CN103254340A - Novel polyoxometallate polymer and preparation method thereof - Google Patents
Novel polyoxometallate polymer and preparation method thereof Download PDFInfo
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- CN103254340A CN103254340A CN2013101927848A CN201310192784A CN103254340A CN 103254340 A CN103254340 A CN 103254340A CN 2013101927848 A CN2013101927848 A CN 2013101927848A CN 201310192784 A CN201310192784 A CN 201310192784A CN 103254340 A CN103254340 A CN 103254340A
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Abstract
The invention innovatively relates to a novel polyoxometallate polymer obtained by directly polymerizing norbornylene functional polyoxometallate monomers by adopting an ROMP (Ring Opening Metathesis Polymerization) method, and measures the molecular weight distribution of the novel polyoxometallate polymer. The method disclosed by the invention is simple, convenient, fast, efficient and controllable, can obtain the target polymers at high yield within several hours through polymerization reaction in an open system, is simple in post processing, can be used for accurately controlling the molecular weight and easy to realize the industrialization; and the novel polyoxometallate polymer retains the excellent property of inorganic polyoxometallate and has potential application value on the aspects of catalysis, materials, medicines, and the like.
Description
Technical field
The present invention relates to polymer chemistry, organic and inorganic and materials chemistry, a kind of polymerization technique that adopts the ring-opening metathesis polymerization legal system to be equipped with the polyoxometallate polymkeric substance particularly, utilize this polymerization process the polyoxometallate direct polymerization of norbornene derivative functionalization can be obtained novel polyoxometallate polymkeric substance.
Background technology
Polyoxometallate (polyoxometallate is called for short POM) is that a class cooperates a class that forms to have the unit molecule duster compound of definite structure by molybdenum (Mo), tungsten (W), vanadium early transition metals such as (V) atom with phosphorus (P), silicon central atoms such as (Si).Because it has abundant chemical ingredients, various topological framework, special redox potential, and show the incomparable excellent properties of other compounds at aspects such as catalysis, medicine and light, electricity, magnetic functional materialss, thereby get more and more people's extensive concerning, and obtain deep research and application.But owing to restricted by the constructional feature of itself and inherent nature, polyoxometallate has defectives such as relatively poor stability, difficult consistency and non-workability as material, thereby has limited its development and application in practice.
Polymkeric substance is contemporary the most widely used organic synthesis material, have easy processing, easily modification, good, the high numerous advantages of stability of solvability, therefore adopt organic polymer that many metal-salts hydrochlorate is modified, expect that resulting material can keep the property of polyoxometallate, also can improve simultaneously it and be difficult for defectives such as processing, this mentality of designing has certain feasibility in theory, but rarely has report about the result of study of this respect.
Ring-opening metathesis polymerization (ROMP) thus be that the polymerization process that chainpropagation forms polymer materials is carried out in cyclic olefin open loop under catalysis.Since finding this living polymerisation process efficiently, it has been widely used in preparing various polymer materialss.But the work of adopting the ring-opening metathesis polymerization legal system to be equipped with the polyoxometallate polymkeric substance does not appear in the newspapers so far yet.
Summary of the invention
Purpose of the present invention: provide a kind of simple and efficient, efficient controlled polymerization process to prepare the polyoxometallate base polymer, to improve polyoxometallate in the defective aspect the material.
Technical scheme of the present invention: the polyoxometallic acid salt monomer (I) that a kind of norbornylene is modified and the preparation of polymkeric substance (II).
The present invention is the compound of the polyoxometallate polymkeric substance of the polyoxometallic acid salt monomer of general structure I and general structure II:
Wherein, n=1～19; M 〉=2; X=NH, O; POM=[(n-Bu)
4N]
5HP
2W
15O
59, [(n-Bu)
4N]
6P
2W
15O
59
The synthetic route of polyoxometallate monomer I 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 is described 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: 1.1,3-dicarboxylic anhydride and 12-amido-laurostearic acid, and reflux in toluene 20 hours, Rotary Evaporators was removed toluene, wash, drying, 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 the ethanol, refluxes precipitation 12 hours; with 20: 1 (v/v) methylene dichloride: the eluent of methyl alcohol carries out column chromatography to be separated, and can obtain target product.
(3) the polyoxometallate hybrid (norb-C of norborneol alkylene
12-POM) synthetic
Mol ratio is 1.1: 1 N-12-[trihydroxymethylaminomethane base]-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 N, in the dinethylformamide, stir and be warming up to 85 ℃, reacted 7 days.Concentrate, ether sedimentation, drying obtains yellow solid.
(4) the polyoxometallate polymkeric substance of norborneol alkylene is synthetic
Polyoxometallate hybrid (the norb-C of norborneol alkylene
12-POM) be dissolved in the DMF solution, add a certain amount of Grubbs three generations catalyzer, room temperature reaction 2h adds the ethyl vinyl ether termination reaction, and ether sedimentation gets subject polymer.
