CN110467721B - Polyaryletherketone porous microsphere and preparation method thereof - Google Patents

Polyaryletherketone porous microsphere and preparation method thereof Download PDF

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CN110467721B
CN110467721B CN201910694207.6A CN201910694207A CN110467721B CN 110467721 B CN110467721 B CN 110467721B CN 201910694207 A CN201910694207 A CN 201910694207A CN 110467721 B CN110467721 B CN 110467721B
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polyaryletherketone
porous
microsphere
microspheres
diphenyl ether
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CN110467721A (en
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杨鹏飞
张志良
白锋
王永清
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Qilu University of Technology
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    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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Abstract

The invention relates to a porous polyaryletherketone microsphere and a preparation method thereof, which takes 1,3, 5-benzene trimethyl acyl chloride and diphenyl ether as raw materials, dichloromethane and the like as solvents and titanium tetrachloride as catalysts to carry out precipitation polymerization through Friedel-crafts acylation reaction to synthesize the polyaryletherketone. And (4) performing characterization by using a scanning electron microscope, a thermogravimetric test, an infrared spectrum and the like. The result shows that the polyaryletherketone material has a regular spherical structure, is insoluble in most organic solvents, has a large number of irregular holes inside, and can be applied to the fields of catalyst carriers, adsorption separation and the like.

