CN103923282A - Copolymers containing polyoxometallate-silsesquioxane, and preparation method thereof - Google Patents
Copolymers containing polyoxometallate-silsesquioxane, and preparation method thereof Download PDFInfo
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Abstract
A norbornene functionalized polyoxometallate monomer and norbornene derivated silsesquioxane are polymerized by innovatively adopting a ring-opening metathesis polymerization (ROMP) method in order to obtain novel segmented copolymers and random copolymers containing polyoxometallate-silsesquioxane, and the controllable molecular weight and the narrow molecular weight distribution of the copolymers are measured. The method has the advantages of simplicity, fastness, high efficiency, controllability, realization of high yield obtaining of the target polymers within several hours by carrying out a polymerization reaction in an open system, simple post-treatment, accurate control of the molecular weight, and easy industrialization. The polymers reserve the excellent performances of the inorganic substance polyoxometallate and silsesquioxane, and the defects of bad dissolvability and difficult processing of polyoxometallate are improved, so the polymers have potential application values in the catalysis field, the material field and the medicine field.
Description
Technical field
The present invention relates to polymer chemistry, organic and inorganic and materials chemistry, particularly a kind of standby polymerization technique that contains polyoxometallate and silsesquioxane hybridized polymer of ring-opening metathesis polymerization legal system that adopts, utilize this polymerization process can be by the silsesquioxane trisome polymerization of the polyoxometallate of norbornylene derivatize and norbornylene derivatize, obtain novel segmented copolymer and random copolymers containing polyoxometallate-silsesquioxane.
Background technology
Along with the continuous progress of science and technology, the polymer materials of single performance has not reached the requirements such as desired cost performance is high, solvability good, easy processing far away.Multipolymer--two or more different monomer obtains through polyreaction--is considered to a kind of method addressing this problem for a long time.Scientist provides unprecedented opportunities in synthetic chemistry and the obtained huge progress of polymer chemistry for the material that preparation has specific function in recent years.
To be a class coordinate the class forming to have the unit molecule duster compound of definite structure by central atoms such as the early transition metal atoms such as molybdenum (Mo), tungsten (W), vanadium (V) and phosphorus (P), silicon (Si) to polyoxometallate (polyoxometalates, be called for short POMs).Because it has abundant chemical composition, various topological framework, special redox potential, and show the incomparable excellent properties of other compounds at aspects such as catalysis, medicine and optical, electrical, magnetic functional materialss, thereby get more and more people's extensive concerning, and obtain deep research and application.But because the constructional feature and the inherent nature that are subject to itself restrict, polyoxometallate has the defects such as poor stability, difficult consistency and non-workability as material, thereby has limited its development and application in practice.
Silsesquioxane (being called for short POSS) is that a class formation skeleton symbol is (RSiO
15)
nthe silicone compounds of hybrid inorganic-organic, the cage modle inorganic framework that its core is made up of Si-O key.POSS not only comprises the special rigid backbone of polyhedral silica nanostructure, there is again excellent performance, as low electrolysis constant, high heat resistance, high mechanical strength, excellent optical property etc., therefore simultaneously, become the focus of material circle research in recent years, and be expected to for multiple Application Areas.
Polymkeric substance is contemporary the most widely used organic synthesis material, the many merits such as there is easy processing, easily modification, solvability is good, stability is high, therefore adopt organic polymer to modify many metal-salts hydrochlorate, expect that the material obtaining can retain the property of polyoxometallate, also can improve it simultaneously and be difficult for the defects such as processing.
Because the solvability of polyoxometallate and silsesquioxane differs greatly, the hybrid inorganic-organic polymkeric substance research that contains POMs and POSS when people connect for covalent linkage is very few.Ring-opening metathesis polymerization (ROMP) thus be that cyclic olefin open loop under catalysis is carried out chainpropagation and formed the polymerization process of polymer materials, since this efficient living polymerisation process of self-discovery, it has been widely used in preparing various polymer materialss.But, adopt ring-opening metathesis polymerization legal system to have not yet to see so far report for the work of the hybrid inorganic-organic polymkeric substance of polyoxometallate-silsesquioxane.
Summary of the invention
Object of the present invention: provide a kind of simple and efficient, efficient controlled polymerization process to prepare the hybrid inorganic-organic polymkeric substance based on polyoxometallate and silsesquioxane, to improve polyoxometallate in the defect aspect material and to provide a class novel functional high molecule material.
