CN109206631B - Method for improving orientation degree of rigid chain segment in copolymer - Google Patents
Method for improving orientation degree of rigid chain segment in copolymer Download PDFInfo
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- CN109206631B CN109206631B CN201811042766.0A CN201811042766A CN109206631B CN 109206631 B CN109206631 B CN 109206631B CN 201811042766 A CN201811042766 A CN 201811042766A CN 109206631 B CN109206631 B CN 109206631B
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Abstract
The invention discloses a method for improving the orientation degree of a rigid chain segment in a copolymer, which is realized by directly adsorbing and wrapping a rigid-flexible block copolymer chain by adopting a metal organic framework MOF with ordered pore channels and matched pore size with the diameter of a polymer chain, wherein the rigid-flexible block copolymer chain comprises the rigid chain segment and a flexible chain segment, after the copolymer chain enters an MOF pore channel, the orientation of the rigid chain segment in the copolymer chain is induced by utilizing the molecular acting force between the pore wall of the MOF and each chain segment, and the orientation degree of the rigid chain segment is further improved by matching with the rotation of a single bond of the flexible chain segment. The method disclosed by the invention can be used for preparing the copolymer material with the highly-oriented rigid chain segment, and provides technical support for developing the high-polarization organic light-emitting material.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric devices, and particularly relates to a method for improving the orientation degree of a rigid chain segment in a copolymer.
Background
Organic luminescent materials are an important optical material, and are widely applied to the fields of illumination, backlight sources, sensing and the like. Among the organic light emitting materials, the polymer light emitting material is an important light emitting material having many advantages. It has many varieties, easy production, low cost and good performance. The optical device based on the polymer luminescent material also has the advantages of simple preparation process, low optical loss, easy adjustment of refractive index, easy integration with other electronic devices and the like. The polymer light emitting material comprises a plurality of polymer chains, wherein the polymer chains are polymer chains formed by polymerization reaction of polymer monomer molecules and are composed of a plurality of repeating units, so that the polymer chains are longer. However, the polymer chains are not generally straightened, but rather curl up and assume various morphologies. These morphologies are caused by the spatially different behavior of the molecule due to internal rotation of single bonds.
Among them, a flexible polymer chain is one in which the internal rotation of a single bond in the chain structure is easy and the number of conformations of the molecule is large; on the other hand, a rigid polymer chain is one in which rotation of a single bond is difficult and the number of conformations of the molecule is small. A great deal of research shows that the luminescent organic matter with a certain rigid polymer chain structure has better fluorescence performance. Furthermore, the strength, modulus and stability of the material of the highly oriented rigid polymer chains are high, and the modulus and strength of the highly oriented rigid polymer chains reach the level of steel wires and glass fibers. However, in the prior art, the luminescent material has low orientation degree and no definite spatial direction in both flexible and rigid polymer chains, and shows low luminescent polarization degree.
The orientation degree of the polymerized luminescent material is improved, so that high luminescent polarization degree is obtained, and the method becomes a key focus target in current scientific research and production. Currently, some methods for increasing the degree of orientation of polymer chains have been disclosed, such as mechanical stretching and methods using Metal-Organic Framework (MOF) nanopores to promote the orientation of polymer molecules and chains. The mechanical stretching method is characterized in that a polymer film is stretched by mechanical force by utilizing the characteristic that the polymer has ductility, and polymer molecules are arranged along the direction of stress, so that the orientation degree is improved; the MOF method is an effective method to increase the degree of orientation of polymer chains, and involves in-situ polymerization of monomers in the nanopores of the MOF and direct incorporation of polymer chains into the nanopores of the MOF. Since the monomer is a small molecule, it can easily enter the MOF pore channels, and the size, shape, etc. of the pore channels can be systematically adjusted by the choice of metal ions and bridging ligands, as in Uemura et al [ Zn2(BDC)2(TED)]nFree Radical polymerization of styrene (St) was performed in one-dimensional nanochannels of (BDC ═ 1, 4-benzenedicarboxylate, TED ═ triethylenediamine) crystals [ Uemura T, et al, radial polymerization of styrene in porous coordination polymers, chemical Communications,2005,48(48):5968-5970.]. However, it is not easy to precisely control the molecular weight and the loading of the polymer using the in situ polymerization method. To overcome these limitations, direct incorporation of polymer chains into MOFs is a simple and straightforward method, one of its significant advantages being the ability to incorporate polymer chains directly that are not readily polymerized in MOFs. The method is simpleMelt processing, solution-mediated incorporation and MOF growth in polymers [ Kitao T, et al, Hybridization of MOFs and polymers, chemical Society Reviews,2017,46(11):3108.]。
It is noteworthy that although direct adsorption of polymer chains is possible with MOFs, this approach has certain limitations, such as the difficulty in rotating the covalent linkage in purely rigid polymer chains, the difficulty in achieving sufficient dissolution in the MOF solution into the MOF channels; moreover, when the rigid polymer chain is long, its corresponding molecular weight is high, and the MOF pore walls have weak intermolecular forces on it, making it difficult to induce its orientation.