Advantage of the present invention is: the present invention is by modifying norbornene derivative on the polyoxometallate with covalent linkage, the organic-inorganic hybrid monomer that has prepared the norborneol alkylene adopts ring-opening metathesis polymerization (ROMP) method directly resulting hybrid monomers to be carried out polymerization first and obtains the chain high molecular polymer.This method synthesis technique is simple, mild condition, easy handling, reaction are controlled easily, the product purity height, be convenient to realize suitability for industrialized production and apply.
Description of drawings
Fig. 1 adopts molecule described in the embodiment 1
1H NMR spectrogram.
Fig. 2 adopts molecule described in the embodiment 1
13C NMR spectrogram.
Fig. 3 adopts molecule described in the embodiment 2
1H NMR spectrogram.
Fig. 4 adopts molecule described in the embodiment 2
13C NMR spectrogram.
Fig. 5 adopts molecule described in the embodiment 3
1H NMR spectrogram.
Fig. 6 adopts molecule described in the embodiment 3
13C NMR spectrogram.
Fig. 7 adopts molecule described in the embodiment 3
31P NMR spectrogram.
Fig. 8 adopts molecule described in the embodiment 4
1H NMR spectrogram.
Fig. 9 adopts molecule described in the embodiment 4
31P NMR spectrogram.
Figure 10 is for adopting the GPC spectrogram of polymkeric substance described in embodiment 3 described molecules and the embodiment 4.
Embodiment
Embodiment 1:N-laurostearic acid-cis-5-norbornylene-outer-2,3-dicarboximide (norb-C
11-COOH) synthetic
In the 25ml single necked round bottom flask of water trap is housed, add 164mg (1mmol) cis-5-norbornylene-outer-2,3-dicarboxylic anhydride, 237mg (1.1mmol) 12-amido-laurostearic acid, 10ml toluene, backflow 20h, stopped reaction.Use the 20ml acetic acid ethyl dissolution, use distilled water and saturated common salt water washing three times respectively, anhydrous sodium sulfate drying filters, and is spin-dried for, and re-crystallizing in ethyl acetate gets white solid 343mg (0.95mmol), yield 95%.
Embodiment 2:N-12-[trihydroxymethylaminomethane base]-lauramide-cis-5-norbornylene-outer-2,3-dicarboximide (norb-C12-tris) synthetic
In the 100ml single necked round bottom flask, with 1.09g (3.02mmol) N-laurostearic acid-cis-5-norbornylene-outer-2,3-dicarboximide, 0.44g (3.63mmol) Tutofusin tris, 1.12g (4.53mmol) be dissolved in the 50ml dehydrated alcohol backflow 12h.Be spin-dried for, methylene dichloride dissolving filters to remove excessive Tutofusin tris, and with 20: 1 (v/v) methylene dichloride: methyl alcohol was eluent, obtains 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 the 50ml single necked round bottom flask, add 46mg (0.098mmol) N-12-[trihydroxymethylaminomethane base]-lauramide-cis-5-norbornylene-outer-2, the 3-dicarboximide, 484mg (0.089mmol) is [(n-Bu)
4N]
6H
3P
2W
15V
3O
62, 20ml N, dinethylformamide, 85 ℃ were reacted 7 days down.Concentrate, ether sedimentation, centrifugal, obtain yellow solid 510mg, yield 98%.
Embodiment 4: the polyoxometallate polymkeric substance (p-10-POM) of norborneol alkylene synthetic
Under the system of opening wide, in the 2ml bottle that has stopper, add 88mg (0.015mmol) norb-C
12-POM, 1ml DMF, 1.33mg (0.0015mmol) Grubbs III catalyzer, room temperature reaction 2h.Add the ethyl vinyl ether stopped reaction, precipitate in the ether, get yellow powder 86mg, yield 98%,
Synthesized the polyoxometallate polymkeric substance of different polymerization degree according to embodiment 4 described methods, concrete GPC data are as shown in the table.
Claims (7)
1. the polyoxometallate polymkeric substance (II) of a norbornylene functionalization is characterized in that it is that monomer by general structure I prepares by the ring-opening metathesis polymerization method, and its preparation method is as shown below:
2. polyoxometallic acid salt monomer according to claim 1 (I) and polymkeric substance (II) is characterized in that n=1～19.
3. according to polyoxometallic acid salt monomer (I) and the polymkeric substance (II) of claim 1 or 2, it is characterized in that X=NH, O.
