CN109851808A - Multi-metal oxygen cluster based supermolecular method for producing polymer - Google Patents
Multi-metal oxygen cluster based supermolecular method for producing polymer Download PDFInfo
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Abstract
The invention discloses a kind of multi-metal oxygen cluster based supermolecular method for producing polymer, the single technical problem of the multi-metal oxygen cluster based supermolecular polymers function for solving existing method preparation.Technical solution is to use the means of organic decoration by ligand groups 2 first, 2 ', 6 '; 2 " terpyridyl is connected to Anderson type multi-metal oxygen cluster both ends, the means modified again with electrostatic by coumarin group block it is surfactant modified act on aggregating into cumarin photodimerization by metal-ligand coordinate to the monomer around oxygen cluster, obtained is crosslinked supermolecule polymer.Coumarin group reversibly dimerization and dissociation under Compound eye, prepared supermolecule polymer has ion stimulating responsive and light stimulus responsiveness simultaneously, functional more abundant.
Description
Technical field
The present invention relates to a kind of multi-metal oxygen cluster based supermolecular method for producing polymer.
Background technique
" Journal of Materials Chemistry C, 2015,3 (30): 7936-7945 " discloses one to document 1
The preparation method of kind multi-metal oxygen cluster based supermolecular polymer, this method use organic means directly modified by 2,6-, bis- (1-
Pyrazolyl) pyridine groups modification is to Anderson type multi-metal oxygen cluster both ends, then passes through metal cation and 2, (the 1- pyrazoles of 6- bis-
Base) the metal-ligand coordinate supermolecule interaction between pyridine groups prepared supermolecule polymer, the structure of polymer
It is as follows:
The polymerization of metal cation supermolecule is added into monomer, when the metal cation in polymer is by other coordination abilities
After stronger ion seizes, supermolecule polymer dissociation.Therefore the multi-metal oxygen cluster based supermolecular polymer that this method is prepared
The polymerization and dissociation of supermolecule polymer can be controlled by ion.Although the supermolecule polymer has embodied ion stimulation
Responsiveness, but it is functional single, it is not able to satisfy increasingly complicated functional requirements.
Summary of the invention
Multi-metal oxygen cluster based supermolecular polymers function in order to overcome the shortcomings of existing method preparation is single, the present invention
A kind of multi-metal oxygen cluster based supermolecular method for producing polymer is provided.This method uses the means of organic decoration by ligand groups first
2,2 ', 6 ', 2 "-terpyridyls are connected to Anderson type multi-metal oxygen cluster both ends, then the means modified with electrostatic are by cumarin
The surfactant modified of group end capping arrives around oxygen cluster, and obtained monomer passes through metal-ligand coordinate effect and cumarin light
Dimerization aggregates into crosslinking supermolecule polymer.Coumarin group reversibly dimerization and dissociation under Compound eye, it is prepared
Supermolecule polymer there is ion stimulating responsive and light stimulus responsiveness simultaneously, it is functional more abundant.
A kind of the technical solution adopted by the present invention to solve the technical problems: multi-metal oxygen cluster based supermolecular polymer preparation
Method, its main feature is that the following steps are included:
Step 1: by C15N3H10C6H4OCH2CONHC(CH2OH)3, it is abbreviated as TPY-Tris, [N (C4H9)4]4[α-Mo8O26]
With Mn (CH3COO)3·2H2O is dissolved in anhydrous polar solvent, Mn (CH3COO)3·2H2O and [N (C4H9)4]4[α-Mo8O26]
Molar ratio is 1~2, TPY-Tris and [N (C4H9)4]4[α-Mo8O26] molar ratio be stirred to react 24 at 3~4,60~80 DEG C~
48 hours.By reaction solution heat filtering, filtrate is placed in ether saturated vapor, has blocky orange crystal to generate after 2~7 days, obtains
To MnMo6- TPY, chemical formula are [(C4H9)4N]3[MnMo6O18{(CH2O)3CNHCOCH2OC21H14N3}2].Respectively by MnMo6-
TPY is dissolved in acetonitrile solution, cumarin terminated surface activating agent (CH3)2N(CnH2n+1)(CH2)mC9H5O3Br, referred to as CS, are dissolved in
In chloroform/acetonitrile mixed solution, volume ratio 1:3.CS and MnMo6- TPY molar ratio is 3~10.By MnMo6- TPY solution is added dropwise
Into CS solution, there is light orange precipitating to generate.Filtration drying after stirring 2~6 hours, obtains product monomer CS-MnMo6- TPY,
Chemical formula is [(CH3)2N(CnH2n+1)(CH2)mC9H5O3]3[MnMo6O18{(CH2O)3CNHCOCH2OC21H14N3}2], wherein m <
19, n < 19.
