CN109206631A - A kind of method of the rigid chain segment degree of orientation in raising co-polymer - Google Patents
A kind of method of the rigid chain segment degree of orientation in raising co-polymer Download PDFInfo
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- CN109206631A CN109206631A CN201811042766.0A CN201811042766A CN109206631A CN 109206631 A CN109206631 A CN 109206631A CN 201811042766 A CN201811042766 A CN 201811042766A CN 109206631 A CN109206631 A CN 109206631A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses a kind of methods of the rigid chain segment degree of orientation in raising co-polymer, the method is orderly using duct, pore size metal organic frame MOF compatible with polymer chain diameter is directly adsorbed and is wrapped up hard and soft block copolymer chain to realize, wherein, it include rigid chain segment and soft segment in hard and soft block copolymer chain, after co-polymer chain enters in the duct MOF, the orientation of rigid chain segment in object chain is closed using the molecular force induced copolymerization between MOF hole wall and each segment, the rotation of cooperation soft segment singly-bound further increases the degree of orientation of rigid chain segment.The co-polymer material with highly oriented rigid chain segment can be prepared using the method disclosed in the present, provides technical support for the high polarization luminous organic material of exploitation.
Description
Technical field
The invention belongs to organic electro-optic device technical fields, and in particular to rigid chain segment orientation in a kind of raising co-polymer
The method of degree.
Background technique
Luminous organic material is a kind of important optical material, is widely used in the neck such as illumination, backlight, sensing
Domain.In numerous luminous organic materials, polymer luminescent material is a kind of important, luminescent material for having many advantages, such as.It
It is wide in variety, produce easy, at low cost and performance it is good.Optical device based on polymer luminescent material also have preparation process it is simple,
The advantages such as optical loss is low, refractive index easily adjusts, is easy to integrate with other electronic devices.Polymer luminescent material includes multiple poly-
Object chain is closed, polymer chain is the macromolecular chain formed by polymer monomer molecule by polymerization reaction, by several repetitive unit groups
At, therefore polymer chain is longer.But polymer chain is generally not to stretch, but be rolled up and various forms are presented.This
Caused by a little forms are the different manifestations of molecule spatially caused by being transferred by the inward turning of singly-bound.
Wherein, in chain structure singly-bound interior rotation be easy and the conformation number of molecule more than situation be flexible polymer chain；And
The situation that the interior rotation of singly-bound is difficult and the conformation number of molecule is few is then inflexible polymer chain.Through a large amount of the study found that having
The luminous organic matter of certain rigid polymer chain structure has preferable fluorescence property.Moreover, highly oriented inflexible polymer chain
Material intensity, modulus and stability it is all very high, such as height-oriented rigid-chain polymer fiber modulus and intensity can
Reach the level of steel wire and glass fibre.But in the prior art, either flexible or rigid polymer chain luminescent material
The degree of orientation is lower, without determining direction in space, shows lower luminous degree of polarization.
The degree of orientation of polymeric light-emitting materials is improved, to obtain high luminous degree of polarization, is become in current scientific research and production
The target paid close attention to.At present, it has been disclosed that the method for some degrees of orientation for being used to improve polymer chain, such as mechanical stretching method and benefit
Promote taking for polymer molecule and chain with the nano pore of metal organic frame (Metal-Organic Framework, MOF)
To method.Mechanical stretching method is that have the characteristics that ductility using polymer, is stretched with mechanical force to thin polymer film,
Polymer molecule is arranged with the direction of stress, to improve the degree of orientation；MOF method is the degree of orientation of a raising polymer chain
Effective ways, this method include that polymer chain in-situ polymerization and is directly introduced MOF in the nano pore of MOF by monomer
Nano pore.It since monomer is lesser molecule, can readily enter in the duct MOF, while pass through metal ion and bridge
Join ligand selection, can system call interception duct size, shape etc., if Uemura et al. is in [Zn2(BDC)2(TED)]n(BDC=
Isosorbide-5-Nitrae-benzene dicarboxylic acid esters, TED=triethylenediamine) crystal 1-dimention nano channel in carried out the free radical of styrene (St)
It polymerize [Uemura T, et al., Radical polymerisation of styrene in porous coordination
polymers.Chemical Communications,2005,48(48):5968-5970.].However, using situ aggregation method
It is not easy to accurately control the molecular weight of polymer and load capacity.To overcome these limitations, directly it is by polymer chain introducing MOFs
One simple and direct method, its remarkable advantage directly draw first is that the polymer chain polymerizeing in MOF can will be not easy
Enter.The introducing and grow the approach such as MOF realization [Kitao in the polymer that this method can be mediated by melt treatment, solution
T,et al.,Hybridization of MOFs and polymers.Chemical Society Reviews,2017,46
(11):3108.]。
Noteworthy point is that although directly adsorpting polymerization object chain, this method also can have a fixed limit using MOF
Property processed, such as link covalent bond in pure inflexible polymer chain are difficult to rotate, it is difficult to sufficiently dissolved in MOF solution and into
Enter the duct MOF；Moreover, corresponding molecular weight is very high when inflexible polymer chain is very long, intermolecular work of the MOF hole wall to it
It is firmly weaker, it is difficult to induce its orientation.
