CN109456486B - Multifunctional high-temperature-resistant POSS nano-molecular material and preparation method thereof - Google Patents
Multifunctional high-temperature-resistant POSS nano-molecular material and preparation method thereof Download PDFInfo
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- CN109456486B CN109456486B CN201811300006.5A CN201811300006A CN109456486B CN 109456486 B CN109456486 B CN 109456486B CN 201811300006 A CN201811300006 A CN 201811300006A CN 109456486 B CN109456486 B CN 109456486B
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Abstract
The invention discloses a multifunctional high-temperature-resistant POSS nano molecular material and a preparation method thereof. The preparation method comprises the following steps: the following reactants were charged to the reactor: amine compound RNHR with carbon chain at two ends1The preparation method comprises the following steps of (1) dissolving reactants added into a solvent, adding a catalyst after the reactants are dissolved and uniformly dispersed, and reacting to obtain a POSS-based hybrid material; respectively washing the POSS-based hybrid material with an organic solvent and deionized water, removing residual free radical initiator and unreacted reactants, and drying in vacuum to obtain the multifunctional high-temperature-resistant POSS nano molecular material. The invention provides a method for preparing a multifunctional nano hybrid material by an amino-epoxy group open loop system, so that the multifunctional nano hybrid material with excellent thermal stability and hydrophobicity is obtained, has the advantages of controllable condensed state form, multifunctional reaction groups and the like, and can be applied to the fields of high-temperature-resistant enhanced composite additive materials, adhesives, reinforcing agents, novel functional materials and the like.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis methods, and relates to a method for preparing a multifunctional high-temperature-resistant silsesquioxane (POSS) nano molecular material by using an amino-epoxy group ring-opening system, in particular to a multifunctional high-temperature-resistant silsesquioxane (POSS) nano molecular material prepared by uniformly stirring polyhedral oligomeric silsesquioxane (EPOSS) containing a polyepoxy functional group, an amine compound, a free radical initiator and a solvent and using an amino-epoxy group ring-opening reaction one-step method and a method thereof.
Background
The solid functional material is a general name of engineering materials mainly used in industry and technology, that is, a material having special properties in the aspects of electricity, magnetism, sound, light, heat, etc., or showing special functions under the action thereof. The development of functional materials is more rapid due to the appearance of nanotechnology, novel functional materials are continuously emerging, and functional materials with high precision and high efficiency are in endless range. The nano material is a material with a composition phase or crystal grain with the size smaller than 100nm in any dimension, and is a solid material consisting of superfine particles with the particle size between 1 nm and 100 nm. They have many excellent properties including mechanical, magnetic, electrical, optical and catalytic properties, with wide high technical applicability. The nano material has very small size, generally has larger specific surface area and high catalytic activity, but also has very high surface energy, which causes the nano particles to be very unstable in thermodynamics and to be very easy to agglomerate especially under the heating treatment condition.
POSS is used as a brand-new nano material, injects new activity into the research of polymer nano composite materials, and provides a new idea for the design of new materials. Because POSS has special physical and chemical properties, the POSS can be easily and uniformly dispersed to other materials or polymer systems in the modes of reaction, polymerization or physical blending and the like, so that the POSS has incomparable advantages compared with other common inorganic nano materials in the field of novel temperature-resistant reinforced material modification. The reactive POSS functional molecule with an inorganic core structure can have the high-temperature stability and mechanical property of inorganic materials, organic components, the bonding property of the POSS molecule and the solubility and compatibility of various high-molecular systems, and can react with various polymers to be used as a terminal capping group or a crosslinking curing center to form an organic-inorganic hybrid composite material so as to meet the modification requirements of various polymers.
