CN111320872A - Red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and preparation method thereof - Google Patents
Red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and preparation method thereof Download PDFInfo
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- CN111320872A CN111320872A CN202010292922.XA CN202010292922A CN111320872A CN 111320872 A CN111320872 A CN 111320872A CN 202010292922 A CN202010292922 A CN 202010292922A CN 111320872 A CN111320872 A CN 111320872A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and a preparation method thereof. The unique porous structure of the polyimide covalent organic framework material is utilized to improve the red phosphorus, and the red phosphorus-loaded porous polyimide covalent organic framework material is coated inside. The red phosphorus/polyimide covalent organic framework composite material has excellent flame retardant property, can be used as a flame retardant modified high-molecular organic material, cannot generate melting and dripping in the combustion process, and has a flame retardant effect which is remarkably improved compared with the flame retardant effect of pure red phosphorus. Furthermore, the invention also provides a feasible way for preparing the red phosphorus flame-retardant material, and the preparation method has strong repeatability and simple process.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to preparation and application of a red phosphorus/covalent organic framework composite material with efficient flame retardance.
Background
Covalent Organic Framework (COF) is a new direction for rapid development in the field of polymer materials research. The crystalline porous polymer is synthesized by a bottom-up method, and molecular building units connected by covalent bonds of the crystalline porous polymer can be pre-designed on secondary and tertiary structures, so that a highly ordered rigid porous structure can be synthesized, and the chemical and physical properties of the crystalline porous polymer can be finely adjusted. At present, covalent organic framework materials are generally prepared by a thermodynamic reversible reaction, and the synthesis method mainly comprises a solvothermal method, an ionothermal method, a microwave radiation method and a mechanochemical grinding method. The reactions for constructing covalent organic frameworks reported at present mainly include boric acid dehydration trimerization, condensation of boric acid and catechol compound, cyano self-polymerization, Schiff base reaction (dehydration condensation reaction of aldehyde and amine, hydrazine, hydrazone, etc.), and the like. The material has the advantages of large specific surface area, low density, diversified structures, extremely high thermal stability, easy modification of pore channels and the like, and is widely concerned by people. The porous characteristic means that the covalent organic framework material has considerable application prospect in the fields of separation, gas storage, sensing, optoelectronics, catalysis, heavy metal ion adsorption treatment and the like.
In recent years, red phosphorus has been found to be a very good flame retardant, but there are some disadvantages, such as: the hydroscopic property is strong, once exposed to the air, the hydroscopic property is easy to hydrolyze, and simultaneously, the toxic phosphine gas is released, thereby seriously polluting the environment. In addition, the compatibility of red phosphorus with many high polymers is poor, and the red phosphorus is not uniformly dispersed when being added into the high polymer material, so that gaps are generated inside the material, and the mechanical processing performance of the polyolefin material is seriously influenced and the mechanical performance of the material is reduced. And is easily ignited under strong impact, and has the danger of burning and explosion.
In the art, in order to make the red phosphorus flame retardant be better applied to organic materials, it is common practice to microencapsulate red phosphorus and wrap fine red phosphorus particles in the red phosphorus by coating one or more layers of dense protective films on the surface of the red phosphorus, so as to obtain the microencapsulated red phosphorus flame retardant. The treatment method of micro-encapsulated red phosphorus can be divided into an inorganic coating method, an organic coating method and an organic-inorganic coating method according to the division of red phosphorus-coated capsule materials. The capsule material used for the inorganic coating can be magnesium hydroxide, zinc hydroxide and the like, and is deposited on the surfaces of red phosphorus particles by a solution-gel method or a chemical precipitation method. The organic coating method is to coat red phosphorus with organic matter, at present, thermosetting resin such as epoxy resin is mostly used for coating, the organic coating method is to coat red phosphorus with organic matter as a capsule material, and high polymer materials are coated on the surfaces of red phosphorus particles by an interfacial polymerization method or an in-situ polymerization method. Although the organic polymer has the advantages of good compatibility with organic polymers, the organic polymer also has the disadvantages of poor hygroscopicity, low ignition point and the like. The organic-inorganic composite coating is to coat an inorganic substance layer and then an organic substance layer. But also can be used as a flame retardant to be applied to materials to improve the flame retardant property of the materials. Therefore, the organic-inorganic coating method is an ideal microcapsule coating method at present, which selects a proper capsule material to carry out secondary coating on the red phosphorus based on inorganic coating, takes the advantages of both the inorganic coating method and the organic coating method into consideration, improves the coating rate and the flame retardant effect of the coated red phosphorus. However, the preparation method of the microencapsulated red phosphorus is complex and strict, has high requirement on the coating rate of the red phosphorus, and requires that the surface of the red phosphorus is completely wrapped by the capsule material.
