reported in succession by free radical polymerization and prepared vinyl-based organic/inorganic hybridization material (1. J.Mater.Sci., 1988,23,3801,2. Chem.Mater., 1996,8,727).But free radical thermal-initiated polymerization method has inevitably been introduced impurity (initiator) on the one hand, make the purity of material be subjected to influence, radical initiator such as benzoyl peroxide are usually at 70 ℃ of-80 ℃ of ability initiated polymerizations on the other hand, and the ununiformity of polymerization process and emit a large amount of heat often takes place sudden and violent poly-or polymerization is incomplete.The method of free radical thermal-initiated polymerization simultaneously is not easy to make the hybrid material of high SiO2 content, and the hybrid material SiO2 content of report such as C.L.Jacson is the highest 23%, and the material transparency under this ratio is very poor.There is the incomplete phenomenon of polymerization equally in uv-light polymerization, and Bruce M.Novac also will add radical initiator with uv-light polymerization the time makes polymerization be tending towards perfect.H.Krug and H.Schmidt have reported that vinyl silane oxycompound not exclusively and to temperature and time has very big dependency (New J.Chem., 1994,18,1125) at uv-light polymerization.The above problem that produces all makes the quality of the preparation of sample and final material restive.
The synthetic method that the purpose of this invention is to provide a kind of vinyl organic/inorganic nano hybrid material, present method adopt the Sol-Gel method vinyl monomer to be joined the inorganic SiO of hydrolysis
2In the colloidal sol, or directly the oxyalkylated vinyl monomer of silicon is hydrolyzed into colloidal sol, forms gel, utilize gamma-ray irradiation in-situ polymerization vinyl monomer again, thereby obtain optically transparent block vinyl organic/inorganic hybridization material.
Synthetic technology of the present invention is based on traditional Sol-Gel method, and inorganic component adopts Sol-Gel precursor tetraethoxy to be hydrolyzed into colloidal sol under hydrochloric acid catalysis, adds vinyl monomer in colloidal sol, forms gel.The gamma-ray irradiation in-situ polymerization is adopted in the polymerization of vinyl monomer in the gel, and the polymerization principle is radical polymerization.
The vinyl monomer structure that adopts among the present invention as shown in the formula:
(CH
2)
3Si (OR)
3[R=Me, Et]
In preparation process, tetraethoxy (TEOS) is hydrolyzed into colloidal sol under hydrochloric acid catalysis, vinyl monomer joins in the colloidal sol, forms gel, and the preparing gel temperature is 30-50 ℃, polymerization under gamma-ray irradiation afterwards, polymerization temperature is at 5-45 ℃, and irradiation dose is 5-100KGy, and irradiation time is 4-20 hour, sample is placed 60-80 ℃ of heat drying 1-2 week inorganic SiO in the final hybrid material of gained then
2Content can reach 60%, in visible-range iuuminting rate at 85%-100%.
Maximum characteristics of the present invention are on the basis of traditional Sol-Gel method, break through general vinyl organic monomer radical initiator initiated polymerization, adopt gamma-ray irradiation in-situ polymerization vinyl monomer, polymerization process is simple, and the whole process of material preparation is easy to industrialization.Radiation polymerization can carry out under lower temperature in addition, makes the stress of sample interior become very little, makes bulk sample can not ftracture in polymerization process, and can be with the SiO of bulk sample
2Content improves greatly.Because polymerization carries out in advance, make the macromolecular chain that has formed relative flexibility in the sample, increased the crack resistance of sample greatly, make the preparation of sample become and be more prone to.The preparation cycle of sample also becomes very short because of the alcohol that the unnecessary water of vaporization at high temperature and hydrolysis are got off.
Specific embodiments of the invention are as follows: embodiment 1.
