CN116102820B - Metal-MPOFs/polymer composite material and preparation method and application thereof - Google Patents
Metal-MPOFs/polymer composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 239000004743 Polypropylene Substances 0.000 claims abstract description 46
- 229920001155 polypropylene Polymers 0.000 claims abstract description 46
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003063 flame retardant Substances 0.000 claims abstract description 20
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 polypropylene Polymers 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 238000004729 solvothermal method Methods 0.000 abstract description 6
- 239000013384 organic framework Substances 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a metal-MPOFs/polymer composite material, a preparation method and application thereof, belonging to the technical field of preparation of flame retardants. The invention mainly adopts a solvothermal method to prepare a metal-organic framework material, reacts with the prepared octacarboxyl POSS (OCP) to obtain a metal-organic framework (metal-MPOFs), and then continuously reacts with polypropylene (PP) to prepare the MPOFs/polymer composite material through a solution casting method. The preparation method provided by the invention has the advantages of simple preparation process, easiness in operation and high yield, and the prepared flame retardant is stable in structure and suitable for mass preparation in industrial application. Compared with a pure polymer, the MPOFs/polymer composite material prepared by the method provided by the invention has the advantages that the peak heat release rate (pHRR) of the metal-MPOFs/polymer composite material is reduced by 28% -52% and the total heat release rate (THR) is reduced by 12% -18% by adding the metal-MPOFs, meanwhile, the release of CO and CO 2 is obviously reduced, and the preparation method has a good application prospect in the aspect of preparing flame retardant materials.
Description
Technical Field
The invention belongs to the technical field of preparation of flame retardants, and relates to a metal-MPOFs/polymer composite material, a preparation method and application thereof.
Background
Polymers such as Polystyrene (PS), polypropylene (PP), epoxy resin (EP), polyurethane (PU), polylactic acid (PLA) and the like have been widely used in various fields of packaging and transportation, biomedical engineering construction, aerospace and the like, and play an important role in national economy development. However, most polymers are flammable and produce a lot of smoke when burned, which seriously threatens the life and property safety of the national population. Therefore, developing a flame retardant with high flame retardant efficiency and wide adaptability becomes an important means for eliminating fire safety hidden trouble.
The metal-organic frameworks (metal-MOFs) are formed by connecting metal center ions and organic ligands, are novel high-crystallization porous materials, and have attracted great attention in the fields of energy storage, catalysis, gas separation, drug delivery, fire safety and the like due to a series of advantages of high specific surface area, high porosity and the like. Compared with the traditional inorganic filler, the organic ligand in the metal-organic framework (metal-MOFs) structure not only helps to improve the compatibility between the organic ligand and the polymer, but also can provide various flame retardant elements or groups to generate synergistic flame retardant effect; in addition, transition metal oxides produced by thermal degradation of metal-organic frameworks (metal-MOFs) have positive catalytic effects on promoting coke formation and inhibiting smoke release, and can effectively reduce fire hazard. The metal-organic frameworks (metal-MOFs) have wide application prospects.
Polyhedral oligomeric silsesquioxane (POSS) is a hybridized cage nano-structure, si-O bonds alternately connected are used as inorganic cores, and stable ceramic silicon dioxide can be formed on the surface of a carbon layer after combustion to strengthen the strength of the carbon layer. In recent years, various kinds of metals are introduced into the internal skeleton of POSS for polymer flame retardance, and the POSS cage-shaped nano structure can obviously enhance the flame retardant property of the flame retardant.