Therefore, in order to obtain a polymer segment with a definite spatial direction and a high degree of light-emitting polarization, and further to improve the strength, modulus and stability of the material, it is necessary to propose a new method capable of improving the degree of orientation of the rigid segment in the copolymer.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for improving the orientation degree of a rigid chain segment in a copolymer.
The specific technical scheme of the invention is as follows:
the invention discloses a method for improving the orientation degree of a rigid chain segment in a copolymer, which is realized by directly adsorbing and wrapping a rigid-flexible block copolymer chain by adopting a Metal Organic Framework (MOF), wherein the rigid-flexible block copolymer chain comprises the rigid chain segment and a flexible chain segment, and the rigid chain segment is oriented by matching the induction of molecular acting force between the wall of a hole of the MOF and each chain segment with the rotation of a single bond of the flexible chain segment; the method specifically comprises the following operation steps:
1) building a rigid-flexible block copolymer chain;
2) selecting MOF materials according to the characteristics of the copolymer chain, and synthesizing MOF by adopting a solvent method volatilization method or a solvothermal method;
3) directly introducing the copolymer chain prepared in the step 1) into the ordered pore channels of the MOF prepared in the step 2) to induce polymerization
Orientation of the rigid segments in the chain.
Further, the characteristics of the copolymer chains in selecting the MOF material in step 2) include the diameter, molecular weight and rigid-flexible structure of the chains.
Further, the MOFs selected in the step 2) are not only ordered in pore channels, but also the pore sizes of the MOFs are matched with the diameters of the copolymer chains, so that the polymer chains can be adsorbed, and the orientation of the rigid chain segments in the copolymer chains can be better induced.
Further, the method for constructing the rigid-flexible block polymer chain in step 1) includes a living polymerization method, a living anion/cation polymerization method, a group transfer polymerization method and a controlled radical polymerization method, and preferably, the living polymerization method is selected to construct the rigid-flexible block polymer chain, and the method can better control the molecular weight and the molecular weight distribution of the polymer.
Further, the method for introducing the copolymer chains into the MOF ordered pore channels in the step 3) comprises a method for in-situ polymerization of monomers in the MOF nanometer pore channels, cross-linking copolymerization of monomers and MOF framework, and a method for directly introducing the polymer chains into the MOF nanometer pore channels.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for improving the orientation degree of a rigid chain segment in a copolymer, which is realized by directly adsorbing a rigid-flexible block polymer chain through MOF. After the copolymer chain enters the MOF, intermolecular force is generated between the MOF pore wall and the polymer chain, so that the directional arrangement of the rigid chain segment is induced; the solubility of the polymer chain can be increased by the flexible chain segment in the copolymer, so that the polymer chain can easily enter the MOF pore canal, and meanwhile, the orientation capability of the rigid chain segment is further improved by the rotation of the single bond of the flexible chain segment, so that the orientation degree of the rigid chain segment is improved. The invention can effectively improve the orientation degree of the rigid chain segment in the copolymer and provides technical support for developing high-polarization organic luminescent materials.