4. according to polyoxometallic acid salt monomer (I) and the polymkeric substance (II) of claim 1 or 2, it is characterized in that POM=(Bu
4N)
5HP
2W
15O
59, (Bu
4N)
6P
2W
15O
59
5. according to polyoxometallic acid salt monomer (I) and the polymkeric substance (II) of claim 3, it is characterized in that POM=(Bu
4N)
5HP
2W
15O
59, (Bu
4N)
6P
2W
15O
59
6. oxometallate polymkeric substance according to claim 1 (II), its preparation method is as follows:
Under sealing or the unlimited system, the polyoxometallic acid salt monomer (I) of norborneol alkylene is dissolved in the DMF solution, adds a certain amount of catalyzer, and room temperature reaction 2h adds the ethyl vinyl ether termination reaction, and ether sedimentation gets subject polymer.
7. oxometallate polymkeric substance according to claim 6 (II), the molecular formula of the catalyzer that adopts during its preparation is [(H
2IMes) (py)
2(Cl)
2Ru=CHPh] (py=pyridine; ) or [(H
2IMes) (3-Br-py)
2(Cl)
2Ru=CHPh] (3-Br-py=3-bromopyridine).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923260A (en) * | 2014-01-08 | 2014-07-16 | 南开大学 | Ring-opening metathesis polymerization method for preparing polyoxometallate based copolymers |
| CN103923282A (en) * | 2014-01-08 | 2014-07-16 | 南开大学 | Copolymers containing polyoxometallate-silsesquioxane, and preparation method thereof |
| CN103992357A (en) * | 2014-06-04 | 2014-08-20 | 宁波高新区夏远科技有限公司 | Macromolecular crosslinking agent containing polyoxometalates and preparation method and application thereof |
| CN104003926A (en) * | 2014-05-30 | 2014-08-27 | 天津大学 | Alkyl ammonium salt-based side chain type magnetic monomer and polymer as well as preparation method and application thereof |
| CN105646851A (en) * | 2014-05-30 | 2016-06-08 | 天津大学 | Magnetic polymer and preparing method thereof |
| CN110229336A (en) * | 2019-06-14 | 2019-09-13 | 南开大学 | Two (polyoxometallates)-organic chain-cage-type silsesquioxane hydridization cluster compound and preparation method |
| CN112675926A (en) * | 2020-10-10 | 2021-04-20 | 南开大学 | Polyacid hybrid polymer with proton type and alkali metal ion type polymerization degree of 100 and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0755938A1 (en) * | 1995-07-28 | 1997-01-29 | The B.F. Goodrich Company | Ligated polyoxometalates and method for their synthesis |
| CN102304152A (en) * | 2011-04-20 | 2012-01-04 | 南开大学 | Molybdenum-containing polyoxometalate and adamantane hybrid compound and preparation method thereof |
-
2013
- 2013-05-23 CN CN201310192784.8A patent/CN103254340B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0755938A1 (en) * | 1995-07-28 | 1997-01-29 | The B.F. Goodrich Company | Ligated polyoxometalates and method for their synthesis |
| CN102304152A (en) * | 2011-04-20 | 2012-01-04 | 南开大学 | Molybdenum-containing polyoxometalate and adamantane hybrid compound and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923260A (en) * | 2014-01-08 | 2014-07-16 | 南开大学 | Ring-opening metathesis polymerization method for preparing polyoxometallate based copolymers |
| CN103923282A (en) * | 2014-01-08 | 2014-07-16 | 南开大学 | Copolymers containing polyoxometallate-silsesquioxane, and preparation method thereof |
| CN103923282B (en) * | 2014-01-08 | 2018-04-06 | 南开大学 | The copolymer and preparation method of the silsesquioxane containing polyoxometallate |
| CN104003926A (en) * | 2014-05-30 | 2014-08-27 | 天津大学 | Alkyl ammonium salt-based side chain type magnetic monomer and polymer as well as preparation method and application thereof |
| CN105646851A (en) * | 2014-05-30 | 2016-06-08 | 天津大学 | Magnetic polymer and preparing method thereof |
| CN104003926B (en) * | 2014-05-30 | 2016-06-15 | 天津大学 | Based on the side chain type magnetic monomer of alkylammonium salt, polymer and its preparation method and application |
| CN103992357A (en) * | 2014-06-04 | 2014-08-20 | 宁波高新区夏远科技有限公司 | Macromolecular crosslinking agent containing polyoxometalates and preparation method and application thereof |
| CN110229336A (en) * | 2019-06-14 | 2019-09-13 | 南开大学 | Two (polyoxometallates)-organic chain-cage-type silsesquioxane hydridization cluster compound and preparation method |
| CN112675926A (en) * | 2020-10-10 | 2021-04-20 | 南开大学 | Polyacid hybrid polymer with proton type and alkali metal ion type polymerization degree of 100 and preparation method thereof |
| CN112675926B (en) * | 2020-10-10 | 2022-05-20 | 南开大学 | Polyacid hybrid polymer with proton type and alkali metal ion type polymerization degree of 100 and preparation method thereof |
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| CN103254340B (en) | 2015-04-29 |
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