Therefore, it is necessary to combine the advantages of both MOFs and POSS, introduce the POSS cage structure into MOFs, and prepare a novel high-efficiency flame retardant based on MOFs so as to replace the traditional flame retardant product to provide fire safety guarantee for the application of the polymer.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a metal-MPOFs/polymer composite; the second object of the present invention is to provide a method for preparing a metal-MPOFs/polymer composite; the invention further aims to provide an application of the metal-MPOFs/polymer composite material in preparing a flame retardant.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a method of preparing a metal-MPOFs/polymer composite, the method comprising the steps of:
(1) Preparation of metal-organic frameworks (metal-MOFs): dispersing hydrated metal nitrate and 2-methylimidazole (2-MIM) in anhydrous methanol, stirring at room temperature to uniformly disperse the materials, washing the solid obtained by centrifugation with methanol for 3-5 times, and drying to obtain metal-organic framework materials (metal-MOFs);
(2) Preparation of octacarboxy POSS (OCP): dissolving octavinyl cage-like silsesquioxane (OVP) and Azodiisobutyronitrile (AIBN) in chloroform, adding mercaptopropionic acid (MPA), heating to 55-75 ℃ and stirring for 4-6 h to obtain an organic solution containing octacarboxyl cage-like silsesquioxane (OCP), and drying to obtain a bright yellow solid product, namely octacarboxyl POSS (OCP);
(3) Preparation of metal organic frameworks (metal-MPOFs): dispersing the metal-organic framework material (metal-MOFs) prepared in the step (1) in absolute ethyl alcohol, carrying out ultrasonic treatment to uniformly disperse the metal-organic framework material to obtain a solution I, dissolving octacarboxyl POSS (OCP) prepared in the step (2) in absolute ethyl alcohol, stirring to uniformly dissolve the octacarboxyl POSS (OCP) to obtain a solution II, mixing the solution I and the solution II, stirring and heating to react, centrifugally washing a product obtained by the reaction with absolute ethyl alcohol for 3-5 times, and drying the product in a vacuum oven at 60-80 ℃ for 4-6 hours to obtain a metal-organic framework (metal-MPOFs);
(4) Preparing a metal-MPOFs/polymer composite: the preparation is carried out by adopting a solution casting method, the metal organic framework (metal-MPOFs) prepared in the step (3) is uniformly dispersed in N, N-Dimethylformamide (DMF) to form uniform dispersion, polypropylene (PP) is added for dissolution, the solid is obtained after stirring reaction for 2-4 h at 60-80 ℃, and the MPOFs/polymer composite material is obtained after drying in an oven at 80-100 ℃ for 10-14 h.
Preferably, in the step (1), the molar ratio of the metal element in the hydrated metal nitrate to the 2-methylimidazole (2-MIM) is 1.0-2.0:6.0.
Preferably, in step (1), the hydrated metal nitrate is Zn (NO 3)26H2O、Ni(NO3)26H2 O or Co (NO 3)26H2 O).
Preferably, in the step (1), the drying is performed in an oven at 80-100 ℃ for 10-14 hours.
Preferably, in the step (2), the mass ratio of the octavinyl cage silsesquioxane (OVP), the Azodiisobutyronitrile (AIBN) and the mercaptopropionic acid (MPA) is 8-8.5:0.2-0.4:1.5-2.
Preferably, in the step (3), the molar mass ratio of the metal-organic framework material to the octacarboxyl POSS (OCP) is 10-15:15, and the mmol is:g.
Preferably, in step (3), the stirring and heating are: stirring and heating at the speed of 300-360 rpm for 4-6 h at the temperature of 60-80 ℃.
Preferably, in the step (4), the molar mass ratio of the metal-organic framework (metal-MPOFs) to the polypropylene (PP) is 0.56:40-50, and the mmol:g.
2. The metal-MPOFs/polymer composite material prepared by the preparation method is prepared.
3. The metal-MPOFs/polymer composite material is applied to the preparation of flame retardant materials.
The invention has the beneficial effects that:
1. The invention discloses a preparation method of MPOFs/polymer composite material, which mainly comprises the steps of preparing a metal-organic framework material by adopting a solvothermal method, reacting the metal-organic framework material with prepared octacarboxyl POSS (OCP) to obtain a metal-organic framework (metal-MPOFs), and continuously preparing MPOFs/polymer composite material with polypropylene (PP) by adopting a solution casting method. The preparation method provided by the invention has the advantages of simple preparation process, easiness in operation and high yield, and the prepared flame retardant is stable in structure and suitable for mass preparation in industrial application.
2. Compared with pure polymer, the MPOFs/polymer composite material provided by the invention has the advantages that the peak heat release rate (pHRR) of the MPOFs/polymer composite material is reduced by 28% -52% and the total heat release rate (THR) is reduced by 12% -18% by adding MPOFs, meanwhile, the release of CO and CO 2 is obviously reduced, and the preparation method has a good application prospect in the aspect of preparing flame retardant materials.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an XRD pattern of the Zn-MPOFs/PP composite material prepared in example 1;
FIG. 2 is an XRD pattern of the Ni-MPOFs/PP composite prepared in example 2;
FIG. 3 is an XRD pattern of the Co-MPOFs/PP composite prepared in example 3;
FIG. 4 is a pHHR trend plot for pure PP, zn-MPOFs/PP composite prepared in example 1, ni-MPOFs/PP composite prepared in example 2, co-MPOFs/PP composite prepared in example 3;
FIG. 5 is a HHR trend graph of pure PP, zn-MPOFs/PP composite prepared in example 1, ni-MPOFs/PP composite prepared in example 2, co-MPOFs/PP composite prepared in example 3.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
A Zn-MPOFs/PP composite material is prepared according to the following method:
(1) A solvothermal method is adopted to prepare a zinc-organic framework material (Zn-MOFs): 1.4g of zinc nitrate hexahydrate (Zn (NO 3)2·6H2 O) and 2.0g of 2-methylimidazole were dispersed in 120ml of absolute methanol, and after mixing, the mixture was magnetically stirred at room temperature for 1.5 hours, and the solid obtained by centrifugation after the reaction was washed 3 to 5 times with methanol and dried in an oven at 90℃to obtain zinc-organic framework materials (Zn-MOFs).
