CN115254055B - Metal organic framework material for adsorbing formaldehyde and preparation method and application thereof - Google Patents
Metal organic framework material for adsorbing formaldehyde and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a metal-organic framework material for absorbing formaldehyde, wherein [ Ni ] exists in the metal-organic framework material 2 (COOH) 8 N 8 ]A secondary construction unit of the quad-core cluster; the [ Ni ] 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2‑ The metal organic framework material is connected into a three-dimensional porous structure in an anion connection mode, formaldehyde molecules can be completely contained in the three-dimensional pore diameter existing in the metal organic framework material, and the surface methyl and phenyl of the three-dimensional porous structure have high affinity to formaldehyde, so that the metal organic framework material has high-efficiency adsorption capacity to formaldehyde, and the composite PBT material prepared by fusing the metal organic framework material and the PBT material has the capability of actively and efficiently adsorbing formaldehyde while the original mechanical property of the PBT material is maintained.
Description
Technical Field
The invention relates to the field of adsorption materials, in particular to a metal organic framework material for adsorbing formaldehyde, and a preparation method and application thereof.
Background
Formaldehyde released from indoor decoration materials and PM2.5 tiny particles suspended in the room are the indoor pollution problems which need to be solved urgently. The current air filter material has single function, mainly aims at tiny particulate matters PM2.5, and cannot absorb harmful substances such as formaldehyde at the same time. Therefore, the novel material for efficiently purifying the indoor air environment is developed, and the material has good application prospect.
Metal Organic Frameworks (MOFs) are coordination polymers formed by self-assembling organic ligands and metal ions through coordination bonds, have large specific surface area, high porosity and various structures and functions, and are widely studied by researchers in the fields of gas adsorption and separation, storage, catalysis and the like. How to provide more novel and diversified MOFs materials to meet the requirements of the formaldehyde adsorption material field is a hot spot problem faced by the current research.
Disclosure of Invention
The invention aims to provide a metal organic framework material for absorbing formaldehyde, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a metal organic framework material for absorbing formaldehyde, which has a chemical formula of [ Ni (mbpc) (IMBM) ]] n A formula I, wherein mbpc in the formula I is 4' -methylbiphenyl-3, 5-dicarboxylic acid, and IMBM is 1, 4-bis (imidazol-1-yl) benzene;
the metal-organic framework material for formaldehyde adsorption has asymmetric structural units, which comprise an anion mbpc 2- One cation Ni 2+ And an IMBM ligand, said building block number n; the Ni is 2+ Unlike two different mbpcs 2- In anions ofIs coordinated to form a hexacoordinated octahedral geometry; the metal organic framework material for adsorbing formaldehyde has [ Ni ] 2 (COOH) 8 N 8 ]A secondary construction unit of the quad-core cluster; the [ Ni ] 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2- The anions are connected into a three-dimensional porous structure in a connecting mode.
The invention also provides a preparation method of the metal organic framework material for adsorbing formaldehyde, which comprises the following steps:
(1) Mixing 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene, a nickel source and N, N-dimethylformamide to obtain a mixed solution;
(2) Performing self-assembly reaction on the mixed solution obtained in the step (1) to obtain a metal organic framework material for adsorbing formaldehyde;
the self-assembly reaction has the following heating mode: heating from room temperature to 95-110 ℃ in 3-5 h, then preserving heat at 95-110 ℃ for 65-80 h, and then cooling from 95-110 ℃ to room temperature in 20-30 h.
Preferably, the ratio of the amounts of the substances of the 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene and the nickel source in the step (1) is (0.6-1.2): 0.5-3.
Preferably, the ratio of the amount of the substance of 4' -methylbiphenyl-3, 5-dicarboxylic acid to the volume of N, N-dimethylformamide in step (1) is 1mol: (2-10) mL.
Preferably, the self-assembly reaction in the step (2) is performed in a temperature rising manner that: raising the temperature from room temperature to 98-105 ℃ within 3.5-4.5 h, then preserving the heat for 70-78 h at 98-105 ℃, and then reducing the temperature from 98-105 ℃ to room temperature within 25-28 h.
The invention also provides a preparation method of the composite PBT material, which comprises the following steps:
a. sequentially drying and melting the PBT to obtain a PBT melt;
b. adding the metal organic framework material for adsorbing formaldehyde prepared by the technical scheme or the metal organic framework material for adsorbing formaldehyde prepared by the preparation method of the technical scheme into the PBT melt obtained in the step a, and then sequentially mixing and extruding to obtain the composite PBT material.