Poly(Hydroxyethyl Methacrylate) (HEA)-SiO
2Nano-hybrid material
The tetraethyl silicate (TEOS) that in the glass Erlenmeyer flask of the 500ml of cleaning, adds 200ml, and add the HCl aqueous solution 48.2ml of 0.1M by stoichiometry, stirring at room made its hydrolysis in 24 hours.Get the good 3ml TEOS of said hydrolyzed and add in the clean 10ml cylindrical glass bucket, add firm distilled HEA 3ml again, stir.Mixing solutions was moved in 40 ℃ of baking ovens gel 48 hours, behind the gel with its radiation polymerization 8 hours under 20 ℃ of room temperatures, 35KGy, put into after the polymerization 70 ℃ of baking ovens with dewater, hydrolysis is got off alcohol and make condensation reaction more thorough, handle with this understanding and promptly get the bulk material that a light golden yellow is optically transparent, contraction is little 1 week.Embodiment 2.
Poly(Hydroxyethyl Methacrylate) (HEA)-SiO
2Nano-hybrid material
Get the TEOS 4ml that hydrolysis is good among the embodiment 1 and add in the clean 10ml glass tank, add firm distilled HEA 1ml again, stir.The preparation method is with embodiment 1, and mixing solutions is moved into gel in 40 ℃ of baking ovens, gel polymerization 4 hours under 30 ℃ of room temperatures, 100Gy irradiation, put into after the polymerization promptly get 70 ℃ of 1 weeks of oven optical transparence good, contraction bulk material little, that do not split.Embodiment 3.
Poly hydroxy ethyl acrylate (HEMA)-SiO
2Nano-hybrid material
The TEOS 4ml that gets as hydrolysis is good among the embodiment 1 adds in the clean 10ml glass tank, adds firm distilled HEMA 2ml again, stirs.The preparation method is with embodiment 1, and gel in 30 ℃ of baking ovens 25 ℃, 5KGy radiation polymerization 20 hours, is put into after the polymerization and promptly got one 60 ℃ of 2 weeks of oven and be close to colourless optics transparent cake material behind the gel.Embodiment 4.
Polyacrylic acid-SiO
2Nano-hybrid material
The TEOS 2ml that gets as hydrolysis is good among the embodiment 1 adds in the clean 10ml glass tank, adds firm distilled polyacrylic acid 4ml again, stirs.The preparation method is with embodiment 1, gel in 40 ℃ of baking ovens, behind the gel under 20 ℃, 35KGy radiation polymerization 10 hours, put into after the polymerization can get 80 ℃ of 1 weeks of oven optical transparence good, shrink bulk material little, that do not split.Embodiment 5.
Methacrylic acid-3-(Trimethoxy silane base) propyl ester (KH570) body nano-hybrid material
Add the KH570 of 200ml in the glass Erlenmeyer flask of the 500ml that cleans, and press the HCl aqueous solution 29.2ml that stoichiometry adds 0.1M, stirring at room made its hydrolysis in 24 hours.Getting the good 5mlKH570 of said hydrolyzed adds in the clean 10ml glass tank, placed 50 ℃ of baking oven gels 24 hours, behind the gel with its radiation polymerization under 45 ℃, 50KGy, put into after the polymerization 80 ℃ of baking ovens with dewater, hydrolysis is got off alcohol and make condensation reaction more thorough, handle with this understanding promptly get in 1 week a light golden yellow optical transparence good, contraction bulk material very little, that do not split.Embodiment 6
KH570-SiO
2Nano-hybrid material
Get the TEOS1ml that hydrolysis is good among good 5ml KH570 of hydrolysis among the embodiment 5 and the embodiment 1 and add in the clean 10ml glass tank, stir.The preparation method is with embodiment 1, mixing solutions was moved in 30 ℃ of baking ovens gel 36 hours, behind the gel with it 20 ℃ of room temperatures, 25KGy radiation polymerization 8 hours, put into after the polymerization promptly get 70 ℃ of 1 weeks of oven a light golden yellow optically transparent, shrink less bulk material.