Therefore, connect section to obtain the determining and luminous higher polymer of degree of polarization of direction in space, and then improve material
Intensity, modulus and stability, it is necessary to propose a kind of new method that can be improved the degree of orientation of rigid chain segment in co-polymer.
Summary of the invention
It is an object of the invention to solving deficiency in the prior art, rigid chain segment in a kind of raising co-polymer is provided
The method of the degree of orientation passes through the adsorpting polymerization object in metal organic frame (Metal-Organic Framework, MOF) material
Strand, using the rotation of the orderly duct of MOF and the molecular force of polymer molecule interchain and soft segment singly-bound,
Promote the orientation of rigid chain segment.
The specific technical solution of the present invention is as described below:
The present invention discloses a kind of method for improving the rigid chain segment degree of orientation in co-polymer, and the method is that had using metal
Machine frame MOF is directly adsorbed and is wrapped up hard and soft block copolymer chain to realize, wherein in hard and soft block copolymer chain
Comprising rigid chain segment and soft segment, rigid chain segment cooperates by the induction of the molecular force between MOF hole wall and each segment
The rotation of soft segment singly-bound is orientated；This method specifically includes following operating procedure:
1) hard and soft block copolymer chain is constructed；
2) MOF material is selected according to the characteristic of co-polymer chain, using solvent method volatility process or solvent structure MOF；
3) co-polymer chain made from step 1) is introduced directly into the orderly duct of MOF made from step 2), induction is poly-
It closes
The orientation of rigid chain segment in object chain.
Further, the characteristic of the co-polymer chain of foundation includes co-polymer when selection MOF material in the step 2)
The multibody system of the diameter of chain, molecular weight and chain itself.
Further, not only duct is orderly by the MOF selected in the step 2), and the pore size and co-polymer of MOF
The diameter of chain is adapted to, so as to adsorpting polymerization object chain, and the preferably induced copolymerization orientation of closing rigid chain segment in object chain.
Further, in the step 1) construction method of Rod-coil copolymer chain include living polymerization, activity yin/
Cationic polymerization, group transfer polymerization method and controllable free-radical polymerisation method, preferably, selection living polymerization is rigid to construct
Soft block polymer chain, this method can preferably control polymer molecular weight and molecular weight distribution.
It further, include that monomer exists by the method that co-polymer chain is introduced into the orderly duct MOF in the step 3)
The method of in-situ polymerization, the copolymerzation with cross-linking of monomer and MOF frame and polymer chain is introduced directly into the nano pore of MOF
The method of the nano pore of MOF.
Compared with prior art, the invention has the following advantages:
The present invention provides a kind of method for improving the rigid chain segment degree of orientation in co-polymer, is directly to be adsorbed by MOF just
What soft block polymer chain was realized.After co-polymer chain enters MOF, intermolecular interaction is generated between MOF hole wall and polymer chain
Power, to induce aligning for rigid chain segment；And the soft segment in co-polymer not only can increase the dissolution of polymer chain
Property, enable polymer chain to be easily accessible the duct MOF, meanwhile, the rotation of the singly-bound of soft segment further improves rigid chain
The alignment capability of section, to improve the degree of orientation of rigid chain segment.The present invention can effectively improve rigid chain segment in co-polymer
The degree of orientation, provide technical support for the high polarization luminous organic material of exploitation.
Detailed description of the invention
Fig. 1 is a kind of flow diagram for improving the method for the rigid chain segment degree of orientation in co-polymer disclosed by the invention；
Fig. 2 is the full atom model of MOF-BDC, wherein a) is side view, b) it is sectional view；
Fig. 3 is the full atom model of PPV inflexible polymer chain；
Fig. 4 is the full atom model of PPV-b-PSt diblock polymer chain；
Fig. 5 isThe motion result of molecular dynamics wherein a) isB) it is
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
It chooses polymerization and hard and soft block copolymer chain is used as to phenylacetylene-b- polystyrene (PPV-b-PSt), choose poly- pair
Phenylacetylene (PPV) chooses [Zn as the inflexible polymer chain that can refer to2(BDC)2TED]n(it is denoted as MOF-BDC, BDC is Isosorbide-5-Nitrae-
Terephthalic acid (TPA), TED are triethyl group diamines) it is used as MOF material.For verify embodiment effect, using molecular dynamics simulation
And calculate the degree of orientation of the rigid chain segment in MOF in the degree of orientation and hard and soft block copolymer chain of inflexible polymer chain.