Technical scheme of the present invention: the diblock copolymer (III) of silsesquioxane (II) and the preparation of random copolymers (IV) that the polyoxometallic acid salt monomer (I) based on norbornene monomer functionalization that a kind of norbornylene is modified and norbornylene are modified.
The present invention is that norbornene derivative monomer and the general structure of general structure I, II is the compound of polyoxometallate-silsesquioxane hybridized polymer of III, IV:
Wherein, n=1～19; X>=1; Y>=1; Z>=0; A=NH, O; R=ethyl, i-butyl, i-octyl, cyclohexyl.phenyl; POM=[(n-Bu)
4n]
5hP
2w
15o
59, [(n-Bu)
4n]
6p
2w
15o
59.
The synthetic route of segmented copolymer III that the present invention is based on polyoxometallate is as follows:
Wherein, Grubbs ' III=[(H
2iMes) (py)
2(Cl)
2ru=CHPh] (py=pyridine); [(H
2iMes) (3-Br-py)
2(Cl)
2ru=CHPh] (3-Br-py=3-bromopyridine);
The synthetic route of polyoxometallate random copolymers IV of the present invention is as follows:
Wherein, Grubbs ' III=[(H
2iMes) (py)
2(Cl)
2ru=CHPh] (py=pyridine); [(H
2iMes) (3-Br-py)
2(Cl)
2ru=CHPh] (3-Br-py=3-bromopyridine);
Concrete synthetic route of the present invention describes in detail as follows:
(1) N-laurostearic acid-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
11-COOH) synthetic
Mol ratio is cis-5-norbornylene-outer-2 of 1: 1.1, and 3-dicarboxylic anhydride and 12-amido-laurostearic acid reflux 6 hours in glacial acetic acid, and Rotary Evaporators is removed acetic acid, and ethyl acetate is dissolved again, and distilled water wash is dried, and precipitation, obtains target compound.(2) N-12-[trihydroxymethylaminomethane base]-lauramide-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
12-tris) synthetic
Mol ratio is N-laurostearic acid-cis-5-norbornylene-outer-2 of 1: 1.2: 1.5,3-dicarboximide (Norb-C
11-COOH); Tutofusin tris (tris); 2-oxyethyl group-1-ethoxy carbonic acyl radical-1; 2-dihydroquinoline (EEDQ) is dissolved in ethanol; reflux 12 hours; precipitation, with 20: 1 (v/v) methylene dichloride: the eluent of methyl alcohol carries out column chromatography separation, can obtain the target product of white solid.
(3) the polyoxometallate hybrid (Norb-C of norborneol alkylene
12-POM) synthetic
Mol ratio is the N-12-[trihydroxymethylaminomethane base of 1.1: 1]-lauramide-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
12-tris) and polyoxometallate TBA
6h
3p
2w
15v
3o
62(POM) be dissolved in DMF, stir and be warming up to 85 DEG C, react 7 days.Concentrated, ether sedimentation, dry, obtain yellow solid.
(4) N-silsesquioxane-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-POSS) synthetic
Mol ratio is cis-5-norbornylene-outer-2 of 1.0: 1.1,3-dicarboxylic anhydride and POSS-NH
2be dissolved in toluene, point water, refluxes 24 hours, and Rotary Evaporators is removed toluene, with 1: 1 (v/v) sherwood oil: the eluent of methylene dichloride carries out column chromatography separation, can obtain target product.
(5) polyoxometallate-silsesquioxane hybridized segmented copolymer Poly (POM)
y-b-Poly (POSS)
xsynthetic
Polyoxometallic acid salt monomer (the Norb-C of norborneol alkylene
12-POM) be dissolved in DMF solution, add a certain amount of Grubbs three generations catalyzer, room temperature reaction 2 hours, then add a certain amount of another kind of monomer N-silsesquioxane-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
3-POSS) methylene dichloride (DCM) solution, react 1 hour, add ethyl vinyl ether termination reaction, methanol extraction, obtains target segmented copolymer.
(6) polyoxometallate-silsesquioxane hydridization random copolymers Poly (POM)
y-r-Poly (POSS)
x+zsynthetic
Polyoxometallate hybrid (the Norb-C of norborneol alkylene
12-POM) and N-silsesquioxane-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
3-POSS) be dissolved in DMF and DCM mixing solutions, add a certain amount of Grubbs three generations catalyzer, room temperature reaction 2 hours, adds ethyl vinyl ether termination reaction, and methanol extraction obtains target segmented copolymer.
