CN1887957A - Prepn of hybridized epoxyresin/silica material - Google Patents
Prepn of hybridized epoxyresin/silica material Download PDFInfo
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- CN1887957A CN1887957A CN 200610019710 CN200610019710A CN1887957A CN 1887957 A CN1887957 A CN 1887957A CN 200610019710 CN200610019710 CN 200610019710 CN 200610019710 A CN200610019710 A CN 200610019710A CN 1887957 A CN1887957 A CN 1887957A
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Abstract
The present invention relates to preparation process of hybridized epoxy resin/silica material. The preparation process includes the following steps: 1. preparing silica sol through mixing organosilicon, ethanol and water in the molar ratio of 1 to 2-6 to 2-6 to form liquid mixture; dropping acid to regulate the pH value of the liquid mixture to 2-5; stirring for 2-10 hr and sealed ageing at room temperature for 1-15 days; and 2. compounding the silica sol with epoxy resin to obtain the hybridized epoxy resin/silica material. The present invention adopts aged inorganic silica sol, and has small silica phase size and no obvious interphase interface in the product.
Description
Technical field
The present invention relates to the preparation method's of organic/inorganic hybridization material, particularly Resins, epoxy/silicon dioxide hybrid materials preparation method.
Background technology
Along with science and technology development, the material of single character can not satisfy people's needs, and compoundization is the trend of modern material development.Function by two or more materials is compound, performance complement and optimization, can prepare the matrix material of excellent performance.For general matrix material, be dispersed in inorganic component size in the polymer-based carbon usually more than micron order, only as filler or weighting agent.The urgent hope of people can prepare a kind of inorganics and polymkeric substance carries out the compound special composite material on molecular level, and this is " organic/inorganic hybridization material " that is referred to as with regard to today.
Hybrid material be after single component material, matrix material, gradient material the 4th generation material.It is a kind of uniform heterogeneous material, and wherein one mutually at least at nano-scale.This material is that inorganics combines formation with organism in nanometer range, and inorganic and organic phase two are alternate by chemical bond, hydrogen bond or only be that Van der Waals force combines on nanometer level.
Organic/inorganic hybridization material combines inorganics hardness height, resistance to chemical corrosion is good and advantage separately such as organism good toughness.Its character not only depends on the character of single component, more depends on biphase pattern and two alternate reactive forces.The performance of organic/inorganic hybridization material be not only form constitutive property simply add and, and usually show many other advantageous properties.
Resins, epoxy is widely used in fields such as heavy-duty coating, engineering plastics with characteristics such as its excellent cementability, solidity to corrosion, chemical stability and cure shrinkage are low.But because the epoxy resin cured product cross-linking density is big, material is more crisp, and resistance toheat is relatively poor, has restricted the large-scale application of Resins, epoxy.
In recent years, the investigator attempts introducing inorganic component (normally silicon-dioxide) in epoxy resin-base, makes the epoxide resin polymer network with inorganic compound on molecular level, forming does not have the Resins, epoxy/silicon dioxide hybrid materials that is separated, and has obtained certain progress.Resins, epoxy/silicon dioxide hybrid materials, combine that the epoxy resin cure shrinking percentage is low, chemical stability is high, good to metal sticking power, and inorganic silicon dioxide good heat resistance, hardness advantages of higher, promoted the using value of Resins, epoxy, have broad application prospects.
Among Resins, epoxy/silicon dioxide hybrid materials preparation technology, because the qualitative greatest differences of silicon-dioxide and Resins, epoxy can not prepare with methods such as usual method such as high-temperature fusion, chemical vapour deposition, electrochemical vapour deposition (EVD)s.How to prepare organic/inorganic hybridization material at present with sol-gel method, prepare organic/inorganic hybridization material with sol-gel method, not only be convenient to select plural components, satisfy the purpose of optimizing, widening material property, and the design by presoma and synthetic route, can optimize compound yardstick and compound interface, reach the compound level of molecule.
Existing Resins, epoxy/silicon dioxide hybrid materials preparation method, (time of disclosure is: in May, 2004) article " Nano-SiO as " University Of Tianjin's journal " the 37th the 5th phase of volume
2/ E-20/TEOS compound system " (400-404 page or leaf) disclosed method, mainly contain by the Sol-Gel legal system and get nano silica powder, form Resins, epoxy/silicon dioxide nano composite material by silicon-dioxide and Resins, epoxy compound step again.The inorganic silicon dioxide phase size that uses in this method is bigger, causes the product two-phase interface of preparation obvious, and it is compound that Resins, epoxy and silicon-dioxide fail to reach comparatively ideal molecular level.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of Resins, epoxy/silicon dioxide hybrid materials is provided, and the Resins, epoxy/silicon dioxide hybrid materials of this method preparation does not have phenomenon of phase separation.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of preparation method of Resins, epoxy/silicon dioxide hybrid materials, it may further comprise the steps:
(1) take by weighing organosilicon, organosilicon and ethanol, water are mixed with mixed solution, the mol ratio of the organosilicon in the mixed solution, ethanol, water is: 1: 2-6: 2-6; Drip acid in mixed solution, the pH that makes mixed solution stirred 2-10 hour between 2-5, with mixed solution room temperature lower seal ageing 1-15 days, obtained silicon dioxide gel again;
(2) silicon-dioxide and Resins, epoxy compound step obtain Resins, epoxy/silicon dioxide hybrid materials.