Chinese patent 201310140789.6 entitled dihydroxy cage type silsesquioxane monomer and its preparation method comprises adding a disilicon hydrogen cage type polysilsesquioxane monomer and a eugenol monomer into a nitrogen-protected container, adding toluene as a solvent according to a feeding molar ratio of 1: 2-16, dropwise adding a Kaster with a Pt mass percentage of 0.3% accounting for 0.1% of the volume fraction of the solvent as a catalyst, and reacting to obtain the dihydroxy cage type silsesquioxane monomer. Chinese patent 201510232826.5 "preparation method of polyhedral oligomeric silsesquioxane-calcium hydroxide composite flame retardant material" is prepared by mixing trichloromethylsilane and acetone, heating, refluxing and filtering to obtain 7-methyl trihydroxy-7-polysilsesquioxane, preparing calcium hydroxide solution from quicklime and distilled water, slowly dripping the calcium hydroxide solution into the prepared siloxane, heating, refluxing, filtering and drying. The synergistic effect between polyhedral silsesquioxane and calcium hydroxide is fully exerted, and the flame retardance is greatly improved. Chinese patent 201710548862.1 entitled POSS/PPS nanocomposite and preparation method and application thereof is prepared from polyphenylene sulfide, reactive-type multi-terminal polyhedral silsesquioxane and auxiliary materials, and can improve thermal performance and mechanical performance by adding POSS into PPS and changing compatibility and dispersibility. The high-strength high-toughness high-temperature oxidation-resistant light-resistant high-fluidity light-resistant alloy has the advantages of high strength, good toughness, high-temperature oxidation resistance, high light resistance, good fluidity, easiness in processing and the like.
The traditional nano particle modification has the defects of complex equipment structure, high manufacturing cost, inconvenient operation and the like. Moreover, collection of the particulate product is also difficult, and the collected particles have low stability.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the traditional nano particle modification has the defects of complex equipment structure, high manufacturing cost, inconvenient operation and the like, and the collection of particle products is difficult and the stability of particles is low.
In order to solve the problems, the invention provides a preparation method of a multifunctional high-temperature-resistant POSS nano molecular material, which is characterized by comprising the following steps of:
step 1): the following reactants were charged to the reactor: amine compound RNHR with carbon chain at two ends1The octa-epoxy POSS and the solvent are added with the catalyst after the added reactants are dissolved and uniformly dispersed;
step 2): reacting the solution obtained in the step 1) for 2-6 h at 30-80 ℃ under the protection of nitrogen to obtain a POSS-based hybrid material;
step 3): respectively washing the POSS-based hybrid material obtained in the step 2) with an organic solvent and deionized water, removing residual free radical initiator and unreacted reactants, and drying in vacuum to obtain the multifunctional high-temperature-resistant POSS nano molecular material.
Preferably, the molar ratio of the amine compound to the octa-epoxy POSS in the step 1) is (1-8): 1.
Preferably, the synthesis method of the octa-epoxy POSS in the step 1) is as follows: hydrolyzing and condensing 3-glycidoxypropyltrimethylsilane under the catalytic action of hydrochloric acid to obtain POSS with eight epoxy groups.
Preferably, the catalyst in step 1) is zirconium chloride, cobalt chloride, lithium bromide, copper fluoroborate, lithium aluminum hydride, lithium perchlorate, aluminum chloride or cuprous iodide.
Preferably, the amine compound RNHR in the step 1)1R or R of1Is hydrogen atom, inert alkane, aromatic hydrocarbon, heterocyclic group or other active functional group.
Preferably, the solvent in step 1) is any one of ethanol, methanol, water, toluene, dichloromethane, DMF, tetrahydrofuran, 1, 4-dioxane, trimethylbenzene and chloroform. DMF, tetrahydrofuran, 1, 4-dioxane are preferred.
Preferably, the temperature of vacuum drying in the step 3) is 40-60 ℃, and the time is 8-24 h.
Preferably, the organic solvent in step 3) is ethanol, methanol or chloroform.
The invention also provides the multifunctional high-temperature-resistant POSS nano molecular material prepared by the preparation method of the multifunctional high-temperature-resistant POSS nano molecular material.
The invention provides a method for preparing a multifunctional nano hybrid material by an amino-epoxy group open loop system, thereby obtaining the multifunctional nano hybrid material with excellent thermal stability and hydrophobicity. The preparation method is simple, pollution-free, capable of realizing mass production, stable in product, easy to store and low in price, the prepared multifunctional nano particles can be chemically or physically compounded with other materials through a solid-phase organic grinding method, a high-temperature melting processing method and the like, various high-temperature-resistant enhanced novel functional materials are prepared, the operation is simple, and the use and preparation process is convenient.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a feasible method by utilizing a method for preparing the multifunctional nano hybrid material through an amino-epoxy group open loop system, the method is simple and easy to implement, the reaction is efficient and rapid, and the reaction conditions are mild;
2. the multifunctional nano hybrid particles prepared by the invention are not easy to dissolve in any solvent, and have stable properties and are not corroded by the solvent;
3. the multifunctional nano hybrid material prepared by the invention has excellent performances such as good heat resistance, high refractivity, hydrolysis resistance and the like, and has wide application prospect in the aspect of functional polymer materials.