How to prepare the red phosphorus coating material without microencapsulation is a technical problem to be solved by the invention, and the problems of compatibility of red phosphorus and organic matters, hygroscopicity, machinability and the like can also be solved.
The invention firstly loads a proper amount of red phosphorus on the covalent organic framework material with larger specific surface area to prepare the composite material, which can obviously improve the defects, simultaneously can reduce the using amount of the flame retardant, and fully utilizes the compatibility of the covalent organic framework material to improve the thermal stability and the mechanical processing performance, the flame retardant performance and other performances of the product. So far, no red phosphorus/covalent organic framework composite material with high-efficiency flame retardant performance, a preparation method thereof and a public report as a flame retardant are found.
Disclosure of Invention
Aiming at the problems in the prior art, red phosphorus is modified by utilizing a polyimide covalent organic framework material, so that the red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property is provided.
The invention also aims to provide a preparation method of the red phosphorus/polyimide covalent organic framework composite material.
In order to solve the technical problems, the invention adopts the technical scheme that:
a red phosphorus/polyimide covalent organic framework composite material is composed of red phosphorus and polyimide covalent organic framework materials.
Further, red phosphorus is in the form of nanopowder, preferably 5nm or less in size.
Further, the polyimide-type covalent organic framework material has a pore diameter of 10nm or less.
Furthermore, the nano red phosphorus powder is loaded in the pore channels of the polyimide type covalent organic framework material.
In order to better load red phosphorus in the polyimide covalent organic framework material, the size of the pore diameter of the polyimide covalent organic framework material is 5-10 nm.
The size of the red phosphorus is matched with the pore size of the polyimide covalent organic framework material, the size of the red phosphorus is preferably 1-5nm, and the red phosphorus is more favorably loaded in the polyimide covalent organic framework material.
In the composite material, the weight content of red phosphorus is 0.5-20%, more preferably 10-20% of the weight content of the polyimide covalent organic framework material, and the higher the red phosphorus load is, the more obvious the advantages of the material are.
The preparation method of the red phosphorus/polyimide covalent organic framework composite material comprises the following steps:
dispersing a polyimide covalent organic framework material and nano red phosphorus powder into a solvent to obtain a mixed suspension, and carrying out ultrasonic treatment on the suspension under a sealing condition of 40-80 ℃, wherein the ultrasonic treatment condition is as follows: the ultrasonic power is 200-600W, and the time is 6-20 hours; and cooling to room temperature after ultrasonic treatment, then carrying out solid-liquid separation on the suspension, repeatedly cleaning the obtained solid with a solvent, and drying after cleaning to obtain the red phosphorus/polyimide covalent organic framework composite material.
The solvent can be water or an organic solvent, and the organic solvent is ethanol or isopropanol, preferably isopropanol.
The ultrasonic treatment temperature is limited to 40-80 ℃, and the dispersion of red phosphorus is more facilitated under the heating condition, so that the loading of nano red phosphorus in a pore channel is more facilitated. The invention adopts a long-time ultrasonic treatment mode which is different from the common short-time ultrasonic treatment mode, the short-time ultrasonic treatment only has a dispersion treatment effect on the red phosphorus and the polyimide covalent organic framework material, and can avoid the agglomeration of the nano-scale red phosphorus. On the premise of meeting certain ultrasonic intensity, the ultrasonic treatment adopted by the invention can ensure that the nanoscale red phosphorus can better enter the pore diameter of the covalent organic framework material after the ultrasonic time reaches a certain length, thereby achieving better dispersion and combination effects.