The full atom model of MOF-BDC is as shown in Figure 2.
The full atom model of PPV inflexible polymer chain is as shown in Figure 3.
Using PPV oligomer as macromole evocating agent, cause obtained from the atom transfer radical polymerization of styrene
The full atom model of PPV-b-PSt diblock polymer chain is as shown in Figure 4.
PPV inflexible polymer chain and PPV-b-PSt diblock polymer chain are introduced into MOFs nano pore respectively, and
It is right respectivelyMolecular dynamics simulation is carried out, two kinds of polymer chain is obtained and exists
Stable state as a result, as shown in Figure 5 in MOF.
It is 0.47 that the rigid chain segment PPV degree of orientation, which is calculated,The average orientation of middle rigidity PPV segment
Degree is 0.874,The degree of orientation of middle rigidity PPV segment is 0.972.By three groups of data it is known that
?Middle rigidity PPV segment is taken under the molecular force induction between MOF hole wall and polymer chain
To；Further, since the rotation of the singly-bound of soft segment,The degree of orientation of middle rigidity PPV segment by into
One step improves.
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (6)
1. a kind of method for improving the rigid chain segment degree of orientation in co-polymer, which is characterized in that the method is that had using metal
Machine frame MOF is directly adsorbed and is wrapped up hard and soft block copolymer chain come what is realized, includes rigid in hard and soft block copolymer chain
Property segment and soft segment, rigid chain segment cooperates flexible chain by the induction of the molecular force between MOF hole wall and each segment
The rotation of Duan Danjian is orientated；This method specifically includes following operating procedure:
1) hard and soft block copolymer chain is constructed；
2) MOF material is selected according to the characteristic of co-polymer chain, using solvent method volatility process or solvent structure MOF；
3) co-polymer chain made from step 1) is introduced directly into the orderly duct of MOF made from step 2), induced polymer
The orientation of rigid chain segment in chain.
2. a kind of method for improving the degree of orientation of rigid chain segment in co-polymer according to claim 1, which is characterized in that institute
The characteristic of the co-polymer chain of foundation includes the diameter of co-polymer chain when stating selection MOF material in step 2), molecular weight and
The multibody system of chain itself.
3. a kind of method for improving the degree of orientation of rigid chain segment in co-polymer according to claim 1, which is characterized in that institute
Stating the MOF that selects in step 2), not only duct is orderly, and the diameter adaptation of the pore size of MOF polymer chain together.
4. a kind of method for improving the degree of orientation of rigid chain segment in co-polymer according to claim 1, which is characterized in that institute
The construction method for stating Rod-coil copolymer chain in step 1) includes living polymerization, active anion/cation polymerization, group turn
Move polymerization and controllable free-radical polymerisation method.
5. a kind of method for improving the degree of orientation of rigid chain segment in co-polymer according to claim 1, which is characterized in that institute
Stating the method that co-polymer chain is introduced into the orderly duct MOF in step 3) includes that monomer is in situ in the nano pore of MOF
The method of polymerization, the copolymerzation with cross-linking of monomer and MOF frame and polymer chain is introduced directly into MOF nano pore method.
6. a kind of method for improving the degree of orientation of rigid chain segment in co-polymer according to claim 4, which is characterized in that institute
The construction method for stating Rod-coil copolymer chain in step 1) is living polymerization.
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| CN201811042766.0A CN109206631B (en) | 2018-09-07 | 2018-09-07 | Method for improving orientation degree of rigid chain segment in copolymer |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102652035A (en) * | 2009-12-15 | 2012-08-29 | 环球油品公司 | Metal organic framework polymer mixed matrix membranes |
| CN104001426A (en) * | 2014-05-29 | 2014-08-27 | 北京工业大学 | Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN107407621A (en) * | 2015-01-27 | 2017-11-28 | 国立研究开发法人物质材料研究机构 | Sensor with porous material or bulk material as receptive layers |
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2018
- 2018-09-07 CN CN201811042766.0A patent/CN109206631B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102652035A (en) * | 2009-12-15 | 2012-08-29 | 环球油品公司 | Metal organic framework polymer mixed matrix membranes |
| CN104001426A (en) * | 2014-05-29 | 2014-08-27 | 北京工业大学 | Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN107407621A (en) * | 2015-01-27 | 2017-11-28 | 国立研究开发法人物质材料研究机构 | Sensor with porous material or bulk material as receptive layers |
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