CN104277069A - Synthesis and application of new nano hybrid - Google Patents
Synthesis and application of new nano hybrid Download PDFInfo
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- CN104277069A CN104277069A CN201310282079.7A CN201310282079A CN104277069A CN 104277069 A CN104277069 A CN 104277069A CN 201310282079 A CN201310282079 A CN 201310282079A CN 104277069 A CN104277069 A CN 104277069A
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- epoxy resin
- poss
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- phenyl aldehyde
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Abstract
The invention discloses synthesis and application of a new nano hybrid; first, gamma-aminopropyl triethoxy silane as a raw material is used for the synthesis of cage type octapoly-aminopropyl silsesquioxane (POSS-NH2), and the cage type octapoly-aminopropyl silsesquioxane (POSS-NH2) is reacted with a benzaldehyde, methanol and water mixed solvent at room temperature to prepare the nano-scale inorganic / organic hybrid. In a three mouth flask, 150ml of distilled water and 8.9 grams of (POSS-NH2) are added, 8.5 grams of benzaldehyde is weighed and mixed with 50ml ethanol, the mixed solution is dripped slowly into the three mouth flask, dripping is finished in 10min, reaction is performed for 1 hour at 25 DEG C, after the reaction is finished, petroleum ether is used to wash impurities, and a white solid matter is obtained by vacuum drying. The nano-scale inorganic / organic hybrid is added into epoxy resin (E-51) for modification to cure the epoxy resin. Tensile strength and impact strength of modified epoxy resin is greatly increased, and the glass transition temperature is greatly improved. Comprehensive performance and application range of the epoxy resin can be greatly improved by the inorganic / organic hybrid.
Description
Technical field
A synthesis for nano inorganic/organic hybrid thing, relates to a kind of containing the inorganic Synthesis and applications with the nano hybrid of organic constituent, belongs to hybrid material technical field.
Background technology
In recent years, the compound research of organic polymer and inorganic materials causes the great interest of people, by the synergy between organic and inorganic component, bill of material can be made to reveal the over-all properties with organic polymer material and inorganic functional material.Inorganic/organic hybrid nano composite material refers to that dispersed phase size has at least one dimension to be less than the matrix material of 100nm magnitude.This matrix material is different from traditional polymer/inorganic filler compound system, and organic phase and inorganic phase are composited in nanometer range.Between two-phase, interfacial area is very large, and the Chemical bond between Presence of an interface, there is desirable adhesiveproperties, inorganic phase and polymeric matrix two kinds of material thermal expansivity mismatch problems can be eliminated.It not only has the processibility of organic material high, toughness and low cost concurrently, remains that inorganic materials is heat-resisting, resistance to oxidation and excellent mechanical property .. simultaneously
Cage modle oligomeric silsesquioxanes (polyhedral oligomeric silsesquioxane, be called for short POSS) be a class novel hybride thing, a cagelike structure is contained at its center, eight drift angles contain dissimilar organic group, along with the size of organic group is different, the size distribution of such hybrid is between for 1-3 nanometer.Due to the structure of its uniqueness, thus have a wide range of applications in the new organic-inorganic nanocomposite research field of preparation.
Epoxy resin has many good characteristics, is therefore widely used in the every field of national economy.No matter be high-technology field, field of general technology, or national defense and military is industrial or civilian industry, and even its trace in daily life, can be seen.Divide by the mode of its application and can be used as: coating material, strongthener, casting material, moulding compound, tackiness agent, properties-correcting agent.Although epoxy resin has many excellent specific properties, there is the shortcoming of poor toughness, non-refractory.Therefore toughening modifying is carried out to epoxy resin on Theory and applications, have important meaning.
The object of the invention is to synthesize a kind of hybrid thing with rigid-skeleton.Reacted by cage modle oligomeric silsesquioxanes and phenyl aldehyde, the POSS drift angle making to have cagelike structure connects the phenyl ring of eight rigidity, this hybrid is used for the toughening modifying of epoxy resin, improves the stretch-proof of epoxy resin, shock resistance and resistance toheat to reach.