Step 2: by metal salt and CS-MnMo6- TPY is dissolved in polar solvent N, N- diformazan with 1~2 molar ratio respectively
In yl acetamide, stirs 0.5~2 hour, obtain coordination supramolecule polymer.
Step 3: the coordination supramolecule polymer obtained with ultraviolet irradiation step two, light application time is 0.5~1.5 small
When, obtain stimuli-responsive multi-metal oxygen cluster based supermolecular polymer.
The metal salt is Fe (OTf)2Or Zn (OTf)2It is any.
The beneficial effects of the present invention are: this method uses the means of organic decoration by ligand groups 2,2 ', 6 ', 2 "-three first
Bipyridyl is connected to Anderson type multi-metal oxygen cluster both ends, then the surface for being blocked coumarin group with the means that electrostatic is modified
Around activating agent modification to oxygen cluster, obtained monomer is aggregated into and is crosslinked by metal-ligand coordinate effect and cumarin photodimerization
Supermolecule polymer.Coumarin group reversibly dimerization and dissociation, prepared supermolecule polymer under Compound eye
There is ion stimulating responsive and light stimulus responsiveness simultaneously, it is functional more abundant.
It elaborates with reference to the accompanying drawings and detailed description to the present invention.
Detailed description of the invention
Fig. 1 is monomer polymerization flow diagram in multi-metal oxygen cluster based supermolecular method for producing polymer of the present invention.
Fig. 2 is multi-metal oxygen cluster based supermolecular polymer monomer CS-MnMo prepared by embodiment of the present invention method 16-TPY
Nucleus magnetic hydrogen spectrum figure.
Fig. 3 is the stereoscan photograph of the coordination supramolecule polymer obtained after embodiment of the present invention method 1 is coordinated.
Fig. 4 is the Fourier transform infrared spectrogram of polymer before and after 1 ultraviolet lighting of embodiment of the present invention method.
Specific embodiment
Following embodiment referring to Fig.1-4.
Embodiment 1:
By 0.63g [N (C4H9)4]4[α-Mo8O26]、0.12g Mn(CH3COO)3·2H2O and 0.50g
C15N3H10C6H4OCH2CONHC(CH2OH)3, it is abbreviated as TPY-Tris and is dissolved in anhydrous DMAc, is stirred to react at 80 DEG C 24 hours.
By reaction solution heat filtering, filtrate is placed in ether saturated vapor, has blocky orange crystal to generate after 2 days, obtains MnMo6-
TPY.By 0.36g MnMo6- TPY is dissolved in acetonitrile solution, 0.84g cumarin terminated surface activating agent (CH3)2N(C12H25)
(CH2)12C9H5O3Br, referred to as CS are dissolved in chloroform/acetonitrile mixed solution, and chloroform and acetonitrile volume ratio are 1:3.By MnMo6-
TPY solution is added drop-wise in CS solution, has light orange precipitating to generate.Filtration drying after stirring 2 hours, obtains product monomer CS-
MnMo6-TPY.By 70mg CS-MnMo6- TPY and 7mg Fe (OTf)2It is dissolved in DMAc respectively, is mixed 0.5 hour, obtains
Coordination supramolecule polymer.Gained mixed liquor is irradiated 0.5 hour under 365nm length ultraviolet lamp, it is poly- to obtain crosslinking supermolecule
Close object.