Compared with the prior art, the invention has the beneficial effects that:
the invention selects the polyimide covalent organic porous polymer as a carrier, the material is a high molecular material which is formed by connecting organic building modules through strong covalent bonds and has a porous structure, the material is used as the carrier to be compounded with red phosphorus, the compounding effect is good, and the obtained red phosphorus/polyimide covalent organic framework composite material can effectively solve the problems of poor moisture absorption and stability of the red phosphorus, poor compounding effect with organic materials and the like. When the flame retardant is used as an organic material flame retardant, the flame retardant property and the mechanical processing property of the material can be obviously improved.
The red phosphorus/polyimide covalent organic framework composite flame retardant prepared by the invention provides a simple and feasible approach to red phosphorus flame retardant, and the required raw materials are simple and easy to obtain, the reaction method is simple, and the conditions are mild.
The specific implementation scheme is as follows:
the present invention will be further described with reference to the following embodiments.
The present invention is further illustrated in detail by the following specific examples, it being understood that the specific examples described herein are for the purpose of illustration only and are not intended to limit the invention, and that various changes may be made within the scope of the invention as defined by the claims.
The starting materials and reagents used in the following examples are all commercially available. Wherein, the polyimide covalent organic framework material is powder, and the aperture size is 5-10 nm; the polyimide covalent organic framework material can be prepared by the currently known method, the source is not particularly required, and the pore size can be regulated and controlled according to the known method.
Red phosphorus is also available in powder form, 1-5nm in size, commercially.
Example 1
Preparation of red phosphorus/polyimide type covalent organic framework material composite material
Firstly, 5g of red phosphorus is added into 200mL of isopropanol dispersion liquid of the polyimide covalent organic framework material with the concentration of 1g/L, the mixture is evenly stirred, and then the dispersion liquid is placed into a constant-temperature ultrasonic water bath for 5 hours of ultrasound (the ultrasound power is 200W), and the temperature is maintained at 40 ℃ during the ultrasound treatment. And then centrifuging the solution after ultrasonic treatment at the speed of 5000r/min, filtering to obtain dark red powder, washing the obtained dark red powder with isopropanol for three times, drying in a forced air drying oven at the temperature of 50 ℃ for 10 hours, and naturally cooling to room temperature to obtain the red phosphorus/polyimide covalent organic framework composite material with the red phosphorus weight content of 1%.
Example 2
Firstly, 5g of red phosphorus is added into 200mL of isopropanol dispersion liquid of the polyimide covalent organic framework material with the concentration of 5g/L, the mixture is evenly stirred, then the dispersion liquid is placed in a constant-temperature ultrasonic water bath for 5 hours of ultrasound (the ultrasound power is 200W), and the temperature is maintained at 40 ℃ during the ultrasound treatment. And then centrifuging the solution after ultrasonic treatment at the speed of 5000r/min, filtering to obtain dark red powder, washing the obtained dark red powder with isopropanol for three times, drying in a forced air drying oven at the temperature of 50 ℃ for 10 hours, and naturally cooling to room temperature to obtain the red phosphorus/polyimide covalent organic framework composite material with the weight content of the red phosphorus of 5%.
Example 3
Firstly, 5g of red phosphorus (with the size of 5nm) is added into 200mL of isopropanol dispersion liquid of a polyimide covalent organic framework material (with the pore size of 5nm) with the concentration of 10g/L, the mixture is evenly stirred, and then the dispersion liquid is placed in a constant-temperature ultrasonic water bath for 5 hours of ultrasound (with the ultrasonic power of 200W), and the temperature is maintained at 40 ℃ during the ultrasound treatment. And then centrifuging the solution after ultrasonic treatment at the speed of 5000r/min, filtering to obtain dark red powder, washing the obtained dark red powder with isopropanol for three times, drying in a forced air drying oven at the temperature of 50 ℃ for 10 hours, and naturally cooling to room temperature to obtain the red phosphorus/polyimide covalent organic framework composite material with the red phosphorus weight content of 10%.