Preferably, the temperature of the mixing in the step b is 210-250 ℃, and the mixing time is 40-120 min.
Preferably, the mass of the metal organic framework material used for absorbing formaldehyde in the step b is 10-22% of the mass of the composite PBT material.
The invention also provides the composite PBT material prepared by the preparation method.
The invention also provides application of the composite PBT material in formaldehyde adsorption.
The invention provides a metal organic framework material for absorbing formaldehyde, which has a chemical formula of [ Ni (mbpc) (IMBM) ]] n A formula I, wherein mbpc in the formula I is 4' -methylbiphenyl-3, 5-dicarboxylic acid, and IMBM is 1, 4-bis (imidazol-1-yl) benzene; the metal-organic framework material for formaldehyde adsorption has asymmetric structural units, which comprise an anion mbpc 2- One cation Ni 2+ And an IMBM ligand, said building block number n; the Ni is 2+ Unlike two different mbpcs 2- The four carboxylic acid oxygen atoms in the anion and the two nitrogen atoms in the two IMBM ligands coordinate to form a hexacoordinated octahedral geometry; the metal organic framework material for adsorbing formaldehyde has [ Ni ] 2 (COOH) 8 N 8 ]A secondary construction unit of the quad-core cluster; the [ Ni ] 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2- In the anion connection mode, the three-dimensional porous structure is formed, the pore size of the three-dimensional porous structure is 0.63 multiplied by 0.71nm, so that the three-dimensional porous structure can completely contain formaldehyde molecules, and the methyl and phenyl which are detected out of the three-dimensional porous surface have higher affinity to formaldehyde, so that the metal organic framework material has high-efficiency adsorption capacity to formaldehyde, and the metal organic framework material is prepared byThe composite PBT material prepared by fusing the framework material and the PBT material has the original mechanical properties of the PBT material and simultaneously endows the composite PBT material with the capability of actively and efficiently adsorbing formaldehyde. The results of the examples show that the complex 1 prepared in the example 1 of the invention has better formaldehyde adsorption capacity compared with activated carbon, and can reduce the formaldehyde concentration to 0.08mg/m after 2 hours 3 The formaldehyde removal rate can reach 96%, and the formaldehyde concentration of the 20wt% complex 1@PBT material can be reduced to 0.22mg/m after 2 hours 3 The formaldehyde removal rate can reach 89%, and the composite PBT material with the content of the complex 1 being 10-20wt% has formaldehyde adsorption effect superior to that of active carbon.
Drawings
FIG. 1 is a thermal ellipsometry chart of an X-ray single crystal diffraction analysis of a crystal of complex 1 prepared in example 1 of the present invention;
FIG. 2 shows mbpc in crystals of complex 1 prepared in example 1 of the present invention 2- And a coordination pattern diagram of IMBM ligands;
FIG. 3 shows [ Ni ] in the crystals of complex 1 prepared in example 1 of the present invention 2 (COO) 8 N 8 ]A schematic view of a club of a four-core cluster secondary construction unit;
FIG. 4 is a three-dimensional porous structure of the complex 1 prepared in example 1 of the present invention;
FIG. 5 is an X-ray powder diffraction pattern of complex 1 prepared in example 1 of the present invention;
FIG. 6 is a thermogravimetric analysis graph of the complex 1 prepared in example 1 of the present invention;
FIG. 7 is a schematic diagram of a formaldehyde adsorption performance testing apparatus used in the present invention;
FIG. 8 is a graph showing formaldehyde adsorption by activated carbon, silica and complex 1 prepared in example 1 of the present invention;
FIG. 9 is a graph showing formaldehyde adsorption for each test object according to the present invention.
Detailed Description
The invention provides a metal organic framework material for absorbing formaldehyde, which has a chemical formula of [ Ni (mbpc) (IMBM) ]] n The mbpc in the formula I is 4' -methylbiphenyl-3, 5-dicarboxylic acid, and the IMBM is 1, 4-bis (imidazole-1)-base) benzene;
the metal-organic framework material for formaldehyde adsorption has asymmetric structural units, which comprise an anion mbpc 2- One cation Ni 2+ And an IMBM ligand, said building block number n; the Ni is 2+ Unlike two different mbpcs 2- The four carboxylic acid oxygen atoms in the anion and the two nitrogen atoms in the two IMBM ligands coordinate to form a hexacoordinated octahedral geometry; the metal organic framework material for adsorbing formaldehyde has [ Ni ] 2 (COOH) 8 N 8 ]A secondary construction unit of the quad-core cluster; the [ Ni ] 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2- The anions are connected into a three-dimensional porous structure in a connection mode;
the pore size of the three-dimensional porous in the three-dimensional porous structure is 0.63 multiplied by 0.71nm, and the three-dimensional porous surface is provided with the methyl and phenyl groups which are detected out.