Advantage of the present invention is: the present invention is by modifying norbornene derivative on polyoxometallate and silsesquioxane with covalent linkage, prepare the organic-inorganic hybrid monomer of the norborneol alkylene that simultaneously contains polyoxometallate and silsesquioxane, adopted first ring-opening metathesis polymerization (ROMP) method directly obtained monomer to be carried out to block copolymerization and random copolymerization obtains linear polymeric polymkeric substance.The method synthesis technique is simple, mild condition, easy handling, reaction are easily controlled, product purity is high, be convenient to realize suitability for industrialized production and apply.
Brief description of the drawings
Fig. 1 adopts molecule described in embodiment 4
1h NMR spectrogram.
Fig. 2 adopts molecule described in embodiment 4
13c NMR spectrogram.
Fig. 3 adopts polymkeric substance described in embodiment 5
1h NMR spectrogram.
Fig. 4 adopts polymkeric substance described in embodiment 5
31p NMR spectrogram.
Fig. 5 adopts polymkeric substance described in embodiment 6
1h NMR spectrogram.
Fig. 6 adopts polymkeric substance described in embodiment 6
31p NMR spectrogram.
Fig. 7 is the GPC spectrogram that adopts block polymer described in embodiment 5.
Fig. 8 is the GPC spectrogram that adopts unregulated polymer described in embodiment 6.
Embodiment
Embodiment 1:N-laurostearic acid-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
11-COOH) synthetic
In 25mL single necked round bottom flask, add 164.1mg (1mmol) cis-5-norbornylene-outer-2,3-dicarboxylic anhydride, 237.0mg (1.1mmol) 12-amido-laurostearic acid, 10mL glacial acetic acid, backflow 6h, stopped reaction, revolves and steams desolventizing.Dissolve by 20mL ethyl acetate again, use respectively distilled water and saturated common salt water washing three times, anhydrous sodium sulfate drying, filters, and is spin-dried for, and re-crystallizing in ethyl acetate, obtains white solid 343mg (0.95mmol), yield 95%.
Embodiment 2:N-12-[trihydroxymethylaminomethane base]-lauramide-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-C
12-tris) synthetic
In 100mL single necked round bottom flask, by 1.09g (3.02mmol) N-laurostearic acid-cis-5-norbornylene-outer-2,3-dicarboximide, 0.44g (3.63mmol) Tutofusin tris, 1.12g (4.53mmol) is dissolved in 50mL dehydrated alcohol, backflow 12h.Be spin-dried for, methylene dichloride dissolves, filter to remove excessive Tutofusin tris, taking 20: 1 (v/v) methylene dichloride: methyl alcohol is as eluent, obtain target compound 998mg (2.15mmol), yield 71% by silica gel (100～200 order) column chromatography for separation.
Embodiment 3: the polyoxometallate hybrid (Norb-C of norborneol alkylene
12-POM) synthetic
In 50mL single necked round bottom flask, add 46mg (0.098mmol) N-12-[trihydroxymethylaminomethane base]-lauramide-cis-5-norbornylene-outer-2,3-dicarboximide, 484mg (0.089mmol) [(n-Bu)
4n]
6h
3p
2w
15v
3o
62, 20mLN, dinethylformamide, reacts 7 days at 85 DEG C.Concentrated, ether sedimentation, centrifugal, obtain yellow solid 510mg, yield 98%.
Embodiment 4:N-silsesquioxane-cis-5-norbornylene-outer-2,3-dicarboximide (Norb-POSS) synthetic
Be equipped with in the 100mL twoport round-bottomed flask of water trap, add 164mg (1.0mmol) cis-5-norbornylene-outer-2,3-dicarboxylic anhydride, 962mg (1.1mmol) 3-amino-1-silsesquioxane, 50mL toluene, backflow 24h, stopped reaction, is spin-dried for.Taking 1: 1 (v/v) sherwood oil: methylene dichloride, as eluent, obtains 842mg (0.83mmol) white solid target compound, yield 83% by silica gel (100～200 order) column chromatography for separation.