Claims (1)
1. the synthetic method of a vinyl organic/inorganic nano hybrid material, be based on traditional Sol-Gel method, it is characterized in that adopting Sol-Gel precursor tetraethoxy under hydrochloric acid catalysis, to be hydrolyzed into colloidal sol, in colloidal sol, add vinyl monomer, form gel, gamma-radiation irradiation in-situ polymerization is adopted in the polymerization of vinyl monomer in the gel, the vinyl monomer structure of employing as shown in the formula:
(CH
2)
3Si (OR)
3[R=Me, Et] in preparation process, tetraethoxy (TEOS) is hydrolyzed into colloidal sol under hydrochloric acid catalysis, and vinyl monomer joins in the colloidal sol, form gel, the preparing gel temperature is at 30-50 ℃, polymerization under gamma-radiation irradiation afterwards, and polymerization temperature is at 5-45 ℃, irradiation dose is 5-100KGy, irradiation time is 4-20 hour, sample is placed 60-80 ℃ of heat drying 1-2 week inorganic SiO in the final hybrid material of gained then
2Content can reach 60%, in visible-range iuuminting rate at 85%-100%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98108617A CN1085679C (en) | 1998-05-09 | 1998-05-09 | Synthesis of vinyl organic/inorganic nano-size hybridized material |
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| CN98108617A CN1085679C (en) | 1998-05-09 | 1998-05-09 | Synthesis of vinyl organic/inorganic nano-size hybridized material |
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| Publication Number | Publication Date |
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| CN1235170A true CN1235170A (en) | 1999-11-17 |
| CN1085679C CN1085679C (en) | 2002-05-29 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532433C (en) * | 2003-03-14 | 2009-08-26 | 中央硝子株式会社 | Organic-inorganic hybrid vitreous material and method for producing same |
| CN1990600B (en) * | 2005-12-27 | 2010-09-22 | 中国石油化工股份有限公司 | Method for preparing composite material |
| CN101812219B (en) * | 2009-02-25 | 2012-05-30 | 中国科学院化学研究所 | In situ growth preparing method of polyester/ silicon dioxide nano-hybrid material and product thereof |
| CN105349034A (en) * | 2015-11-30 | 2016-02-24 | 苏州太湖电工新材料股份有限公司 | Low-viscosity high-temperature-resistance corona-resistant environment-friendly insulating paint and preparation method thereof |
| CN105348534A (en) * | 2015-11-30 | 2016-02-24 | 苏州太湖电工新材料股份有限公司 | Nanometer silicon dioxide hybrid vinyl phenyl silicon intermediate material and preparing method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031396C (en) * | 1993-07-20 | 1996-03-27 | 浙江大学 | Method for preparing alpha-alumina particles with nanometers size |
| CN1050817C (en) * | 1995-03-14 | 2000-03-29 | 中国科学院固体物理研究所 | Prepn of silicon dioxide powder with controllable nanon size |
-
1998
- 1998-05-09 CN CN98108617A patent/CN1085679C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532433C (en) * | 2003-03-14 | 2009-08-26 | 中央硝子株式会社 | Organic-inorganic hybrid vitreous material and method for producing same |
| CN1990600B (en) * | 2005-12-27 | 2010-09-22 | 中国石油化工股份有限公司 | Method for preparing composite material |
| CN101812219B (en) * | 2009-02-25 | 2012-05-30 | 中国科学院化学研究所 | In situ growth preparing method of polyester/ silicon dioxide nano-hybrid material and product thereof |
| CN105349034A (en) * | 2015-11-30 | 2016-02-24 | 苏州太湖电工新材料股份有限公司 | Low-viscosity high-temperature-resistance corona-resistant environment-friendly insulating paint and preparation method thereof |
| CN105348534A (en) * | 2015-11-30 | 2016-02-24 | 苏州太湖电工新材料股份有限公司 | Nanometer silicon dioxide hybrid vinyl phenyl silicon intermediate material and preparing method and application thereof |
| CN105349034B (en) * | 2015-11-30 | 2017-06-20 | 苏州太湖电工新材料股份有限公司 | A kind of low viscosity, fire resistant Inverter fed motor environmental protection insulated paint and preparation method thereof |
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| CN1085679C (en) | 2002-05-29 |
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