(2) Preparation of octacarboxy POSS (OCP): 8.2g of octavinyl cage silsesquioxane (OVP) and 360mg of Azobisisobutyronitrile (AIBN) were dissolved in 130ml of chloroform, then 1.8g of mercaptopropionic acid (MPA) was further added, heated to 65℃and stirred for 4.5 hours, extracted with chloroform, and the extracted solution was dried for 12 hours, and a pale yellow solid product, octacarboxyl POSS (OCP), was obtained.
(3) Preparation of zinc-organic framework (Zn-MPOFs) Synthesis: dispersing 4.5g of zinc-organic framework materials (Zn-MOFs) in 1000ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, dissolving 15g of octacarboxyl POSS (OCP) in 1000ml of absolute ethyl alcohol, stirring at a speed of 330rpm until a uniform solution is formed, mixing the two solutions in a three-neck flask, heating and reacting for 5.0h at a speed of 330rpm under a 65 ℃ environment, centrifugally washing a product obtained by the reaction with absolute ethyl alcohol for 3-5 times, and finally drying in a vacuum oven at 65 ℃ for 4.5h to obtain a dark brown solid, namely the zinc-organic framework (Zn-MPOFs) is synthesized.
(4) Preparing a Zn-MPOFs/PP composite material: zn-MPOFs/PP composite was prepared by solution casting, 1.5g of zinc-organic framework (Zn-MPOFs) was dispersed in 320ml of N, N-Dimethylformamide (DMF) to give a uniform dispersion, 45.0g of polypropylene (PP) was slowly dissolved in the above dispersion, stirred at 65℃for 2.5 hours, and the resulting solid was dried in an oven at 90℃for 12.0 hours to give Zn-MPOFs/PP composite (XRD pattern shown in FIG. 1).
Example 2
The Ni-MPOFs/PP composite material is prepared according to the following method:
(1) The method adopts a solvothermal method to prepare a nickel-organic framework material (Ni-MOFs): 1.6g of nickel nitrate hexahydrate (Ni (NO 3)2·6H2 O) and 2.4g of 2-methylimidazole are dispersed in 140ml of absolute methanol, and after being uniformly mixed, the mixture is magnetically stirred at room temperature for 1.5 hours, and after the reaction, the solid obtained by centrifugation is washed 3 to 5 times with methanol, and dried in an oven at 90 ℃ to obtain a nickel-organic framework material (Ni-MOFs).
(2) Preparation of octacarboxy POSS (OCP): 8.5g of octavinyl cage silsesquioxane (OVP) and 380mg of Azobisisobutyronitrile (AIBN) were dissolved in 140ml of chloroform, then 2.0g of mercaptopropionic acid (MPA) was further added, heated to 65℃and stirred for 4.5 hours, extracted with chloroform, and the extracted solution was dried for 12 hours, and a pale yellow solid product, octacarboxyl POSS (OCP), was obtained.
(3) Preparation of Nickel-organic framework (Ni-MPOFs) Synthesis: dispersing 5.8g of nickel-organic framework materials (Ni-MOFs) in 1200ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, dissolving 18g of octacarboxyl POSS (OCP) in 1200ml of absolute ethyl alcohol, stirring at a speed of 330rpm until a uniform solution is formed, mixing the two solutions in a three-neck flask, heating and reacting for 5.0h at a speed of 330rpm under a 65 ℃ environment, centrifugally washing a product obtained by the reaction with absolute ethyl alcohol for 3-5 times, and finally drying in a vacuum oven at 65 ℃ for 4.5h to obtain a dark brown solid, namely the nickel-organic framework (Ni-MPOFs) to be synthesized.
(4) Preparation of Ni-MPOFs/PS composite preparation: ni-MPOFs/PS composite material was prepared by solution casting method, 1.8g of organic framework (MPOFs) was dispersed in 350ml of N, N-Dimethylformamide (DMF) to produce a uniform dispersion, 50.0g of Polystyrene (PS) was slowly dissolved in the above dispersion, and after stirring reaction at 65℃for 2.5 hours, the obtained solid was dried in an oven at 90℃for 12.0 hours to obtain Ni-MPOFs/PS composite material (XRD pattern of which is shown in FIG. 2).