The three-dimensional porous pore size of the metal organic framework material for absorbing formaldehyde provided by the invention is 0.63 multiplied by 0.71nm, so that formaldehyde molecules can be completely contained in the three-dimensional porous pore, and the detected methyl and phenyl groups on the surface of the three-dimensional porous pore have higher affinity to formaldehyde, so that the metal organic framework material has high-efficiency adsorption capacity to formaldehyde.
The invention also provides a preparation method of the metal organic framework material for adsorbing formaldehyde, which comprises the following steps:
(1) Mixing 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene, a nickel source and N, N-dimethylformamide to obtain a mixed solution;
(2) Performing self-assembly reaction on the mixed solution obtained in the step (1) to obtain a metal organic framework material for adsorbing formaldehyde;
the self-assembly reaction has the following heating mode: heating from room temperature to 95-110 ℃ in 3-5 h, then preserving heat at 95-110 ℃ for 65-80 h, and then cooling from 95-110 ℃ to room temperature in 20-30 h.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
The invention mixes 4' -methyl biphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazole-1-yl) benzene, nickel source and N, N-dimethylformamide to obtain mixed solution.
In the present invention, the nickel source is preferably one or more of nickel nitrate hexahydrate, nickel nitrate, nickel sulfate, nickel chloride or nickel chloride hexahydrate.
In the present invention, the ratio of the amounts of the substances of the 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene and nickel source is preferably (0.6 to 1.2): 0.5 to 3, more preferably (0.8 to 1.1): 0.8 to 2, further preferably 1:1:1. the invention controls the ratio of the amounts of the substances of the 4' -methylbiphenyl-3, 5-dicarboxylic acid, the 1, 4-bis (imidazole-1-yl) benzene and the nickel source in the range so as to promote the complete reaction of the three substances and prepare the metal organic framework material with high yield for absorbing formaldehyde.
In the present invention, the ratio of the amount of the substance of 4' -methylbiphenyl-3, 5-dicarboxylic acid to the volume of N, N-dimethylformamide is 1mol: (2-10) mL, more preferably 1mol: (3-8) mL. The invention controls the volume ratio of the substance of 4' -methylbiphenyl-3, 5-dicarboxylic acid and N, N-dimethylformamide in the above range, is favorable for generating metal organic framework materials for absorbing formaldehyde, avoids the too small amount of solvent N, N-dimethylformamide, ensures that the metal organic framework materials have too high crystal generation speed and too large crystal volume, simultaneously avoids too large amount of solvent N, N-dimethylformamide, ensures that the metal organic framework materials have too slow crystal generation and even have no crystal generation.
In the present invention, the mixing of the 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene, the nickel source and the N, N-dimethylformamide is preferably carried out under ultrasonic conditions. The invention has no special limit to the power and time of the ultrasonic wave, and can realize the uniform mixing of the components.
After the mixed solution is obtained, the mixed solution is subjected to self-assembly reaction to obtain the metal organic framework material for adsorbing formaldehyde.
In the invention, the self-assembly reaction has the following heating mode: heating from room temperature to 95-110 ℃ in 3-5 h, then preserving heat at 95-110 ℃ for 65-80 h, and then cooling from 95-110 ℃ to room temperature in 20-30 h, wherein the preferable steps are as follows: raising the temperature from room temperature to 98-105 ℃ within 3.5-4.5 h, then preserving the heat for 70-78 h at 98-105 ℃, and then reducing the temperature from 98-105 ℃ to room temperature within 25-28 h.
The invention adopts the heating mode of the self-assembly reaction to control the heating time from room temperature to 95-110 ℃ so as to control the heating rate, thereby controlling the reaction rate, being beneficial to the self-assembly of various substances in a reaction system, avoiding the influence of the too low reaction rate on the reaction efficiency, controlling the heat preservation time at 95-110 ℃ so as to ensure the full progress of the self-assembly reaction, improving the product yield, maintaining the efficiency, controlling the cooling time from 95-110 ℃ to room temperature, controlling the cooling rate, preventing the crystal breakage caused by the too fast cooling, and simultaneously ensuring the efficiency.
