CN104277069B

CN104277069B - Synthesis and application of new nano hybrid

Info

Publication number: CN104277069B
Application number: CN201310282079.7A
Authority: CN
Inventors: 倪才华; 袁广; 张丽萍
Original assignee: Jiangnan University
Current assignee: NANTONG ORIENT PLASTIC Co.,Ltd.
Priority date: 2013-07-08
Filing date: 2013-07-08
Publication date: 2017-02-08
Anticipated expiration: 2033-07-08
Also published as: CN104277069A

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

A kind of synthesis of novel nano hybrid and application

Technical field

A kind of synthesis of nano inorganic/organic hybrid thing, be related to a kind of containing inorganic and organic component nano hybrid Preparation and application, belong to hybrid material technical field.

Background technology

In recent years, the compound research of organic polymer and inorganic material causes the great interest of people, by organic and Synergy between inorganic component, can make material show and have the comprehensive of high-molecular organic material and inorganic functional material Energy.Inorganic/organic hybrid nano composite material refers at least one-dimensional composite less than 100nm magnitude of dispersed phase size. This composite is different from traditional polymer/inorganic filler compound system, and organic phase and inorganic phase are in nanometer range It is composited.Between two-phase, interfacial area is very big, and the chemical bond between Presence of an interface, has preferable adhesive property, can Eliminate inorganic phase and two kinds of material thermal coefficient of expansion mismatch problems of polymer substrate.It not only has adding of organic material high concurrently Work, toughness and low cost, remain that inorganic material is heat-resisting, resistance to oxidation and excellent mechanical property .. simultaneously

Cage modle oligomeric silsesquioxanes (polyhedral oligomeric silsesquioxane, abbreviation POSS) are one Class novel hybride thing, a cagelike structure is contained at its center, and eight drift angles contain different types of organic group, with organic group The size of group is different, and the particle diameter distribution of such hybrid is between for 1-3 nanometer.Due to its unique structure, thus in preparation New organic-inorganic nanocomposite research field has a wide range of applications.

Epoxy resin has many good characteristics, is therefore widely used in the every field of national economy.Either In high-technology field, field of general technology, or national defense and military industry or civilian industry, or even daily life It can be seen that its trace.To divide in the way of it is applied can conduct：Coating material, reinforcing material, casting material, moulding compound, Adhesive, modifying agent.Although epoxy resin has many excellent specific properties, there is poor toughness, non-refractory.Therefore Epoxy resin is carried out with toughening modifying has important meaning theoretical with applying.

It is an object of the invention to synthesizing a kind of hybrid thing with rigid-skeleton.Neat by cage modle Polysilsesquioxane is reacted with benzaldehyde, makes to connect the phenyl ring of eight rigidity on the POSS drift angle have cagelike structure, and this is miscellaneous Compound is used for the toughening modifying of epoxy resin, to reach stretch-proof, shock resistance and the heat resistance improving epoxy resin.

Content of the invention：

1. it is prepared for a kind of novel inorganic/organic hybrid thing, center has the cagelike structure of silicon oxygen bond composition, eight drift angles Symmetrically and evenly it is distributed in around cage modle skeleton by the organic group that benzaldehyde contracting aminopropyl forms, product has accompanying drawing 1 institute The structure shown.

2. this hybrid is used for the modification of epoxy resin E-51, substantially increases tensile strength, the anti-impact of epoxy resin Hit intensity and high temperature resistance.Enhance the comprehensive serviceability of epoxy resin.

Advantages of the present invention：

1. because the structure leading role of center cage modle skeleton is so that this material has preferable 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, epoxy can be greatly improved The tensile strength of resin, impact strength and vitrification point.Improve the comprehensive serviceability of epoxy resin.Modified ring The tensile strength of oxygen tree fat brings up to modified 43Mpa by 27Mpa before modified, and impact strength is by 1.48KJ/ before modified m²Bring up to modified 8.1KJ/m².The glass transition temperature of epoxy resin is brought up to modified by 53 DEG C before modified 108℃.