Drawings
FIG. 1 is a schematic flow chart of a method for increasing the degree of orientation of a rigid segment in a copolymer according to the present invention;
FIG. 2 is a full atomic model of MOF-BDC, wherein a) is a side view and b) is a cross-sectional view;
FIG. 3 is a full atom model of a PPV rigid polymer chain;
FIG. 4 is a full atom model of a PPV-b-PSt diblock polymer chain;
FIG. 5 is a drawing showing
The result of the kinetic movement of molecular dynamics, wherein a) is
b) Is composed of
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Selecting polymerized p-phenylene vinylene-b-polystyrene (PPV-b-PSt) as a rigid-soft block copolymer chain, selecting the polymerized p-phenylene vinylene (PPV) as a referential rigid polymer chain, and selecting [ Zn ]2(BDC)2TED]n(denoted as MOF-BDC, BDC 1, 4-terephthalic acid, TED triethyldiamine) as MOF material. To verify the effects of the examples, the degree of orientation of the rigid polymer chains and the degree of orientation of the rigid segments in the rigid-flexible block copolymer chains in the MOF were calculated using molecular dynamics simulation.
The full atomic model of MOF-BDC is shown in FIG. 2.
The full atom model of the PPV rigid polymer chain is shown in fig. 3.
The full atom model of the PPV-b-PSt diblock polymer chain obtained by initiating atom transfer radical polymerization of styrene by using PPV oligomer as a macroinitiator is shown in FIG. 4.
Respectively introducing a PPV rigid polymer chain and a PPV-b-PSt diblock polymer chain into the MOFs nanometer pore canal, and respectively aligning the PPV rigid polymer chain and the PPV-b-PSt diblock polymer chain
Molecular dynamics simulations were performed to obtain the results of the two polymer chains in a stable state in MOFs, as shown in fig. 5.
The degree of orientation of the PPV of the rigid segment was calculated to be 0.47,
the average degree of orientation of the middle rigid PPV segment was 0.874,
the degree of orientation of the medium rigid PPV segment was 0.972. From the three sets of data, it can be seen that
The medium-rigidity PPV chain segment is oriented under the induction of molecular acting force between the MOF pore wall and the polymer chain; in addition, due to the rotation of the single bond of the soft segment,
the degree of orientation of the medium rigid PPV segment is further improved.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (4)
1. A method for improving the orientation degree of a rigid chain segment in a copolymer is characterized in that the method is realized by directly adsorbing and wrapping a rigid-flexible block copolymer chain by adopting a Metal Organic Framework (MOF), wherein the rigid-flexible block copolymer chain comprises the rigid chain segment and a flexible chain segment, and the rigid chain segment is oriented by matching the induction of molecular acting force between the pore wall of the MOF and each chain segment with the rotation of a single bond of the flexible chain segment; the method specifically comprises the following operation steps:
1) building a rigid-flexible block copolymer chain;
2) selecting MOF materials according to the characteristics of the copolymer chain, and synthesizing MOF by adopting a solvent method volatilization method or a solvothermal method;
3) directly introducing the copolymer chain prepared in the step 1) into the ordered pore channels of the MOF prepared in the step 2) to induce the orientation of the rigid chain segment in the polymer chain;
the characteristics of the copolymer chains according to which the MOF material is selected in the step 2) comprise the diameter and molecular weight of the copolymer chains and the rigid-flexible structure of the chains;
the MOF selected in the step 2) is not only ordered in pore channels, but also the pore size of the MOF is matched with the diameter of a copolymer chain.
2. The method of claim 1, wherein the rigid-flexible block polymer chain in step 1) is constructed by living polymerization, living anionic/cationic polymerization, group transfer polymerization, and controlled radical polymerization.
3. The method for improving the orientation degree of the rigid chain segments in the copolymer according to claim 1, wherein the method for introducing the copolymer chains into the MOF ordered pore channels in the step 3) comprises a method for in-situ polymerization of monomers in the MOF nanometer pore channels, a method for cross-linking copolymerization of the monomers and an MOF framework, and a method for directly introducing the polymer chains into the MOF nanometer pore channels.
4. The method of claim 1, wherein the rigid-flexible block polymer chain in step 1) is constructed by a living polymerization method.
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