A kind of preparation method of Resins, epoxy/silicon dioxide hybrid materials, it may further comprise the steps:
(1) take by weighing organosilicon, organosilicon and ethanol, water are mixed with mixed solution, the mol ratio of the organosilicon in the mixed solution, ethanol, water is: 1: 2-6: 2-6; Drip acid in mixed solution, the pH that makes mixed solution stirred 2-10 hour between 2-5, with mixed solution room temperature lower seal ageing 1-15 days, obtained silicon dioxide gel again;
Add organo-siloxane in silicon dioxide gel, organo-siloxane and organosilyl mol ratio are: 0.05-0.3: 1; After stirring, under the room temperature ageing 1-21 days, obtain the silicon dioxide gel after the modification;
(2) silicon-dioxide and Resins, epoxy compound step obtain Resins, epoxy/silicon dioxide hybrid materials.
In the such scheme, silicon-dioxide and Resins, epoxy compound step are specially:
Take by weighing Resins, epoxy, Resins, epoxy is dissolved in the N-Methyl pyrrolidone, be made into the solution that mass percent concentration is 50-80%, the product that adds step (1) preparation, stirred 0.5-4 hour, add epoxy curing agent again, be cast in the mould, being heating and curing obtains Resins, epoxy/silicon dioxide hybrid materials;
Resins, epoxy with organosilyl mass parts ratio is: 0.5-10: 1, and Resins, epoxy with the mass parts ratio of epoxy curing agent is: 100: 20-30.
In the such scheme, organosilicon is tetraethoxy or methyl silicate or butyl silicate.
In the such scheme, acid is formic acid or acetate or hydrochloric acid or nitric acid or sulfuric acid.
In the such scheme, the general formula of organo-siloxane is RSi (OR ')
3Or R
2Si (OR ')
2Wherein, R is the organic chain that contains epoxy-functional, and OR ' is methoxyl group, oxyethyl group or butoxy.
In the such scheme, organo-siloxane is γ-glycidyl ether propyl trimethoxy silicane.
Compared with prior art, the invention has the advantages that:
1, the colloidal sol of the inorganic silicon dioxide that uses after as ageing, the silicon-dioxide phase size is less, and the product of preparation does not have obvious two-phase interface.
2, on inorganic silicon dioxide rigidity network, contain the organosilicon molecule of epoxy-functional in the grafting, between the two with the effect of Si-O-Si key.Epoxy-functional in the grafting makes silicon-dioxide and epoxy resin compatibility strengthen greatly, can obtain not having and be separated or the organic-inorganic hybridized material of microphase-separated, make organic phase strengthen with inorganic two alternate consistencies mutually, but inhibitory phase separates, and obtains the organic-inorganic hybridized material of better performances.
Description of drawings
Fig. 1 is the SEM photo of the Resins, epoxy/silicon dioxide hybrid materials of the embodiment of the invention 1 preparation
Fig. 2 is the SEM photo of Resins, epoxy/silicon dioxide hybrid materials in the Comparative Examples
Fig. 3 is the SEM photo of the Resins, epoxy/silicon dioxide hybrid materials of the embodiment of the invention 2 preparations
Embodiment
The inventive method embodiment 1: it may further comprise the steps:
(1) takes by weighing 5 gram tetraethoxys, under the room temperature, in the 500ml beaker, tetraethoxy and dehydrated alcohol, deionized water are mixed with mixed solution, stir; The mol ratio of the organosilicon in the mixed solution, ethanol, water is: 1: 2: 4; Drip the hydrochloric acid of pH=1 in mixed solution, the pH value to 3 of regulation system utilizes magnetic stirring apparatus to be stirred 2-10 hour, with mixed solution room temperature lower seal ageing 7 days, obtains as clear as crystal silicon dioxide gel again.