Summary of the invention:
1. prepared a kind of novel inorganic/organic hybrid thing, center has the cagelike structure of siloxane bond composition, and the organic group that eight drift angles are made up of phenyl aldehyde contracting aminopropyl is distributed in around cage modle skeleton symmetrically and evenly, and product has the structure shown in accompanying drawing 1.
2. this hybrid is used for the modification of epoxy resin E-51, substantially increases the tensile strength of epoxy resin, resistance to impact shock and high temperature resistance.Enhance the comprehensive use properties of epoxy resin.
Advantage of the present invention:
1., due to the structure leading role of center cage modle skeleton, make this material have good symmetry and stability, there is nano-scale.
2., because eight drift angles of cagelike structure are uniform-distribution with the benzene radicals of 8 rigidity, greatly can improve the tensile strength of epoxy resin, resistance to impact shock and second-order transition temperature.Improve the comprehensive use properties of epoxy resin.The tensile strength of modified epoxy resin brings up to modified 43Mpa by 27Mpa before modified, and shock strength is by 1.48KJ/m before modified
2bring up to modified 8.1KJ/m
2.The second-order transition temperature of epoxy resin brings up to modified 108 DEG C by 53 before modified DEG C.
3. this inorganic/organic hybrid thing preparation method is convenient, and equipment is simple, and room temperature reaction, raw material is easy to get, low price, easy large-scale promotion application.
Accompanying drawing illustrates:
The structural formula of accompanying drawing 1 inorganic/organic nano hybrid eight-(phenyl aldehyde contracting aminopropyl) cage modle eight polysilsesquioxane (POSS-PhM)
Accompanying drawing 2POSS-NH
2nucleus magnetic hydrogen spectrum figure
Accompanying drawing 3 is inorganic/organic hybrid thing (POSS-PhM) and POSS-NH
2infrared spectrogram contrasts
Accompanying drawing 4 POSS-PhM schemes the DSC of hybrid material after epoxy resin modification
Accompanying drawing 5 POSS-PhM changes the tensile strength of hybrid material after epoxy resin modification
Accompanying drawing 6 POSS-PhM changes the resistance to impact shock of hybrid material after epoxy resin modification
Embodiment
Embodiment 1: under room temperature, 135ml deionized water, 60ml n-propyl alcohol, 15ml acetonitrile, 7.5ml tetraethyl ammonium hydroxide are added in 500ml there-necked flask, stirring makes solution fully mix. then under violent stirring, slowly drip 330gKH-550, within 10 minutes, dropwise. temperature is risen to 54 DEG C. react and be down to room temperature after 24 hours. with tetrahydrofuran (THF), product partial crystallization is out obtained white solid powder, then clean 3 suction filtrations with tetrahydrofuran (THF). the vacuum chamber being finally put into 100 DEG C is dried for 24 hours.
Embodiment 2: in 250ml there-necked flask, adds 150ml deionized water and the 8.9 grams of poly-aminopropyl silsesquioxane of cage modle eight (POSS-NH
2), then press POSS-NH
2phenyl aldehyde 8.5 grams is taken with the mol ratio of phenyl aldehyde 1: 8, slowly the mixing solutions of phenyl aldehyde and 50ml ethanol is slowly instilled in there-necked flask under room temperature, dropwise in 10min, 25 DEG C are reacted 1 hour, after question response completes, outwell the liquid on upper strata, obtain the solid matter of thickness, clean impurity with sherwood oil, be placed in vacuum drying oven decompression drying, obtain white solid matter.
Embodiment 3: with embodiment 2, but phenyl aldehyde consumption is 10.2 grams, and other operations are the same, obtain white product.