3. this inorganic/organic hybrid thing preparation method facility, equipment is simple, room temperature reaction, and raw material is easy to get, low price, Easily large-scale promotion application.

Brief description：

Accompanying drawing 1 inorganic/organic nano hybrid eight-(benzaldehyde contracting aminopropyl) cage modle eight polysilsesquioxane (POSS- PhM structural formula)

Accompanying drawing 2 POSS-NH₂Nucleus magnetic hydrogen spectrum figure

Accompanying drawing 3 is inorganic/organic hybrid thing (POSS-PhM) and POSS-NH₂Infrared spectrogram contrasts

Accompanying drawing 4 DSC figure to hybrid material after epoxy resin modification with POSS-PhM

Accompanying drawing 5 tensile strength change to hybrid material after epoxy resin modification with POSS-PhM

Accompanying drawing 6 impact strength change to hybrid material after epoxy resin modification with POSS-PhM

Specific embodiment

Embodiment 1：By 135ml deionized water, 60ml normal propyl alcohol, 15ml acetonitrile, 7.5ml tetraethyl ammonium hydroxide under room temperature Add in 500ml there-necked flask, stirring makes solution be sufficiently mixed. and then slowly drip 330gKH-550 under violent stirring, 10 minutes completion of dropping. temperature is risen to 54 DEG C. reaction was down to room temperature after 24 hours. with oxolane, product partial crystallization out obtained White solid powder, then 3 suction filtrations are cleaned with oxolane. finally it is put into 100 DEG C of vacuum tank drying in 24 hours.

Embodiment 2：In 250ml there-necked flask, add 150ml deionized water and the poly- aminopropyl sesquialter of 8.9 grams of cage modles eight Siloxanes (POSS-NH₂), then press POSS-NH₂Weigh 8.5 grams of benzaldehyde with the mol ratio of benzaldehyde 1: 8, slowly will at room temperature Benzaldehyde is slowly dropped in there-necked flask with the mixed solution of 50ml ethanol, completion of dropping in 10min, and 25 DEG C are reacted 1 hour, treat After the completion of reaction, outwell the liquid on upper strata, obtain sticky solid matter, clean impurity with petroleum ether, be placed in vacuum drying oven Decompression drying, obtains white solid matter.

Embodiment 3：With embodiment 2, but benzaldehyde consumption is 10.2 grams, and other operations are the same, obtain white product.

Embodiment 4：With embodiment 2, but benzaldehyde consumption is 11.9 grams, and other operations are the same, obtain white product.

Embodiment 5：With embodiment 2, but benzaldehyde consumption is 13.6 grams, and other operations are the same, obtain white product.

Embodiment 6：Embodiment 2 gained sample is measured with pellet technique, using Fourier infrared spectrograph The infrared spectrogram of (2000-104 type) determination sample, in 4500～500cm^-1Carry out INFRARED ABSORPTION scanning in wave-number range, sweep Retouching speed is 32 times/second, and resolution ratio is 4cm^-1.Infrared spectrogram is shown in accompanying drawing 3.By collection of illustrative plates it can be seen that 3358cm^-1And 3305cm^-1It is N-H asymmetric stretching vibration absworption peak；2930cm^-1And 2855cm^-1It is the C-H stretching vibration absworption peak of methylene； 1558cm^-1For N-H flexural vibrations peak；1486cm^-1It is methylene C-H flexural vibrations peak；1032cm^-1And 1123cm^-1It is Si-O- The asymmetric stretching vibration absworption peak of Si.By POSS-NH₂Infrared spectrogram is contrasted with KH-550 infrared spectrogram, can see 2974cm to KH-550^-1Methyl C-H flexural vibrations peak in POSS-NH₂Absworption peak on spectrogram becomes very weak and does not occur O-H stretching vibration absworption peak, illustrates that KH-550 is fully hydrolyzed in building-up process and is condensed.