(2) take by weighing 5 gram bisphenol A type epoxy resins, tetraethoxy with the mass parts ratio of bisphenol A type epoxy resin is: 1: 1; Bisphenol A type epoxy resin is dissolved in the N-Methyl pyrrolidone, be made into the solution that mass percent concentration is 50-80%, the product that adds step (1) preparation, stirred 0.5-4 hour, add the 30phr epoxy resin E-44 solidifying agent of (per 100 gram Resins, epoxy add 30 gram solidifying agent) again, continue to stir.When mixing solutions viscosity reaches 50-100 second (with being coated with 4 glasss of surveys), be poured in the tetrafluoroethylene mould.Put into baking oven, solidified 24 hours down at 50 ℃, solidified 4 hours under 120 ℃ of conditions the back, obtains water white Resins, epoxy/silicon dioxide hybrid materials.
As shown in Figure 1, the SEM of material section shows: in the Resins, epoxy/silicon dioxide hybrid materials of the inventive method embodiment 1 preparation, two-phase macroface do not occur and separates, and two-phase interface is fuzzy.
Comparative Examples: in the embodiment of the invention 1, without the room temperature ageing process, other step is constant in the step (1).As shown in Figure 2, the sem analysis of hybrid material section shows: in the Comparative Examples, silicon-dioxide is that the nanometer ball form with 30-50nm is dispersed in the epoxy resin-base, occurs more significantly being separated.
The embodiment of the invention 2:
(1) takes by weighing 5.2 gram (0.025mol) tetraethoxys, under the room temperature, in the 50ml beaker, 0.025mol tetraethoxy, 0.05mol dehydrated alcohol, 0.10mol deionized water are mixed, and, utilize magnetic stirring apparatus to be stirred 2-10 hour, with this colloidal sol sealing with the pH value to 2 of the hydrochloric acid regulation system of pH=1, ageing is 7 days under the room temperature, obtains as clear as crystal silicon dioxide gel.
The step of silicon dioxide gel modification: γ-glycidyl ether propyl trimethoxy silicane (GPTMS) of 0.005mol is added in the silicon dioxide gel, after stirring, plastics film is sealed the beaker mouth, placed again under the room temperature ageing 7-10 days, obtain modification after, the silicon dioxide gel of surface grafting epoxide group.
(2) with the step (2) of the embodiment of the invention 1.
As shown in Figure 3, the SEM of material section shows: do not occur macroface in the hybrid material and separate, do not see tangible two-phase interface, two-phase is compound with the molecular level level.
The embodiment of the invention 3:
(1) take by weighing 0.025mol methyl silicate (TMOS) 3.8 gram, under the room temperature, in the 50ml beaker, 0.025mol methyl silicate (TMOS), 0.1mol anhydrous methanol 3.2 grams and 0.10mol deionized water 1.8 grams are mixed, and with the oxalic acid (H of 0.1mol/L
2C
2O
4) the pH value to 3 of solution regulation system, stirred 2 hours under the room temperature, with this colloidal sol sealing, ageing 5 days obtains as clear as crystal silicon dioxide gel.
The silicon dioxide gel modification is with the embodiment of the invention 2
(2) with the step (2) of the embodiment of the invention 1.
The SEM of material section shows: occur faint being separated in the hybrid material, but two-phase interface is fuzzy, the two-phase intermiscibility is better.
The step of the inventive method embodiment 4-8 is that following parameter changes with the embodiment of the invention 1:
| Embodiment | Organosilicon (0.025mol) | Ethanol (mol) | Water (mol) | Acid | The pH of mixed solution | The sealing ageing (my god) | Resins, epoxy (gram) | Solidifying agent D230 (phr) |
| 4 | Tetraethoxy 5.2 grams | 0.05 | 0.05 | The formic acid of pH=1 | 2 | 7 | 52 | 20phr |
| 5 | Tetraethoxy 5.2 grams | 0.05 | 0.15 | The acetate of pH=1 | 3 | 7 | 52 | 25phr |
| 6 | Methyl silicate 3.8 grams | 0.075 | 0.075 | The hydrochloric acid of pH=1 | 5 | 15 | 38 | 30phr |
| 7 | Tetraethoxy 5.2 grams | 0.1 | 0.1 | The nitric acid of pH=1 | 3 | 2 | 26 | 30phr |
| 8 | Butyl silicate 8.0 grams | 0.15 | 0.1 | The sulfuric acid of pH=1 | 4 | 1 | 4 | 30phr |
The step of the inventive method embodiment 9-12 is that following parameter changes with the embodiment of the invention 2:
| Embodiment | Organosilicon (0.025mol) | Ethanol (mol) | Water (mol) | Organo-siloxane | Organo-siloxane (mol) | The modification ageing (my god) |
| 9 | Tetraethoxy 5.2 grams | 0.05 | 0.05 | γ-glycidyl ether propyl trimethoxy silicane | 0.0025mol | 7-10 |
| 10 | Tetraethoxy 5.2 grams | 0.05 | 0.1 | γ-glycidyl ether propyl-triethoxysilicane | 0.00125mol | 1-2 |
| 11 | Methyl silicate 3.8 grams | 0.075 | 0.15 | γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane | 0.005mol | 20-21 |
| 12 | Tetraethoxy 5.2 grams | 0.1 | 0.1 | γ-glycidyl ether oxygen base propyl group methyldiethoxysilane | 0.0075mol | 15 |
Among the present invention 2,3, the 9-12, SiO
2Sol-gel modified dose---the general formula of organo-siloxane is RSi (OR ')
3Or R
2Si (OR ')
2Wherein, R is the organic chain that contains epoxy-functional, and OR ' is methoxyl group, oxyethyl group or butoxy.Wherein, because the hydrolysis rate of methoxyl group is moderate in the Sol-Gel process, above-mentioned SiO
2In sol-gel modified dose with γ-glycidyl ether propyl trimethoxy silicane (RSi (OCH
3)
3) the best.