Fig. 2 is multi-metal oxygen cluster based supermolecular polymer monomer CS-MnMo manufactured in the present embodiment6The nucleus magnetic hydrogen spectrum of-TPY
Figure.Label belongs to the hydrogen on terpyridine moieties for~18 signal peak in spectrogram, and 6~10 signal peak belongs to tonka-bean
Hydrogen on plain group, integral area ratio and chemical shift are consistent with theoretical value, and above data, which may indicate that in monomer, includes
Two kinds of active groups of terpyridyl and cumarin.
Fig. 3 is the stereoscan photograph for the coordination supramolecule polymer that the present embodiment coordination obtains after the completion.It can from figure
Can be clearly seen that many linear fibres, it was demonstrated that the formation of one-dimensional linear coordination supramolecule polymer.
Fig. 4 is the Fourier transform infrared spectrogram of polymer before and after the present embodiment ultraviolet lighting.A curve is ultraviolet lighting
Before, B curve is after ultraviolet lighting.Compared with A curve, 1724cm on B curve-1Place belongs to C=O oscillation intensity under free state
It is opposite to weaken, while 1701cm-1Place belongs to the opposite enhancing of vibration peak of C=O under dimerization state, this variation demonstrates tonka-bean
Plain group photodimerization occurs, that is, is crosslinked the generation of supermolecule polymer.
Embodiment 2:
By 0.63g [N (C4H9)4]4[α-Mo8O26]、0.12g Mn(CH3COO)3·2H2O and 0.50g
C15N3H10C6H4OCH2CONHC(CH2OH)3, it is abbreviated as TPY-Tris and is dissolved in anhydrous DMAc, is stirred to react at 70 DEG C 36 hours.
By reaction solution heat filtering, filtrate is placed in ether saturated vapor, has blocky orange crystal to generate after 5 days, obtains MnMo6-
TPY.By 0.36g MnMo6- TPY is dissolved in acetonitrile solution, 0.90g cumarin terminated surface activating agent (CH3)2N(C12H25)
(CH2)16C9H5O3Br, referred to as CS are dissolved in chloroform/acetonitrile mixed solution, and chloroform and acetonitrile volume ratio are 1:3.By MnMo6-
TPY solution is added drop-wise in CS solution, has light orange precipitating to generate.Filtration drying after stirring 4 hours, obtains product monomer CS-
MnMo6-TPY.By 72mg CS-MnMo6- TPY and 7mg Zn (OTf)2It is dissolved in DMAc respectively, is mixed 1 hour, is matched
Position supermolecule polymer.Gained mixed liquor is irradiated 1 hour under 365nm length ultraviolet lamp, obtains crosslinking supermolecule polymer.
Embodiment 3:
By 0.63g [N (C4H9)4]4[α-Mo8O26]、0.12g Mn(CH3COO)3·2H2O and 0.50g
C15N3H10C6H4OCH2CONHC(CH2OH)3, it is abbreviated as TPY-Tris and is dissolved in anhydrous DMAc, is stirred to react at 60 DEG C 48 hours.
By reaction solution heat filtering, filtrate is placed in ether saturated vapor, has blocky orange crystal to generate after 7 days, obtains MnMo6-
TPY.By 0.70g MnMo6- TPY is dissolved in acetonitrile solution, 1.70g cumarin terminated surface activating agent (CH3)2N(C18H37)
(CH2)12C9H5O3Br, referred to as CS are dissolved in chloroform/acetonitrile mixed solution, and chloroform and acetonitrile volume ratio are 1:3.By MnMo6-
TPY solution is added drop-wise in CS solution, has light orange precipitating to generate.Filtration drying after stirring 6 hours, obtains product monomer CS-
MnMo6-TPY.By 70mg CS-MnMo6- TPY and 9mg Fe (OTf)2It is dissolved in DMAc respectively, is mixed 2 hours, is matched
Position supermolecule polymer.Gained mixed liquor is irradiated 1.5 hours under 365nm length ultraviolet lamp, obtains crosslinking supermolecule polymerization
Object.