Embodiment 7：Just proportioning as shown in table 2 is blended respectively for embodiment 2 gained sample and epoxy resin (E-51), It is thoroughly mixed.Pour into after again blend being mixed with a certain amount of triethylene tetramine in the mould scribbling releasing agent, heat up Solidification：30min at 50 DEG C, 30min at 80 DEG C, 2h at 30min. post-processing temperature is 110 DEG C at 100 DEG C.It is prepared into standard sample Bar, carries out tensile strength and impact strength test on the micro-processor controlled electronic universal tester of KQL.Tensile strength is real Test result and see Fig. 5, impact strength experimental result Fig. 6.

Embodiment 8：Respectively embodiment 2, embodiment 3, embodiment 4, embodiment 5 gained sample 5mg are placed in pressure in aluminium dish Close sealing, in N₂(N under atmosphere₂Flow is 200mL/min) heated up with certain heating rate, carry out dsc analysis.Fig. 4 is to use The DSC collection of illustrative plates of POSS-PhM modified epoxy, can be found that the increasing with POSS-PhM addition by this figure of com-parison and analysis Plus, Tg can be gradually increased.The glass transition temperature being not added with the modified epoxy resin of POSS-PhM is 53 DEG C, works as POSS-PhM When addition is 15%, modified glass epoxy transition temperature rises to 108 DEG C.

Table 1 novel inorganic/organic hybrid thing synthesizing formula list

POSS-NH₂Molecular weight：888；Benzaldehyde molecular weight：106：

Table 2 is inorganic/and organic hybrid thing is to epoxy resin modification formula

Claims

1. a kind of novel nano inorganic/organic hybrid thing, the feature of hybrid is the cagelike structure that center has silicon oxygen bond composition, Eight drift angles are symmetrically and evenly distributed in around cage modle skeleton by the organic group that benzaldehyde contracting aminopropyl forms, and haveStructure.

2. a kind of synthetic method of inorganic shown in claim 1/organic hybrid thing, is characterized in that poly- for cage modle eight aminopropyl times Half siloxanes (POSS-NH₂) in the mixed solvent with methyl alcohol for the water, room temperature reaction is obtained with benzaldehyde, in 250ml there-necked flask In, add 150ml deionized water and the poly- aminopropyl silsesquioxane (POSS-NH of 8.9 grams of cage modles eight₂), then press POSS-NH₂With The mol ratio of benzaldehyde 1: 8 weighs 8.5 grams of benzaldehyde, is slowly dropped into the mixed solution of benzaldehyde and 50ml ethanol at room temperature In there-necked flask, completion of dropping in 10min, 25 DEG C are reacted 1 hour, after the completion of question response, outwell the liquid on upper strata, obtain sticky Solid matter, with petroleum ether clean impurity, be placed in decompression drying in vacuum drying oven, obtain white solid matter.

3. the synthetic method of novel inorganic shown in a kind of claim 2/organic hybrid thing, is characterized in that the poly- aminopropyl of cage modle eight Silsesquioxane (POSS-NH₂) it is 1: 8 with the mol ratio of benzaldehyde.

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：To weigh Measure the POSS-NH for 8.9g₂Mix with the benzaldehyde for 8.5g for the weight, novel inorganic/have is obtained by claim 2 methods described Machine hybrid, by the curing agent of this hybrid and 8%, its entitled triethylene tetramine, 10% diluent, its entitled Isosorbide-5-Nitrae- Butanediol glycidol ether, mixes, and is then added to go among epoxy resin, thus improving hybrid sample in asphalt mixtures modified by epoxy resin Dispersed degree among fat, is solidified in the mould pouring the mixture into pre-production, and epoxy resin cure technique is Temperature-gradient method solidifies：30min at 50 DEG C, 30min at 80 DEG C, 30min at 100 DEG C, post-processing temperature is 2h at 110 DEG C, preparation One-tenth standard batten, carries out tensile strength and elongation at break test on the micro-processor controlled electronic universal tester of KQL.