Claims (7)
1, a kind of preparation method of Resins, epoxy/silicon dioxide hybrid materials, it is characterized in that: it may further comprise the steps:
(1) take by weighing organosilicon, organosilicon and ethanol, water are mixed with mixed solution, the mol ratio of the organosilicon in the mixed solution, ethanol, water is: 1: 2-6: 2-6; Drip acid in mixed solution, the pH that makes mixed solution stirred 2-10 hour between 2-5, with mixed solution room temperature lower seal ageing 1-15 days, obtained silicon dioxide gel again;
(2) silicon-dioxide and Resins, epoxy compound step obtain Resins, epoxy/silicon dioxide hybrid materials.
2, a kind of preparation method of Resins, epoxy/silicon dioxide hybrid materials, it is characterized in that: it may further comprise the steps:
(1) take by weighing organosilicon, organosilicon and ethanol, water are mixed with mixed solution, the mol ratio of the organosilicon in the mixed solution, ethanol, water is: 1: 2-6: 2-6; Drip acid in mixed solution, the pH that makes mixed solution stirred 2-10 hour between 2-5, with mixed solution room temperature lower seal ageing 1-15 days, obtained silicon dioxide gel again;
Add organo-siloxane in silicon dioxide gel, organo-siloxane and organosilyl mol ratio are: 0.05-0.3: 1; After stirring, under the room temperature ageing 1-21 days, obtain the silicon dioxide gel after the modification;
(2) silicon-dioxide and Resins, epoxy compound step obtain Resins, epoxy/silicon dioxide hybrid materials.
3, preparation method as claimed in claim 1 or 2 is characterized in that: silicon-dioxide and Resins, epoxy compound step are specially:
Take by weighing Resins, epoxy, Resins, epoxy is dissolved in the N-Methyl pyrrolidone, be made into the solution that mass percent concentration is 50-80%, the product that adds step (1) preparation, stirred 0.5-4 hour, add epoxy curing agent again, be cast in the mould, being heating and curing obtains Resins, epoxy/silicon dioxide hybrid materials;
Resins, epoxy with organosilyl mass parts ratio is: 0.5-10: 1, and Resins, epoxy with the mass parts ratio of epoxy curing agent is: 100: 20-30.
4, preparation method as claimed in claim 1 or 2 is characterized in that: organosilicon is tetraethoxy or methyl silicate or butyl silicate.
5, preparation method as claimed in claim 1 or 2 is characterized in that: acid is formic acid or acetate or hydrochloric acid or nitric acid or sulfuric acid.
6, preparation method as claimed in claim 2 is characterized in that: the general formula of organo-siloxane is RSi (OR ')
3Or R
2Si (OR ')
2Wherein, R is the organic chain that contains epoxy-functional, and OR ' is methoxyl group, oxyethyl group or butoxy.
7, preparation method as claimed in claim 2 is characterized in that: organo-siloxane is γ-glycidyl ether propyl trimethoxy silicane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525466B (en) * | 2009-04-03 | 2012-07-04 | 复旦大学 | Epoxy/organosilicon/inorganic nano-hybrid material, and preparation method and application thereof |
| CN108084659A (en) * | 2017-12-23 | 2018-05-29 | 陈建峰 | A kind of preparation method of high intensity Antistatic type glass-reinforced plastic material |
-
2006
- 2006-07-25 CN CN200610019710A patent/CN100591720C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525466B (en) * | 2009-04-03 | 2012-07-04 | 复旦大学 | Epoxy/organosilicon/inorganic nano-hybrid material, and preparation method and application thereof |
| CN108084659A (en) * | 2017-12-23 | 2018-05-29 | 陈建峰 | A kind of preparation method of high intensity Antistatic type glass-reinforced plastic material |
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| CN100591720C (en) | 2010-02-24 |
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