Embodiment 4: with embodiment 2, but phenyl aldehyde consumption is 11.9 grams, and other operations are the same, obtain white product.
Embodiment 5: with embodiment 2, but phenyl aldehyde consumption is 13.6 grams, and other operations are the same, obtain white product.
Embodiment 6: measured by embodiment 2 gained sample pellet technique, adopts the infrared spectrogram of Fourier infrared spectrograph (2000-104 type) working sample, at 4500 ~ 500cm
-1carry out infrared absorption scanning in wave-number range, sweep velocity is 32 times/second, and resolving power is 4cm
-1.Infrared spectrogram is shown in accompanying drawing 3.3358cm can be found out by collection of illustrative plates
-1and 3305cm
-1it is N-H asymmetrical stretching vibration absorption peak; 2930cm
-1and 2855cm
-1it is the C-H stretching vibration absorption peak of methylene radical; 1558cm
-1for N-H flexural vibration peak; 1486cm
-1methylene radical C-H flexural vibration peaks; 1032cm
-1and 1123cm
-1it is the asymmetrical stretching vibration absorption peak of Si-O-Si.Pass through POSS-NH
2infrared spectrogram and KH-550 infrared spectrogram contrast, and can see the 2974cm of KH-550
-1methyl C-H flexural vibration peak at POSS-NH
2absorption peak on spectrogram becomes very weak and does not occur O-H stretching vibration absorption peak, and KH-550 fully hydrolysis also condensation in building-up process is described.
Embodiment 7: just embodiment 2 gained sample and epoxy resin (E-51) are undertaken blended by proportioning shown in table 2 respectively, are fully uniformly mixed.Pouring into after being mixed with a certain amount of triethylene tetramine by blend scribbles in the mould of releasing agent again, elevated cure: 30min at 50 DEG C, 30min at 80 DEG C, and at 100 DEG C, 30min. post-processing temperature is 2h at 110 DEG C.Be prepared into standard batten, the micro-processor controlled electronic universal tester of KQL carries out tensile strength and resistance to impact shock test.Tensile strength experimental result is shown in Fig. 5, resistance to impact shock experimental result Fig. 6.
Embodiment 8: respectively embodiment 2, embodiment 3, embodiment 4, embodiment 5 gained sample 5mg are placed in aluminium dish pressing sealing, at N
2(N under atmosphere
2flow is 200mL/min) heat up with certain temperature rise rate, carry out dsc analysis.Fig. 4 is the DSC collection of illustrative plates with POSS-PhM modified epoxy, and can find the increase along with POSS-PhM add-on by this figure of com-parison and analysis, Tg can increase gradually.The second-order transition temperature not adding the epoxy resin of POSS-PhM modification is 53 DEG C, and when POSS-PhM addition is 15%, modified glass epoxy transition temperature rises to 108 DEG C.
Table 1 novel inorganic/organic hybrid thing synthesizing formula table look-up
POSS-NH
2molecular weight: 888; Phenyl aldehyde molecular weight: 106:
Table 2 is inorganic/and organic hybrid thing is to epoxy resin modification formula
Claims (4)
1. novel nano inorganic/synthesis of organic hybrid thing, the feature of hybrid is the cagelike structure that center has siloxane bond composition, and the organic group that eight drift angles are made up of phenyl aldehyde contracting aminopropyl is distributed in around cage modle skeleton symmetrically and evenly.
2. a synthetic method for inorganic shown in claim 1/organic hybrid thing, is characterized in that poly-for cage modle eight aminopropyl silsesquioxane (POSS-NH
2) obtained with phenyl aldehyde room temperature reaction in the mixed solvent of water and methyl alcohol.In 250ml there-necked flask, add 150ml deionized water and the 8.9 grams of poly-aminopropyl silsesquioxane of cage modle eight (POSS-NH
2), then press POSS-NH
2phenyl aldehyde 8.5 grams is taken with the mol ratio of phenyl aldehyde 1: 8, under room temperature, the mixing solutions of phenyl aldehyde and 50ml ethanol is slowly instilled in there-necked flask, dropwise in 10min, 25 DEG C are reacted 1 hour, after question response completes, outwell the liquid on upper strata, obtain the solid matter of thickness, clean impurity with sherwood oil, be placed in vacuum drying oven decompression drying, obtain white solid matter.