Embodiment 5: the segmented copolymer Poly (POM) of polyoxometallate-silsesquioxane
20-b-Poly (POSS)
20synthetic
Under the system of opening wide, in the 2mL bottle with stopper, add 200.7mg (0.034mmol) Norb-C
12-POM, 0.38mL DMF, 1.7mg (0.0034mmol) Grubbs III catalyzer, room temperature reaction 2h, then add 0.34mL0.1mmol/mLDMF: DCM=1: 1 Norb-POSS solution, continues reaction 1h.Add ethyl vinyl ether stopped reaction, stir 10min.In methyl alcohol, precipitate, obtain yellow solid 228.4mg, yield 97%,
Embodiment 6: random copolymers Poly (POM) 20-r-Poly (POSS) of polyoxometallate-silsesquioxane
20synthetic
Under the system of opening wide, in the 2mL bottle with stopper, add 158.0mg (0.027mmol) Norb-C
12-POM, 27.6mg (0.027mmol) Norb-POSS, 1.2mg (0.0014mmol) Grubbs III catalyzer, the mixing solutions of 0.2mLDMF:DCM, room temperature reaction 2h.Add ethyl vinyl ether stopped reaction, stir 10min.In ether, precipitate, obtain yellow solid 177.5mg, yield 96%,
Claims (10)
1. the multipolymer (III) of the polyoxometallate of a covalent linkage connection, structural formula is as follows:
。
2. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 1 connects, is characterized in that n=1～19, x >=1, y >=1.
3. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 1 and 2 connects, is characterized in that A=NH, O.
4. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 1 and 2 connects, is characterized in that R=ethyl, i-butyl, i-octyl, cyclohexyl, phenyl.
5. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 3 connects, is characterized in that R=ethyl, i-butyl, i-octyl, cyclohexyl.phenyl.
6. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 1 and 2 connects, is characterized in that POM=(Bu
4n)
5hP
2w
15o
59, (Bu
4n)
6p
2w
15o
59.
7. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 3 connects, is characterized in that POM=(Bu
4n)
5hP
2w
15o
59, (Bu
4n)
6p
2w
15o
59.
8. the multipolymer (III) of polyoxometallate-silsesquioxane that a kind of covalent linkage according to claim 4 connects, is characterized in that POM=(Bu
4n)
5hP
2w
15o
59, (Bu
4n)
6p
2w
15o
59.
9. the preparation method of oxometallate-silsesquioxane polymer III as claimed in claim 1, it is characterized in that it is that monomer by general structure I and II is under Grubbs'III catalyst action, prepare by ring-opening metathesis polymerization method (ROMP), its preparation method is as follows:
。
10. the preparation method of oxometallate-silsesquioxane polymer polymkeric substance III according to claim 9, it is characterized in that: under sealing or unlimited system, the polyoxometallate monomer I of norborneol alkylene is dissolved in DMF solution, add a certain amount of catalyzer, after room temperature reaction 2h, then add another kind of monomer Norb-POSS, continue reaction 1h, add ethyl vinyl ether termination reaction, methanol extraction, obtains subject polymer.
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Cited By (6)
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| CN108997563A (en) * | 2018-08-09 | 2018-12-14 | 上海应用技术大学 | A kind of method of ROMP polymerization preparation based polyalcohol containing POSS |
| KR20190031190A (en) * | 2017-09-15 | 2019-03-25 | 광주과학기술원 | Polymeric polymeric materials containing polyhedral oligomeric silsesquioxane (POSS) |
| EP3386599A4 (en) * | 2015-12-10 | 2019-05-01 | Emory University | Polymers of polyoxometalates and hydroxy-terminated monomer units and uses in degrading noxious agents |
| KR20200034054A (en) * | 2018-09-20 | 2020-03-31 | 광주과학기술원 | Polymeric polymeric materials containing polyhedral oligomeric silsesquioxane (POSS) |
| CN112142979A (en) * | 2020-09-20 | 2020-12-29 | 南开大学 | Pyramid type polyoxometallate-cage type silsesquioxane hybrid molecule and preparation method and application thereof |
| WO2022267271A1 (en) * | 2021-06-24 | 2022-12-29 | 华南理工大学 | Hybrid polymer, preparation method therefor and use thereof |
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Cited By (9)
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| EP3386599A4 (en) * | 2015-12-10 | 2019-05-01 | Emory University | Polymers of polyoxometalates and hydroxy-terminated monomer units and uses in degrading noxious agents |
| US11174352B2 (en) | 2015-12-10 | 2021-11-16 | Emory University | Polymers of polyoxometalates and hydroxy-terminated monomer units and uses in degrading noxious agents |
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| CN112142979A (en) * | 2020-09-20 | 2020-12-29 | 南开大学 | Pyramid type polyoxometallate-cage type silsesquioxane hybrid molecule and preparation method and application thereof |
| WO2022267271A1 (en) * | 2021-06-24 | 2022-12-29 | 华南理工大学 | Hybrid polymer, preparation method therefor and use thereof |
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