Description

Polyaryletherketone porous microsphere and preparation method thereof
Technical Field
The invention relates to a polyaryletherketone porous microsphere and a preparation method thereof, belonging to the technical field of porous materials.
Background
The porous polymer microsphere is a polymer spherical particle with a porous structure prepared by adopting a macromolecular synthesis method. The material has the characteristics of various preparation methods, easy modification, adjustable pore size and the like, and has wide application in the aspects of chromatographic packing, catalyst carriers, biological analysis, composite materials and the like. The suspension polymerization method is a main method for preparing porous microspheres, and comprises the steps of firstly adding a pore-forming agent into a monomer for suspension polymerization, and removing the pore-forming agent after the polymerization is finished, wherein the originally occupied space of the pore-forming agent is reserved, so that the microspheres have a porous structure. A polystyrene porous microsphere with good monodispersity is synthesized by using a mixed solution of dibutyl phthalate (DBP) and toluene as a pore-foaming agent and adopting a two-step seed swelling polymerization method, wherein the particle size of the microsphere is 5 mu m, and the specific surface area is 562m2(ii) in terms of/g. Researches show that after diazotization modification and illumination crosslinking, the polymer porous microspheres have advantages in the aspects of porous structure, high crosslinking degree, stable mechanical properties and the like. The porous structure results in large specific surface area and small osmotic pressure, and the high crosslinking degree can ensure that the composite material has stable mechanical propertiesThe chromatographic stationary phase can be used for separating various nonpolar substances from polar substances. (see: Tao Xu, Bing Yu, Xiaoyuan Zhuang, Hongbo Zhuang, Hailin Cong, Shujing Yang. Synthesis and application of regulators of PS possus microspheres. Integrated Ferroeletrics,2016,171,101-107.)
The porous polyurea microspheres are prepared by a one-step precipitation polymerization method by taking toluene diisocyanate as a raw material and a mixed solvent of water and acetone as a pore-forming agent, the particle size is distributed between 10 mu m and 40 mu m, the pore diameter is distributed between 2nm and 1000nm, and the specific surface area can reach 161.68m2(ii) in terms of/g. And then activating the polyurea porous microspheres by glutaraldehyde, and fixing pseudomonas fluorescens lipase for catalyzing p-nitrophenylpalmitate hydrolysis reaction, 1-phenethyl alcohol and vinyl acetate transesterification reaction and chiral resolution of (R, S) -1-phenethyl alcohol. The results show that the immobilized enzyme has improved temperature and pH adaptability and better catalytic activity in organic solvents and selectivity to chiral compounds than the free enzyme. (see: Hui Han, Shusing Li, Xiaooli Zhu, Xiubao Jiang, Xiagzheng Kong. one step prediction of pore poly urea by reaction of cellulose diisocyanate with water and cellulose characterization. RSC Advances,2014,4:33520 and 33529.)
Although the material, size, pore diameter, specific surface area, application, etc. of porous microspheres have been studied and explored a lot, porogens are indispensable in the preparation of most porous microspheres, such as dibutyl phthalate, toluene, water, acetone, etc. in the above studies. Since a pore-forming agent is needed to be used in the preparation process and the pore-forming agent needs to be removed from the final product, more or less pore-forming agent residues exist in the porous microspheres obtained by the method, and certain influence is generated on the subsequent application. In addition, the existing preparation process mostly uses cross-linking agents, conditions such as stirring, heating and the like, and not only is the process complicated, but also the energy consumption is high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyaryletherketone porous microsphere and a preparation method thereof. The invention develops a new method, takes rigid benzophenone in polyaryletherketone as a basic structure of the microsphere, and leads the obtained polyaryletherketone microsphere to generate a large amount of cavities because of the support of the rigid structure, thereby avoiding using pore-forming agents, simplifying the steps of synthesis and post-treatment and improving the purity of the chemical structure of the microsphere. Moreover, the chemical synthesis principle of the microspheres is simple, the microspheres can be obtained through a self-precipitation process at room temperature, the processes such as stirring and heating are not needed, and the energy consumption is relatively low.
The technical scheme of the invention is as follows:
a polyaryletherketone porous microsphere, the chemical structure of which has a spatially repeating unit represented by formula (I):
Figure BDA0002148836350000021
(I)。
according to the present invention, preferably, the pore channel distribution of the porous microsphere is irregular, and further preferably, the pore diameter is 100-3000 nm.
According to the present invention, it is preferable that the porous microspheres have a specific surface area of 20 to 200m2/g。
According to the present invention, preferably, the thermogravimetric curve (TG) of the porous microsphere shows that the initial decomposition temperature is 390-410 ℃ and the termination temperature is 710-730 ℃.
According to the invention, the preparation method of the polyaryletherketone porous microsphere comprises the following steps:
1,3, 5-benzene trimethyl acyl chloride and diphenyl ether are used as raw materials, titanium tetrachloride is used as a catalyst, and polymerization reaction is carried out at room temperature to obtain the polyaryletherketone porous microsphere.
According to the present invention, it is preferable that the molar ratio of 1,3, 5-benzenetricarbonyl chloride to diphenyl ether is (0.8-1.6): 1.
according to the invention, the molar ratio of the catalyst aluminum trichloride to the diphenyl ether is preferably (3-10): 1.
according to the present invention, it is preferable that the polymerization reaction is carried out in a solvent selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and dimethylsulfoxide.
The principle of the invention is as follows:
Figure BDA0002148836350000031
the reaction mechanism is as follows: the Friedel-Crafts reaction is an abbreviation of Friedel-Crafts reaction, and the reaction in which hydrogen in an organic compound molecule is substituted by an acyl group under the action of a catalyst is called a Friedel-Crafts acylation reaction. When titanium tetrachloride is used as a catalyst, a reactant, the catalyst and a solvent form a homogeneous mixture, and the titanium tetrachloride can be complexed with carbonyl groups to show a catalytic effect. Under the catalytic action of carbon tetrachloride, Friedel-crafts reaction occurs between 1,3, 5-benzene tri-formyl chloride and diphenyl ether to carry out polymerization.