Drawings
FIG. 1 is a synthesis route diagram of a preparation method of POSS nano-molecular material provided by the present invention;
FIGS. 2 and 3 are thermogravimetric analysis diagrams of POSS nano-molecular materials prepared in examples 1-4.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of a multifunctional high-temperature-resistant POSS nano molecular material comprises the following steps:
1): synthesis of POSS-diethylamine ratio (1/1): 3.5g (2mmol) of E-POSS were dissolved in 30mL of chloroform and 0.0027g (0.02mmol) of AlCl was added to a three-necked flask3Catalyzing ring opening of the epoxy group;
2): under nitrogen protection, 0.21mL (2mmol) of diethylamine was slowly injected into the mixed solution. Rapidly stirring, and carrying out reflux reaction at 60 ℃ for 4h to obtain a light yellow solid-liquid mixture;
3): vacuum filtering to collect residue, repeatedly cleaning and purifying the obtained crude product with chloroform and distilled water, and drying in a vacuum oven at 40 ℃ for 24h to obtain light yellow powder.
The yield of this example was 97%. The synthetic route and the molecular formula are shown in the synthetic route 1. 13C NMR,. delta.8.29, 22.81,43.65,50.40,63.99, 72.58.29Si NMR, delta-68.31, -130.96. Its decomposition temperature: 177.88 deg.C; maximum decomposition temperature: 239.20 deg.C; residual carbon content: 32.50 percent.
Example 2
A preparation method of a multifunctional high-temperature-resistant POSS nano molecular material comprises the following steps:
the present embodiment is different from embodiment 1 in that:
the step 1) is as follows: synthesis of POSS-diethylamine ratio (1/4): the amount of diethylamine added was 0.84mL (8mmol), the amount of E-POSS added was 3.5g (2mmol), and the amount of catalyst added was 0.01068g (0.08mmol) of AlCl3。
The yield of this example was 97%. The synthetic route and the molecular formula are shown in the synthetic route 1. 13C NMR,. delta.8.29, 22.81,43.65,50.40,63.99, 72.58. 29Si NMR, delta-68.31, -130.96. The decomposition temperature is as follows: 261.10 deg.C; maximum decomposition temperature: 274.1 deg.C; residual carbon content: 42.1 percent.
Example 3
A preparation method of a multifunctional high-temperature-resistant POSS nano molecular material comprises the following steps:
the present embodiment is different from embodiment 1 in that:
the step 1) is as follows: synthesis of POSS-dibutylamine ratio (1/1): the addition amount of dibutylamine is 0.33mL (2mmol), the addition amount of E-POSS is 3.5g (2mmol), and AlCl3The amount of catalyst added was 0.0027g (0.02 mmol).
The yield of this example was 96%. 13C NMR Δ 8.89,13.54,24.01,46.11,51.29,64.09, 71.61. 29Si NMR, delta-68.31, -130.96. The decomposition temperature is as follows: 227.50 deg.C; maximum decomposition temperature: 330.60 deg.C; residual carbon content: 40.2 percent.
Example 4
A preparation method of a multifunctional high-temperature-resistant POSS nano molecular material comprises the following steps:
the present embodiment is different from embodiment 1 in that:
the step 1) is as follows: synthesis of POSS-dibutylamine ratio (1/4): dibutylamine was added in an amount of 1.32mL (8 mmol). The addition amount of E-POSS was 3.5g (2mmol), and the addition amount of catalyst was 0.0107g (0.08mmol) of AlCl3。
The yield of this example was 96%. 13C NMR Δ 8.89,13.54,24.01,46.11,51.29,64.09, 71.61. 29Si NMR, delta-68.31, -130.96. The decomposition temperature is as follows: 272.4 deg.C; maximum decomposition temperature: 395.9 deg.C; residual carbon content: 50.8 percent.