Claims (2)
1. a kind of multi-metal oxygen cluster based supermolecular method for producing polymer, it is characterised in that the following steps are included:
Step 1: by C15N3H10C6H4OCH2CONHC(CH2OH)3, it is abbreviated as TPY-Tris, [N (C4H9)4]4[α-Mo8O26] and Mn
(CH3COO)3·2H2O is dissolved in anhydrous polar solvent, Mn (CH3COO)3·2H2O and [N (C4H9)4]4[α-Mo8O26] mole
Than for 1~2, TPY-Tris and [N (C4H9)4]4[α-Mo8O26] molar ratio is that be stirred to react 24~48 small at 3~4,60~80 DEG C
When；By reaction solution heat filtering, filtrate is placed in ether saturated vapor, has blocky orange crystal to generate after 2~7 days, obtains
MnMo6- TPY, chemical formula are [(C4H9)4N]3[MnMo6O18{(CH2O)3CNHCOCH2OC21H14N3}2]；Respectively by MnMo6-TPY
It is dissolved in acetonitrile solution, cumarin terminated surface activating agent (CH3)2N(CnH2n+1)(CH2)mC9H5O3Br, referred to as CS, are dissolved in chlorine
In imitative/acetonitrile mixed solution, volume ratio 1:3；CS and MnMo6- TPY molar ratio is 3~10；By MnMo6- TPY solution is added drop-wise to
In CS solution, there is light orange precipitating to generate；Filtration drying after stirring 2~6 hours, obtains product monomer CS-MnMo6- TPY changes
Formula is [(CH3)2N(CnH2n+1)(CH2)mC9H5O3]3[MnMo6O18{(CH2O)3CNHCOCH2OC21H14N3}2], wherein m < 19,
n<19；
Step 2: by metal salt and CS-MnMo6- TPY is dissolved in polar solvent N, N- dimethylacetamide with 1~2 molar ratio respectively
In amine, stirs 0.5~2 hour, obtain coordination supramolecule polymer；
Step 3: the coordination supramolecule polymer obtained with ultraviolet irradiation step two, light application time is 0.5~1.5 hour, is obtained
To stimuli-responsive multi-metal oxygen cluster based supermolecular polymer.
2. multi-metal oxygen cluster based supermolecular method for producing polymer according to claim 1, it is characterised in that: the metal
Salt is Fe (OTf)2Or Zn (OTf)2It is any.
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| CN110387047A (en) * | 2019-08-11 | 2019-10-29 | 兰州大学 | Polyacid base star supermolecule polymer, preparation method and application |
| CN111450890A (en) * | 2020-04-09 | 2020-07-28 | 通化师范学院 | Mixed isopolymolybdate organic-inorganic hybrid material and preparation method and application thereof |
| CN113174055A (en) * | 2021-04-27 | 2021-07-27 | 吉林大学 | Porous ion super-molecular framework material, preparation method and application |
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| CN111450890A (en) * | 2020-04-09 | 2020-07-28 | 通化师范学院 | Mixed isopolymolybdate organic-inorganic hybrid material and preparation method and application thereof |
| CN113174055A (en) * | 2021-04-27 | 2021-07-27 | 吉林大学 | Porous ion super-molecular framework material, preparation method and application |
| CN113174055B (en) * | 2021-04-27 | 2023-08-18 | 吉林大学 | Porous ion supermolecular framework material, preparation method and application |
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