After the self-assembly reaction is completed, the invention preferably sequentially carries out suction filtration and drying on the product of the self-assembly reaction.
The suction filtration mode is not particularly limited, and the purpose of solid-liquid separation can be achieved. In the present invention, the drying apparatus is preferably a vacuum drying oven. The temperature and time of the drying are not particularly limited, and the purpose of sufficiently removing water can be achieved.
The preparation method of the metal organic framework material for adsorbing formaldehyde provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The invention also provides a preparation method of the composite PBT material, which comprises the following steps:
a. sequentially drying and melting the PBT to obtain a PBT melt;
b. adding the metal organic framework material for adsorbing formaldehyde prepared by the technical scheme or the metal organic framework material for adsorbing formaldehyde prepared by the preparation method of the technical scheme into the PBT melt obtained in the step a, and then sequentially mixing and extruding to obtain the composite PBT material.
The PBT is sequentially dried and melted to obtain a PBT melt.
In the present invention, the drying equipment is preferably an electrothermal constant temperature blast drying oven. In the present invention, the drying temperature is preferably 100 to 120 ℃, more preferably 105 to 110 ℃; the drying time is preferably 22 to 26 hours, more preferably 23 to 25 hours. The invention controls the drying temperature and time within the above range to ensure that the moisture in the PBT is sufficiently removed, thereby ensuring that the subsequent molding of the composite PBT material is not affected.
In the present invention, the melting apparatus is preferably a twin-roll mixer. The invention has no special limitation on the melting temperature and time, and can achieve the purpose of fully melting the PBT and obtaining the PBT melt.
After obtaining a PBT melt, adding the metal-organic framework material for adsorbing formaldehyde prepared by the technical scheme or the metal-organic framework material for adsorbing formaldehyde prepared by the preparation method of the technical scheme into the PBT melt, and sequentially mixing and extruding to obtain the composite PBT material
In the present invention, the temperature of the kneading is preferably 210 to 250 ℃, more preferably 220 to 245 ℃, and the time of the kneading is preferably 40 to 120 minutes, more preferably 50 to 70 minutes. The invention controls the mixing temperature and time in the above range to promote the uniform mixing of the components, thereby improving the formaldehyde adsorption capacity of the prepared composite PBT material and maintaining the mechanical properties thereof.
In the present invention, the extrusion apparatus is preferably a twin screw extruder. The extrusion mode is not particularly limited, and the conventional technical scheme in the field can be adopted.
In the present invention, the mass of the metal organic framework material for adsorbing formaldehyde is preferably 8% to 22%, more preferably 9% to 21%, and even more preferably 10% to 20% of the mass of the composite PBT material. The invention controls the mass consumption of the metal organic framework material for absorbing formaldehyde in the composite PBT material in the range so as to improve the formaldehyde absorption performance of the composite PBT material and simultaneously maintain the original good heat resistance, electrical insulation and mechanical properties of the PBT.
After extrusion is complete, the present invention preferably provides for grinding and sieving the extruded pellet product in sequence.
The grinding mode is not particularly limited, and conventional technical schemes in the field can be adopted. The sieving mode is not particularly limited, and the conventional technical scheme in the field can be adopted.
The preparation method of the composite PBT material provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The invention also provides the composite PBT material prepared by the preparation method.
The composite PBT material provided by the invention has excellent formaldehyde adsorption performance, and simultaneously keeps the original good heat resistance, electrical insulation and mechanical properties of PBT.
The invention also provides application of the composite PBT material in formaldehyde adsorption. In the invention, the composite PBT material can be applied to the fields of automobiles, machinery and household appliances.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Product example 1
Metal organic framework material for adsorbing formaldehyde and having a chemical formula of [ Ni (mbpc) (IMBM) ]] n A formula I, wherein mbpc in the formula I is 4' -methylbiphenyl-3, 5-dicarboxylic acid, and IMBM is 1, 4-bis (imidazol-1-yl) benzene;
the metal-organic framework material for formaldehyde adsorption has asymmetric structural units, which comprise an anion mbpc 2- One cation Ni 2+ And an IMBM ligand, providedThe number of the structural units is n; the Ni is 2+ Unlike two different mbpcs 2- The four carboxylic acid oxygen atoms in the anion and the two nitrogen atoms in the two IMBM ligands coordinate to form a hexacoordinated octahedral geometry; the metal organic framework material for adsorbing formaldehyde has [ Ni ] 2 (COOH) 8 N 8 ]A secondary construction unit of the quad-core cluster; the [ Ni ] 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2- The anions are connected into a three-dimensional porous structure in a connection mode;
the pore size of the three-dimensional porous in the three-dimensional porous structure is 0.63 multiplied by 0.71nm, and the three-dimensional porous surface is provided with the methyl and phenyl groups which are detected out.