Example 3
The Co-MPOFs/PP composite material is prepared according to the following method:
(1) The cobalt-organic framework material (Co-MOFs) is prepared by adopting a solvothermal method, 2.0g of cobalt nitrate hexahydrate (Co (NO 3)2·6H2 O) and 2.6g of 2-methylimidazole are dispersed in 160ml of absolute methanol, the mixture is stirred for 1.5 hours under magnetic force at room temperature after being uniformly mixed, the solid obtained after the reaction and centrifugation is washed for 3 to 5 times by using the methanol, and the cobalt-organic framework material (Co-MOFs) is obtained after drying in an oven at 90 ℃.
(2) Preparation of octacarboxy POSS (OCP) synthesis: 9.0g of octavinyl cage silsesquioxane (OVP) and 390mg of Azobisisobutyronitrile (AIBN) were dissolved in 150ml of chloroform, then 2.2g of mercaptopropionic acid (MPA) was further added, heated to 65℃and stirred for 4.5 hours, extracted with chloroform, and the extracted solution was dried for 12 hours, and a pale yellow solid product, octacarboxyl POSS (OCP), was obtained.
(3) Preparation of cobalt-metal organic framework (Co-MPOFs) Synthesis: dispersing 6.4g of cobalt-organic framework materials (Co-MOFs) in 1300ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, dissolving 20.0g of octacarboxyl POSS (OCP) in 1300ml of absolute ethyl alcohol, stirring at a speed of 330rpm until a uniform solution is formed, mixing the two solutions in a three-neck flask, heating and reacting for 5.0h at a speed of 330rpm under the environment of 65 ℃, centrifugally washing a product obtained by the reaction with absolute ethyl alcohol for 3-5 times, and finally drying for 4.5h in a vacuum oven at 65 ℃ to obtain a dark brown solid, namely the cobalt-organic framework (Co-MPOFs) is synthesized.
(4) Preparing a Co-MPOFs/PLA composite material: co-MPOFs/PLA composite material was prepared by solution casting method, 2.0g of cobalt-organic framework (Co-MPOFs) was dispersed in 350ml of N, N-Dimethylformamide (DMF) to produce uniform dispersion, 52.0g of polylactic acid (PLA) was slowly dissolved in the above dispersion, after stirring at 65℃for 2.5 hours, the obtained solid was dried in an oven at 90℃for 12.0 hours to obtain Co-MPOFs/PS composite material (XRD pattern is shown in FIG. 3).
Performance testing
FIG. 1 is an XRD pattern of the Zn-MPOFs/PP composite prepared in example 1, FIG. 2 is an XRD pattern of the Ni-MPOFs/PP composite prepared in example 2, and FIG. 3 is an XRD pattern of the Zn-MPOFs/PP composite prepared in example 3. It can be seen from fig. 1 to 3 that the corresponding metal-MPOFs/polymer composite can indeed be produced by the process according to the invention.
FIG. 4 is a pHHR trend plot for pure PP, zn-MPOFs/PP composite prepared in example 1, ni-MPOFs/PP composite prepared in example 2, co-MPOFs/PP composite prepared in example 3. FIG. 5 is a HHR trend graph of pure PP, zn-MPOFs/PP composite prepared in example 1, ni-MPOFs/PP composite prepared in example 2, co-MPOFs/PP composite prepared in example 3. As can be seen from fig. 4 and 5, the peak heat release rate (pHRR) of the metal-MPOFs/polymer composite material prepared by the preparation method is reduced by 28-52%, the total heat release rate (THR) is reduced by 12-18%, and simultaneously, the release of CO and CO 2 is obviously reduced, so that the preparation method has a good application prospect in the aspect of preparing flame retardant materials.
Further, it is found through experiments that the conditions in the preparation methods of the composite materials in the above examples 1 to 3 may vary, and the concrete steps are as follows: (1) In the process of preparing metal-organic framework materials (metal-MOFs), the molar ratio of metal elements in hydrated metal nitrate to 2-methylimidazole (2-MIM) is 1.0-2.0:6.0, the temperature in the drying process is 80-100 ℃ and the time is 10-14 h; (2) In the process of preparing octacarboxyl POSS (OCP), the mass ratio of octavinyl cage-shaped silsesquioxane (OVP), azodiisobutyronitrile (AIBN) and mercaptopropionic acid (MPA) is in the range of 8-8.5:0.2-0.4:1.5-2; (3) In the process of preparing the metal-organic framework (metal-MPOFs), the molar mass ratio of the metal-organic framework material to octacarboxyl POSS (OCP) is 10-15:15, mmol/g, the temperature in stirring and heating is 60-80 ℃, the stirring speed is 300-360 rpm, the time is 4-6 h (4), and in the process of preparing the metal-MPOFs/polymer composite material, the molar mass ratio of the metal-organic framework (metal-MPOFs) to polypropylene (PP) is 0.56:40-50, and mmol/g.