The balling mechanism is as follows: at the initial stage of reaction, the molecular weight of the product polyaryletherketone is small and can be dissolved in a reaction system; at this time, the polymerization reaction is based on collision between molecules, and the reaction rate is fast. Along with the continuous increase of molecular weight, the cross-linking structure of the polyaryletherketone is gradually obvious and is separated out from the reaction liquid to generate a non-fusible and insoluble polymer; at this time, the collision probability between the microspheres is greatly reduced, so that the microspheres are relatively independent and are not easy to bond. In addition, the polyaryletherketone is spherical because the precipitation process is not constrained by any external force.
The pore-forming mechanism is as follows: the polymer molecule contains a large number of benzophenone structures which are rigid conjugated structures, and carbon-carbon double bonds can not rotate. Such molecular frameworks cannot interpenetrate and stack with each other, resulting in formation of a large number of pore structures within the microspheres.
The invention has the beneficial effects that:
1. the invention uses trifunctional 1,3, 5-benzene tricarboxy chloride and bifunctional diphenyl ether to prepare the crosslinked polyaryletherketone, so that the crosslinked polyaryletherketone is insoluble in most organic solvents and does not need to use a crosslinking agent.
2. The invention utilizes the room temperature precipitation polymerization method to prepare the polyaryletherketone microsphere with a regular shape, does not need heating and stirring, and has simple preparation process and low energy consumption.
3. According to the characteristic that benzene rings have rigid structures, a plurality of benzene rings in the polymer are connected to generate a porous structure, a pore-forming agent is not needed, so that the porous microsphere does not contain pore-forming agent residues, and the subsequent application is facilitated.
4. The polyaryletherketone porous microsphere is of a regular spherical structure, is insoluble in most organic solvents, is provided with a large number of irregular holes inside, and can be applied to the fields of catalyst carriers, adsorption separation and the like.
Drawings
FIG. 1 is an attenuated total reflection infrared spectrum of porous polyaryletherketone microspheres prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of porous polyaryletherketone microspheres prepared in example 1 of the present invention.
FIG. 3 is a transmission electron micrograph of porous polyaryletherketone microspheres prepared in example 1 of the present invention.
FIG. 4 is a graph showing TG and DTG curves of porous polyaryletherketone microspheres prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto, in conjunction with the accompanying drawings.
Example 1
0.500g of 1,3, 5-benzenetricarboxylic acid chloride, 0.481g of diphenyl ether were quickly weighed into a 250mL three-necked flask, and 100mL of methylene chloride was added. 5.359g of titanium tetrachloride were quickly weighed into a three-necked flask and shaken on a shaker for about 1 min. After standing and reacting for 72 hours at room temperature, the orange-red transparent liquid gradually becomes turbid, and precipitates are separated out. The reaction mixture was separated in a centrifuge tube at 10000rpm for 1 min. Washing the obtained solid with dichloromethane, centrifuging for 3 times, and drying the solid in a centrifugal tube in a drying oven overnight to obtain dark yellow solid powder, namely the polyaryletherketone porous microspheres.
Example 2
0.700g of 1,3, 5-benzenetricarboxylic acid chloride, 0.481g of diphenyl ether were quickly weighed into a 250mL three-necked flask, and 100mL of chloroform was added thereto. 5.359g of titanium tetrachloride were quickly weighed into a three-necked flask and shaken on a shaker for about 1 min. Standing at room temperature for 12h, the orange-red transparent liquid gradually becomes turbid, and precipitates are separated out. The reaction mixture was separated in a centrifuge tube at 10000rpm for 1 min. Washing the obtained solid with acetone and centrifuging for 3 times, putting the solid in a centrifugal tube into a drying oven to dry overnight, and finally obtaining dark yellow solid powder, namely the polyaryletherketone porous microspheres.
Example 3
0.800g of 1,3, 5-benzenetricarboxylic acid chloride, 0.481g of diphenyl ether were quickly weighed into a 250mL three-necked flask, and 100mL of dimethyl sulfoxide was added. 5.359g of titanium tetrachloride were quickly weighed into a three-necked flask and shaken on a shaker for about 1 min. After standing at room temperature for 24h, the clear liquid gradually became cloudy and precipitates. The reaction mixture was separated in a centrifuge tube at 10000rpm for 1 min. Washing the obtained solid with acetone and centrifuging for 3 times, putting the solid in a centrifugal tube into a drying oven to dry overnight, and finally obtaining dark yellow solid powder, namely the polyaryletherketone porous microspheres.
Test example 1, structural characterization
The solid sample obtained in example 1 was tested by attenuated total reflectance infrared spectroscopy, and the results are shown in FIG. 1. It is clear from FIG. 1 that at 1650cm-1The existence of absorption peaks at the left and the right indicates that the synthesized solid really has the existence of carbonyl and is 1815-1770 cm-1There was no absorption peak, indicating that the absorption peak of the acid chloride group had disappeared. And 1250-1000 cm-1There are also absorption peaks with similar values and intensities on the left and right sides, which are caused by the existence of ether bonds.
Test example 2 morphology characterization
The pore structure of the surface of the sample prepared in example 1 was measured by a scanning electron microscope, and the result is shown in fig. 2. The surface structure of the polyaryletherketone material can be clearly seen from fig. 2, and thus it is known that the material is really a porous material and the distribution of the channels is not regular.
The edge of the sample prepared in example 1 was tested for pore structure by transmission electron microscopy and the results are shown in FIG. 3. As can be seen from FIG. 3, the nano-scale light and dark channels are seen at the edge of the microsphere, and the distribution is dense.
Test example 3, thermal Property test
Thermogravimetric testing was performed on the sample prepared in example 1 to obtain a thermogravimetric plot of the solid material, as shown in figure 4. It can be seen from fig. 4 that the decomposition of the solid was substantially completed when the temperature was measured to 800 c. From the TG curve, it can be seen that the initial decomposition temperature of the porous material of polyaryletherketone is 400 ℃, the termination temperature is 720 ℃, the solid mass is always reduced in the interval, and the weight loss rate of polyaryletherketone is 35% by calculation. According to the DTG curve, the decomposition speed of the solid material is fastest around 513 ℃, the temperature of the maximum weight loss rate is 513.81 ℃, and the weight loss rate reaches 0.2163%.
Test example 4, specific surface area test
The sample prepared in example 1 was tested by nitrogen adsorption and the specific surface area of the polyaryletherketone material was calculated by BET method. The result shows that the specific surface area of the porous polyaryletherketone microspheres prepared in example 1 is 26.56 +/-0.69 m2/g。