3. the synthetic ratio of novel inorganic shown in claim 1/organic hybrid thing, is characterized in that the poly-aminopropyl silsesquioxane of cage modle eight (POSS-NH
2) be 1: 8 with the mol ratio of phenyl aldehyde; 1: 9.6; 1: 11.2 and 1: 12.8.
4. novel inorganic shown in claim 1/organic hybrid thing is applied to the modification of epoxy resin (E-51).It is characterized in that in table 1 No. 1 sample and the solidifying agent (triethylene tetramine) of 8%, the thinner (1 of 10%, 4-butyleneglycol glycidyl ether) mix, then join among epoxy resin and go, thus improve the dispersed degree of hybrid sample among epoxy resin.Poured in the mould made in advance by mixture and be cured, epoxy resin cure technique is temperature-gradient method solidification: 30min at 50 DEG C, 30min at 80 DEG C, 30min at 100 DEG C, post-processing temperature is 2h at 110 DEG C.Be prepared into standard batten, the micro-processor controlled electronic universal tester of KQL carries out tensile strength and elongation at break test.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698740A (en) * | 2017-11-02 | 2018-02-16 | 合众（佛山）化工有限公司 | A kind of low form epoxy hardener and its epoxide terrace paint based on POSS |
| CN111118639A (en) * | 2019-09-20 | 2020-05-08 | 江苏华力索菲新材料有限公司 | Preparation method of titanium dioxide delustering agent for high-dispersity textile fabric |
| CN116643049A (en) * | 2023-07-27 | 2023-08-25 | 云南省农业科学院质量标准与检测技术研究所 | Profenofos pesticide colloidal gold marker based on modified nano gold material and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6055031A (en) * | 1983-09-06 | 1985-03-29 | Tokuyama Soda Co Ltd | Polysilsesquioxane |
| CN103087088A (en) * | 2011-10-28 | 2013-05-08 | 江南大学 | Preparation and applications of novel alkyl cage silsesquioxane nanometer hybrid |
-
2013
- 2013-07-08 CN CN201310282079.7A patent/CN104277069B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| VINICIUS PISTOR ET AL.: "Influence of different concentrations of N-phenylaminopropyl - POSS on the thermodynamic fragility of the cured epoxy resin", 《POLYMER》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698740A (en) * | 2017-11-02 | 2018-02-16 | 合众（佛山）化工有限公司 | A kind of low form epoxy hardener and its epoxide terrace paint based on POSS |
| CN111118639A (en) * | 2019-09-20 | 2020-05-08 | 江苏华力索菲新材料有限公司 | Preparation method of titanium dioxide delustering agent for high-dispersity textile fabric |
| CN116643049A (en) * | 2023-07-27 | 2023-08-25 | 云南省农业科学院质量标准与检测技术研究所 | Profenofos pesticide colloidal gold marker based on modified nano gold material and application thereof |
| CN116643049B (en) * | 2023-07-27 | 2023-09-29 | 云南省农业科学院质量标准与检测技术研究所 | Profenofos pesticide colloidal gold marker based on modified nano gold material and application thereof |
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Effective date of registration: 20201125 Address after: Gangzha District of Jiangsu city of Nantong province Changtai 226000 Road on the eastern side of the tip of the hook head village 9 groups of 1. Patentee after: NANTONG ORIENT PLASTIC Co.,Ltd. Address before: School of chemical engineering Jiangnan University No. 1800 214122 Jiangsu city of Wuxi Province Li Lake Avenue Patentee before: Jiangnan University |