Example 1
Preparation method of metal organic framework material for adsorbing formaldehyde in product example 1
(1) Weighing 3mmol of 4' -methylbiphenyl-3, 5-dicarboxylic acid, 3mmol of 1, 4-bis (imidazol-1-yl) benzene and 3mmol of nickel nitrate hexahydrate, putting the reaction kettle into an ultrasonic cleaner, and vibrating after adding 12mL of DMF solution to completely dissolve all components into DMF to obtain a transparent light green mixed solution;
the ratio of the amounts of the substances of 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene and nickel nitrate hexahydrate is 1:1:1, a step of;
the ratio of the amount of the substance of the 4' -methylbiphenyl-3, 5-dicarboxylic acid to the volume of the N, N-dimethylformamide was 1mmol:4mL;
(2) And (3) carrying out self-assembly reaction on the mixed solution obtained in the step (1), heating by using a constant temperature box, controlling the temperature of a reaction system in a reaction kettle to be raised to 100 ℃ from room temperature within 4 hours, then maintaining the constant temperature of 100 ℃ for 72 hours, cooling the reaction system in the reaction kettle to room temperature from 100 ℃ within 24 hours, carrying out suction filtration on a product of the self-assembly reaction after the self-assembly reaction is finished, and drying by using a vacuum drying box after the suction filtration is finished to obtain a green solid substance, namely the metal-organic framework material for absorbing formaldehyde, and marking as a complex 1.
The compound 1 crystal prepared in example 1 was subjected to X-ray single crystal diffraction analysis by using an X-ray single crystal diffraction analyzer, and specific experimental results are shown in FIGS. 1, 2, 3, 4 and 5.
FIG. 1 is a thermal ellipsometry of X-ray single crystal diffraction analysis of crystals of complex 1 prepared in example 1. As can be seen from FIG. 1, ni in the crystals of complex 1 prepared in example 1 2+ Ion and two different mbpcs 2- The four carboxylic acid oxygen atoms in the anion and the two nitrogen atoms in the two IMBM ligands coordinate to form a hexacoordinated octahedral geometry.
FIG. 2 shows mbpc in crystals of complex 1 prepared in example 1 2- And the coordination pattern of the IMBM ligand, as can be seen from FIG. 2, in complex 1, mbpc 2- The anion is coordinated in only one way, and the mode of the complex for connecting 2 nickel (II) ions is a chelate-chelate mode; the two nickel (II) ions are linked by an IMBM ligand.
FIG. 3 shows [ Ni ] in the crystals of complex 1 prepared in example 1 2 (COO) 8 N 8 ]FIG. 4 is a schematic view showing a club of a secondary building block of a tetranuclear cluster, and FIG. 3 and FIG. 4 show three-dimensional porous structures of the complex 1 prepared in example 1. As can be seen from FIGS. 3 and 4, [ Ni ] in the crystals of the complex 1 prepared in example 1 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2- The anions are connected into a three-dimensional porous structure in a connecting mode.
FIG. 5 is an X-ray powder diffraction pattern of the complex 1 prepared in example 1, wherein a simulated pattern was obtained by collecting single crystal data on a Bruker APEX II diffractometer, and as can be seen from FIG. 5, the complex 1 prepared in example 1 synthesized by a self-assembly reaction, i.e., each main peak position of the metal organic framework material, was substantially coincident with the simulated pattern), which indicates that the complex 1 was successfully synthesized in example 1 of the present invention.
X-ray diffraction data of the complex 1 prepared in example 1, which were corrected for Lp factor and absorption (multi-scan) and the crystal structure was solved by direct method (SHELXS-97) to obtain the crystallographic parameters and partial bond length angles of the complex 1 prepared in example 1, were subjected to data reduction using a crystal clear program, and specific results are shown in tables 1 and 2.