Claims (8)

1. A polyaryletherketone porous microsphere, wherein the chemical structure of the porous microsphere has a spatially repeating unit represented by formula (I):
Figure DEST_PATH_IMAGE002
（I）。
2. the porous polyaryletherketone microsphere of claim 1, wherein the pore size of the porous microsphere is 100-3000 nm.
3. The porous polyaryletherketone microsphere of claim 1, wherein the porous microsphere has a specific surface area of 20-200m2/g。
4. The porous polyaryletherketone microsphere of claim 1, wherein the thermogravimetric curve (TG) of the porous microsphere shows that the initial decomposition temperature is 390-410 ℃ and the termination temperature is 710-730 ℃.
5. The method for preparing porous polyaryletherketone microspheres of any one of claims 1-4, comprising the steps of:
1,3, 5-benzene trimethyl acyl chloride and diphenyl ether are used as raw materials, titanium tetrachloride is used as a catalyst, and polymerization reaction is carried out at room temperature to obtain the polyaryletherketone porous microsphere.
6. The method for preparing porous polyaryletherketone microspheres of claim 5, wherein the molar ratio of 1,3, 5-benzenetricarbonyl chloride to diphenyl ether is (0.8-1.6): 1.
7. the method for preparing porous polyaryletherketone microspheres of claim 5, wherein the molar ratio of titanium tetrachloride and diphenyl ether used as catalysts is (3-10): 1.
8. the method for preparing porous polyaryletherketone microspheres of claim 5, wherein the polymerization reaction is performed in a solvent selected from dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and dimethylsulfoxide.
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