Claims (8)
1. A preparation method of a multifunctional high-temperature-resistant POSS nano molecular material is characterized by comprising the following steps:
step 1): the following reactants were charged to the reactor: amine compound RNHR with carbon chain at two ends1Octa-epoxy group POSS and solvent, amine compound RNHR1R or R of1The catalyst is inert alkyl, and after the added reactants are dissolved and uniformly dispersed, the catalyst is added;
step 2): reacting the solution obtained in the step 1) for 2-6 h at 30-80 ℃ under the protection of nitrogen to obtain a POSS-based hybrid material;
step 3): respectively washing the POSS-based hybrid material obtained in the step 2) with an organic solvent and deionized water, removing residual catalyst and unreacted reactants, and drying in vacuum to obtain the multifunctional high-temperature-resistant POSS nano molecular material.
2. The method for preparing the multifunctional high-temperature POSS nano-molecular material as claimed in claim 1, wherein the molar ratio of the amine compound to the octa-epoxy POSS in the step 1) is (1-8): 1.
3. The method for preparing the multifunctional high temperature resistant POSS nano-molecular material as claimed in claim 1, wherein the synthesis method of the octa-epoxy POSS in the step 1) is: 3-glycidoxy propyl trimethoxy silane is hydrolyzed and condensed under the catalytic action of hydrochloric acid to obtain POSS with eight epoxy groups.
4. The method for preparing the multifunctional high temperature resistant POSS nano-molecular material as claimed in claim 1, wherein the catalyst in the step 1) is zirconium chloride, cobalt chloride, lithium bromide, copper fluoroborate, lithium aluminum hydride, lithium perchlorate, aluminum chloride or cuprous iodide.
5. The method for preparing the multifunctional high temperature resistant POSS nano-molecular material as claimed in claim 1, wherein the solvent in the step 1) is any one of ethanol, methanol, water, toluene, dichloromethane, DMF, tetrahydrofuran, 1, 4-dioxane, trimethylbenzene and chloroform.
6. The method for preparing the multifunctional high-temperature POSS nano-molecular material as claimed in claim 1, wherein the temperature of vacuum drying in the step 3) is 40-60 ℃ and the time is 8-24 h.
7. The method for preparing the multifunctional high temperature resistant POSS nano-molecular material as claimed in claim 1, wherein the organic solvent in step 3) is ethanol, methanol or chloroform.
8. A multifunctional high temperature resistant POSS nanomolecular material prepared by the method of any of claims 1-7.
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| CN111253860A (en) * | 2020-02-09 | 2020-06-09 | 西北工业大学 | Ablation-resistant organic silicon resin coating material and preparation method thereof |
| CN112724404B (en) * | 2021-01-18 | 2023-10-10 | 东华大学 | Hyperbranched phosphorus-nitrogen POSS-EP flame retardant, and preparation and application thereof |
| CN114045689A (en) * | 2021-11-22 | 2022-02-15 | 国佳凝胶科创中心(深圳)有限公司 | Preparation method of hydrogel cooling cloth |
| CN116333317A (en) * | 2023-02-22 | 2023-06-27 | 安徽中烟工业有限责任公司 | POSS-based hydrophobic material and preparation method thereof |
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| CN102372734A (en) * | 2010-08-24 | 2012-03-14 | 江南大学 | Synthesis of novel nano hybrid reinforcing agent containing POSS |
| CN106832287A (en) * | 2017-02-09 | 2017-06-13 | 南京大学 | The multifunctional active POSS of one class and its preparation method and purposes |
| CN107033354A (en) * | 2017-04-27 | 2017-08-11 | 湘潭大学 | A kind of liquid cage-type silsesquioxane and preparation method thereof |
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| CN102372734A (en) * | 2010-08-24 | 2012-03-14 | 江南大学 | Synthesis of novel nano hybrid reinforcing agent containing POSS |
| CN107057517A (en) * | 2016-12-22 | 2017-08-18 | 广东通科技股份有限公司 | A kind of silicon nitrogen phosphorus cooperative flame retardant aqueous epoxy resins of silsesquioxane crosslinking and preparation method thereof |
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| 《Synthesis and Characterization of Organic–Inorganic Hybrid Polymers with a Well-Defined Structure from Diamines and Epoxy-Functionalized Polyhedral Oligomeric Silsesquioxanes》;Hongyao Xu et al.;《Journal of Applied Polymer Science》;20060915;第101卷(第6期);3730–3735 * |
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