Example 4
The steps and parameters of the method for preparing the red phosphorus/polyimide covalent organic framework composite material are basically the same as those of the method in the embodiment 1, and the difference is that the ultrasonic treatment time is as follows: ultrasonic treatment is carried out for 10 hours, and the solvent is changed into water.
Comparative example 1
Comparative example 1 is compared to example 3 with the difference that the polyimide covalent organic framework composite is replaced with graphene, and the other operations are the same as example 3.
Comparative example 2
Comparative example 2 is compared with example 3 except that the polyimide covalent organic framework composite material is replaced with a conventional organic porous material such as a polyurethane porous material, and the other operations are the same as in example 3.
And (3) performance detection:
(1) moisture absorption test
The examples, comparative examples and fully dried red phosphorus were exposed to air for 7 days, and the change in mass of the recording material was weighed after 7 days. Moisture absorption rate (%) is a mass change rate (%).
(2) Mechanical and flame retardant Property testing
Adding the flame retardant into the ABS high polymer material in the same mass (the adding amount is 12 percent of the mass of the ABS material), putting the ABS high polymer material into a high-speed mixer for fully mixing for 10min, adding the mixture into a double-screw extruder for melt mixing, and then extruding to obtain the flame-retardant composite material.
Flame performance was measured by the vertical burn test with test bars of 120mm × 75mm × 12mm and the flame and flameless burn times were recorded.
And (4) testing mechanical properties, wherein the test sample bar specification is 70mm × 10mm × 4mm, and an electronic universal tester is adopted for testing.
TABLE 1
The red phosphorus/polyimide covalent organic framework composite material is used as the flame retardant, so that the moisture absorption of the red phosphorus can be obviously improved, the compatibility with a high polymer material is good, the flame retardant grade of the high polymer material can be obviously improved, the mechanical processing performance is better, and the application of the red phosphorus in the flame retardant is of positive significance.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property is characterized in that: the composite material consists of red phosphorus and a polyimide type covalent organic framework material; wherein, red phosphorus is loaded in a polyimide covalent organic framework.
2. The covalent organic framework composite material of red phosphorus/polyimide type having excellent flame retardant property as claimed in claim 1, wherein the size of red phosphorus is 5nm or less.
3. The red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property as claimed in claim 1, wherein the weight of red phosphorus in the composite material is 0.5-20% of the weight content of the polyimide covalent organic framework material.
4. The method for preparing the red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property according to any one of claims 1 to 3, which is characterized by comprising the following steps:
dispersing a polyimide covalent organic framework material and nano red phosphorus powder into a solvent to obtain a suspension, carrying out ultrasonic treatment on the suspension under a heating condition, carrying out solid-liquid separation on the suspension after the ultrasonic treatment, washing the obtained solid with the solvent, and drying in a forced air drying oven after washing to obtain the red phosphorus/polyimide covalent organic framework composite material.
5. The method for preparing the red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property according to claim 4 is characterized in that: the temperature of ultrasonic treatment is 40-80 ℃; the ultrasonic power is 200-600W, and the time is 6-20 hours.
6. The red phosphorus/polyimide covalent organic framework composite material prepared by the method according to the claim 4 is used as a flame retardant in organic materials.
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| CN112980182A (en) * | 2021-04-02 | 2021-06-18 | 泉州师范学院 | COFs/nylon 6 composite material and preparation method thereof |
| CN114031817A (en) * | 2021-09-28 | 2022-02-11 | 河北大学 | COFs modified ammonium polyphosphate flame retardant, preparation method and application thereof, and flame-retardant epoxy resin |
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Denomination of invention: A red phosphorus/polyimide covalent organic framework composite material with excellent flame retardancy and its preparation method Effective date of registration: 20230927 Granted publication date: 20230425 Pledgee: Bank of China Limited Yancheng Yandu sub branch Pledgor: YANCHENG SHENYUAN PLASTIC Co.,Ltd. Registration number: Y2023980059023 |
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