TABLE 1 crystallographic parameters of Complex 1 prepared in example 1
In table 1, r= Σ (|f) o ︱－︱F c ‖)/∑︱F o ︱.wR＝[∑w(F o 2 –F c 2 ) 2 /∑w(F o ) 2 ] 1/2 。
TABLE 2 partial bond long bond angles (nm, °) for Complex 1 prepared in example 1
| Key length | Numerical value | Key angle | Numerical value |
| Ni1-O1 i | 0.2173(4) | O2 i -Ni1-O1 i | 62.11(12) |
| Ni1-O2 i | 0.2065(3) | O2 i -Ni1-O3 | 162.99(15) |
| Ni1-O3 | 0.2076(3) | O2 i -Ni1-O4 | 103.87(13) |
| Ni1-O4 | 0.2153(4) | O3-Ni1-O1 i | 106.02(14) |
| Ni1-N2 | 0.2030(4) | N2-Ni1-O1 i | 153.96(15) |
| Ni1-N4 ii | 0.2026(4) | O2 i -Ni1-N2 | 92.44(15) |
| O1 i -Ni1-N4 ii | 89.36(15) | ||
| N4 ii -Ni1-O2 i | 96.16(15) | ||
| O3-Ni1-N4 ii | 95.80(15) | ||
| N2-Ni1-N4 ii | 99.42(18) |
In table 2, the operation symmetry codes i=1-y, 1/2+x,2-z; ii=y, 1/2-x,1+z.
TGA thermogravimetric analysis is performed on the complex 1 prepared in example 1 to obtain a thermogravimetric analysis graph, as shown in fig. 6, it can be seen from fig. 6 that in the process of heating from room temperature to 800 ℃ and then cooling to below 30min to 50 ℃ under nitrogen atmosphere, the thermogravimetric analysis graph of the complex 1 prepared in example 1 loses weight for the first time between 30 and 315 ℃ possibly due to insufficient drying, water molecules remain, and the mass is reduced by about 6.51%; a second weight loss between 315 and 414 ℃ may be due to loss of DMF solvent molecules, a mass reduction of about 34.57%; when the temperature reached above 414 ℃, the structure of the complex 1 collapsed, indicating that the complex 1 prepared in example 1 had better thermal stability at 315 ℃.
Example 2
A preparation method of a composite PBT material comprises the following steps:
a. 92g of PBT particles are firstly dried for 24 hours at 110 ℃ in an electrothermal constant-temperature blast drying oven, and then melted in a double-roller mixer to obtain a PBT melt;
b. adding 8g of the metal organic framework material for adsorbing formaldehyde prepared in the embodiment 1 into the PBT melt obtained in the step a, mixing for 1h at 230 ℃, extruding and granulating by a double-screw extruder, and then sequentially grinding and sieving by a nine-sieve to obtain a composite PBT material, wherein the composite PBT material is 8wt% of complex 1@PBT;
the mass of the metal organic framework material for adsorbing formaldehyde prepared in the embodiment 1 is 8% of the mass of the composite PBT material.
Example 3
A composite PBT material was prepared as in example 2, denoted 10 wt.% complex 1@PBT;
unlike example 2, the mass of the metal organic framework material for adsorbing formaldehyde prepared in example 1 in step b is 10% of the mass of the composite PBT material.
Example 4
A composite PBT material was prepared as in example 2, denoted 15 wt.% of the complex 1@PBT;
unlike example 2, the mass of the metal organic framework material for adsorbing formaldehyde prepared in example 1 in step b is 15% of the mass of the composite PBT material.
Example 5
A composite PBT material was prepared as in example 2, denoted 20 wt.% of the complex 1@PBT;
unlike example 2, the mass of the metal organic framework material for adsorbing formaldehyde prepared in example 1 in step b was 20% of the mass of the composite PBT material.
Comparative example 1
Composite 1, designated 5wt% Complex 1@PBT, was prepared as in example 2;
unlike example 2, the mass of the metal organic framework material for adsorbing formaldehyde prepared in example 1 in the step b is 5% of the mass of the composite material 1.
Comparative example 2
Composite 2, designated 10wt% activated carbon @ PBT, was prepared as in example 2;
unlike example 2, activated carbon that can pass through a 250 mesh sieve is used as a raw material in the step b, and the mass of the activated carbon is 10% of that of the composite material 2.
Comparative example 3
Composite 3, designated 10wt% silica @ PBT, was prepared as in example 2;
unlike example 2, silica capable of passing through a 250 mesh sieve was used as the raw material in the step b, and the mass of silica was 10% of the mass of the composite material 3.