In summary, the invention discloses a preparation method of a metal-MPOFs/polymer composite material, which mainly comprises the steps of preparing a metal-organic framework material by adopting a solvothermal method, reacting the metal-organic framework material with the prepared octacarboxyl POSS (OCP) to obtain a metal-organic framework (metal-MPOFs), and continuously preparing the MPOFs/polymer composite material with polypropylene (PP) by adopting a solution casting method. The preparation method provided by the invention has the advantages of simple preparation process, easiness in operation and high yield, and the prepared flame retardant is stable in structure and suitable for mass preparation in industrial application. Meanwhile, compared with a pure polymer, the metal-MPOFs/polymer composite material prepared by the method has the advantages that the peak heat release rate (pHRR) of the metal-MPOFs/polymer composite material is reduced by 28% -52%, the total heat release rate (THR) is reduced by 12% -18%, and meanwhile, the release of CO and CO 2 is obviously reduced, so that the metal-MPOFs/polymer composite material has good application prospect in the aspect of preparing flame retardant materials.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (10)
1. A method of preparing a metal-MPOFs/polymer composite, the method comprising the steps of:
(1) Preparing a metal-organic framework material: dispersing hydrated metal nitrate and 2-methylimidazole in anhydrous methanol, stirring at room temperature to uniformly disperse the hydrated metal nitrate and the 2-methylimidazole, washing the solid obtained by centrifugation with methanol for 3-5 times, and drying to obtain a metal-organic framework material;
(2) Preparation of octacarboxyl POSS: dissolving octavinyl cage-shaped silsesquioxane and azodiisobutyronitrile in chloroform, adding mercaptopropionic acid, heating to 55-75 ℃ and stirring for 4-6 hours to obtain an organic solution containing octacarboxyl cage-shaped silsesquioxane, and drying to obtain a fresh yellow solid product, namely octacarboxyl POSS;
(3) Preparing a metal organic framework: dispersing the metal-organic framework material prepared in the step (1) in absolute ethyl alcohol, carrying out ultrasonic treatment to uniformly disperse the metal-organic framework material to obtain a solution I, dissolving the octacarboxyl POSS prepared in the step (2) in absolute ethyl alcohol, stirring to uniformly dissolve the octacarboxyl POSS to obtain a solution II, mixing the solution I and the solution II, stirring and heating the mixture to react, centrifugally washing the product obtained by the reaction with absolute ethyl alcohol for 3-5 times, and drying the product in a vacuum oven at 60-80 ℃ for 4-6 hours to obtain the metal-organic framework;
(4) Preparing a metal-MPOFs/polymer composite: the preparation is carried out by adopting a solution casting method, the metal organic framework prepared in the step (3) is uniformly dispersed in N, N-dimethylformamide to form uniform dispersion, polypropylene is added for dissolution, the solid is obtained after stirring reaction for 2-4 h at 60-80 ℃, and the metal-MPOFs/polymer composite is obtained after drying for 10-14 h in an oven at 80-100 ℃.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the metal element in the hydrated metal nitrate to the 2-methylimidazole is 1.0 to 2.0:6.0.
3. The method according to claim 1, wherein in the step (1), the hydrated metal nitrate is any one of zinc nitrate hexahydrate, nickel nitrate hexahydrate, and cobalt nitrate hexahydrate.
4. The method according to claim 1, wherein in the step (1), the drying is performed in an oven at 80 to 100 ℃ for 10 to 14 hours.
5. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the octavinyl cage silsesquioxane, the azobisisobutyronitrile and the mercaptopropionic acid is 8-8.5:0.2-0.4:1.5-2.
6. The preparation method according to claim 1, wherein in the step (3), the molar mass ratio of the metal-organic framework material to octacarboxyl POSS is 10-15:15.
7. The method according to claim 1, wherein in the step (3), the stirring and heating are: stirring and heating at the speed of 300-360 rpm for 4-6 h at the temperature of 60-80 ℃.
8. The method according to claim 1, wherein in the step (4), the molar mass ratio of the metal-organic framework to the polypropylene is 0.56:40-50.
9. The metal-MPOFs/polymer composite material prepared by the method according to any one of claims 1 to 8.
10. Use of the metal-MPOFs/polymer composite according to claim 9 for the preparation of flame retardant materials.
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