Formaldehyde adsorption performance test
The detection process comprises the following steps: build a closed space, as shown in fig. 7, formaldehyde solution and deionized water were mixed according to a ratio of 1:50, and adopting a formaldehyde tester (Si Le Zhi formaldehyde tester MEF 500) to observe the change of formaldehyde data in the space in real time, wherein when the formaldehyde tester detection data tend to be stable, the initial concentration of formaldehyde in the sealing device is controlled at 2mg/m 3 The method comprises the steps of taking 0.1g of activated carbon capable of passing through a 250-mesh sieve, silicon dioxide capable of passing through the 250-mesh sieve, complex 1 powder prepared in example 1, 8wt% of complex 1@PBT prepared in examples 2-5, 10wt% of complex 1@PBT, 15wt% of complex 1@PBT, 20wt% of complex 1@PBT, 5wt% of complex 1@PBT prepared in comparative example 1, 10wt% of activated carbon@PBT prepared in comparative example 2 and 10wt% of silicon dioxide@PBT prepared in comparative example 3 as substances to be detected, respectively wrapping, putting the substances to be detected in 10 formaldehyde adsorption performance test devices, and putting the substances to be detected in the formaldehyde adsorption performance test devices for formaldehyde adsorption performance test to obtain a formaldehyde adsorption graph.
The formaldehyde removal rate was calculated as follows:
Q＝(C 0 -C 1 )/C 0 ×100％
wherein Q represents formaldehyde removal rate (%), C 0 Represents the initial concentration of formaldehyde (mg/m) 3 )，C 1 Represents the final concentration of formaldehyde (mg/m) 3 )。
FIG. 7 is a schematic diagram of a formaldehyde adsorption performance testing apparatus used in the present invention;
FIG. 8 is a graph showing the formaldehyde adsorption of activated carbon, silica and the complex 1 prepared in example 1. As can be seen from FIG. 8, the complex 1 prepared in example 1 has better formaldehyde adsorption capacity than activated carbon, and the formaldehyde concentration can be reduced to 0.08mg/m after 2 hours 3 The formaldehyde removal rate can reach 96%; the formaldehyde removal rate of silica within 2h was 74% and the formaldehyde removal rate of the activated carbon material within 2h was 58%, indicating that complex 1 exhibited excellent formaldehyde adsorption performance due to the large specific surface area and high porosity of complex 1 prepared in example 1.
Fig. 9 is a graph showing formaldehyde adsorption of each object to be detected, and as can be seen from fig. 9:
(1) The formaldehyde removal rate of the activated carbon material in 2h is 58%, the formaldehyde removal rate of the silicon dioxide in 2h is 74%, and 10wt% of the complex 1@PBT can reduce the formaldehyde concentration to 0.65mg/m after 2h 3 The formaldehyde removal rate can reach 67.5%, and the formaldehyde removal rate of 10wt% of silicon dioxide @ PBT is 33.8%, which is far lower than that of the PBT material added with the same content of the complex 1, and the formaldehyde removal rate is probably caused by poor dispersibility and compatibility in the PBT when the silicon dioxide is added as powder;
(2) The formaldehyde removal rate of the 10wt% active carbon@PBT material is 19.6%, and the color of the active carbon-added PBT material is deepened due to the color of the active carbon, which is unfavorable for the use of the material as a surface coating in the later period, and the 10wt% complex 1@PBT material has a larger specific surface area and a higher porosity and shows higher formaldehyde adsorption performance due to the complex 1;
(3) 5wt% of complex 1@PBT material can reduce formaldehyde concentration to 1.02mg/m after 2 hours 3 The formaldehyde removal rate is 49%, the formaldehyde removal rate of the activated carbon material is 58% in 2h, and as can be seen, the formaldehyde adsorption capacity of the 5wt% complex 1@PBT material is not as good as that of the activated carbon;
(4) 15wt% of complex 1@PBT material can reduce formaldehyde concentration to 0.42mg/m after 2 hours 3 The formaldehyde removal rate is 79%, the formaldehyde removal rate of the activated carbon material is 58% in 2h, and the formaldehyde adsorption capacity of 15wt% of the complex 1@PBT material is superior to that of the activated carbon;
(5) 20wt% of complex 1@PBT material can reduce formaldehyde concentration to 0.22mg/m after 2 hours 3 The formaldehyde removal rate is 89%, the formaldehyde removal rate of the activated carbon material is 58% in 2h, and the formaldehyde adsorption capacity of 20wt% of the complex 1@PBT material is superior to that of the activated carbon;
as can be seen from the above examples, the complex 1 prepared in example 1 has a better formaldehyde adsorption capacity than activated carbon, and the formaldehyde concentration can be reduced to 0.08mg/m after 2 hours 3 The formaldehyde removal rate can reach 96%, and the formaldehyde concentration of the 20wt% complex 1@PBT material can be reduced to 0.22mg/m after 2 hours 3 The formaldehyde removal rate can reach 89%, and the composite PBT material with the content of the complex 1 being 10-20wt% has formaldehyde adsorption effect superior to that of active carbon.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the composite PBT material comprises the following steps:
a. sequentially drying and melting the PBT to obtain a PBT melt;
b. adding a metal organic framework material for absorbing formaldehyde into the PBT melt obtained in the step a, and then sequentially mixing and extruding to obtain a composite PBT material;
the chemical formula of the metal organic framework material for adsorbing formaldehyde is [ Ni (mbpc) (IMBM) ] n, wherein mbpc in the formula I is 4' -methylbiphenyl-3, 5-dicarboxylic acid, and IMBM is 1, 4-bis (imidazol-1-yl) benzene;
the metal-organic framework material for formaldehyde adsorption has asymmetric structural units, which comprise an anion mbpc 2- One cation Ni 2+ And an IMBM ligand, said building block number n; the Ni is 2+ Unlike two different mbpcs 2- The four carboxylic acid oxygen atoms in the anion and the two nitrogen atoms in the two IMBM ligands coordinate to form a hexacoordinated octahedral geometry; the metal organic framework material for adsorbing formaldehyde has [ Ni ] 2 (COOH) 8 N 8 ]A secondary construction unit of the quad-core cluster; the [ Ni ] 2 (COO) 8 N 8 ]The secondary building unit of the four-core cluster is based on IMBM and mbpc 2- The anions are connected into a three-dimensional porous structure in a connection mode;
the pore size of the three-dimensional porous in the three-dimensional porous structure is 0.63×0.71 and nm, and the three-dimensional porous surface has methyl and phenyl groups which protrude.
2. The preparation method of the composite PBT material as claimed in claim 1, wherein the preparation method of the metal-organic framework material for adsorbing formaldehyde comprises the following steps:
(1) Mixing 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene, a nickel source and N, N-dimethylformamide to obtain a mixed solution;
(2) Performing self-assembly reaction on the mixed solution obtained in the step (1) to obtain a metal organic framework material for adsorbing formaldehyde;
the self-assembly reaction is heated in the following way: and heating from room temperature to 95-110 ℃ within 3-5 h, then preserving heat at 95-110 ℃ for 65-80 h, and then cooling from 95-110 ℃ to room temperature within 20-30 h.
3. The method according to claim 2, wherein the ratio of the amounts of the substances of 4' -methylbiphenyl-3, 5-dicarboxylic acid, 1, 4-bis (imidazol-1-yl) benzene and nickel source in the step (1) is (0.6 to 1.2): 0.5 to 3.
4. The process according to claim 2, wherein the ratio of the amount of the substance of 4' -methylbiphenyl-3, 5-dicarboxylic acid to the volume of N, N-dimethylformamide in the step (1) is 1mol: (2-10) mL.
5. The method according to claim 2, wherein the self-assembly reaction in step (2) is performed at a temperature rising mode of: and heating from room temperature to 98-105 ℃ within 3.5-4.5 h, then preserving heat for 70-78 h at 98-105 ℃, and then cooling from 98-105 ℃ to room temperature within 25-28 h.
6. The method according to claim 1, wherein the temperature of the mixing in the step b is 210-250 ℃, and the mixing time is 40-120 min.
7. The preparation method according to claim 1, wherein the mass of the metal organic framework material for adsorbing formaldehyde in the step b is 10% -22% of the mass of the composite PBT material.
8. The composite PBT material prepared by the preparation method of any one of claims 1-7.
9. The use of the composite PBT material in formaldehyde adsorption according to claim 8.
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| EP3047969B1 (en) * | 2015-01-22 | 2018-04-25 | Kautex Textron Gmbh&Co. Kg | Multi-layer composite material and articles comprising the same |
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| CN101330978A (en) * | 2005-11-14 | 2008-12-24 | 巴斯夫欧洲公司 | Porous organo-metallic skeleton material containing an additional polymer |
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