CN101353402A - Inorganic heteropoly compound-organic polymer hybrid block copolymer and preparation thereof - Google Patents
Inorganic heteropoly compound-organic polymer hybrid block copolymer and preparation thereof Download PDFInfo
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Abstract
The invention relates to a hybrid block multipolymer of inorganic hybrid compound-organic polymer; the inorganic hybrid compound and the organic polymer are formed by the connection of a connection molecule through a covalent bond; the relative independence is maintained on the molecular scale so as to maintain the self-owned performance; the preparation method comprises the following steps: the inorganic hybrid compound and a micromolecule initiation agent are prepared into the giant molecule initiation agent of the inorganic hybrid compound by the connection molecule, thereby initiating the monomer polymerization, thus preparing the hybrid block multipolymer of inorganic hybrid compound-organic polymer. The hybrid block multipolymer of inorganic hybrid compound-organic polymer has the advantage that the active radical polymerization is firstly applied to realize the block polymerization of the hybrid compound and the polymer; the block multipolymer is connected by the covalent bond, and has the advantages of firm load, stability improving, easy recycling, being repeatedly used, cost saving and environment pollution reducing; both the original functions of the inorganic hybrid compound and the organic polymer are maintained; the hybrid block multipolymer can be dissolved in more organic solvents; the preparation method is simple and practical; the cost is low; in addition, the preparation method is easy for realizing industrial production.
Description
(1) technical field
The present invention relates to organic and inorganic, polymer chemistry and materials chemistry field, particularly a class inorganic heteropoly compound-organic polymer hybrid segmented copolymer and a preparation method.
(2) background technology
Heteropoly compound is a class multi-metal oxygen cluster compound (Polyoxometalate is called for short POM), by heteropolyanion, gegenion and crystal water and solvation molecular composition.If the gegenion of heteropoly compound is a proton, then form heteropolyacid, if gegenion is the non-proton heteropolyacid salt that just forms.The formation of heteropoly compound is based on heteropolyanion, and the space structure of heteropolyanion is the basis of classification.Heteropolyanion is by central atom (cry not only heteroatoms) and join atom (but also being polyatom) and form.Joining atom generally is made up of molybdenum (Mo), tungsten (W), vanadium (V), niobium (Nb), tantalum (Ta) etc.Found at present that nearly 70 kinds of atoms of elements can be used as the formation that central atom participates in heteropoly compound, these elements comprise whole and most second, third transition series elements and the part group of the lanthanides and the actinide elements of first transition system, add main group elements such as B, Al, Ga, In, Tl, Si, Ge, Sn, P, As, Sb, Bi, Se, Te, I.Every kind of central atom can be present in the heteropolyanion with different valence state again, so the heteropoly compound that forms is of a great variety.In this numerous heteropoly compound, have two big characteristics to can be used as the basis of classification: the one, central atom and the ratio of joining atom; The 2nd, the ligancy of central atom in the heteropolyanion (referring to " heteropoly compound outline ", Niu Jingyang, Wang Jingping work, press of He'nan University).
The history in existing more than 100 year so far of Chemistry of Polyacids is an important field of research in the inorganic chemistry.The most extensive and the sophisticated application of heteropolyacid (salt) is as a kind of novel effective catalyst.Industrial traditional strong acid catalyst has that equipment corrosion is serious, operational condition is harsh, side reaction is many, yield is low, catalyzer is poisonous and difficult separation, produce a large amount of acid waste water in handling and cause shortcomings such as environment dirt, long reaction time.Heteropolyacid (salt) receives increasing concern as a kind of novel efficient green catalyzer, makes progress very fast.J.Berzelius successfully synthesized the heteropolyacid that first has literature record in 1826---and the 12-ammonium phosphomolybdate (referring to Berzelius J.Pogg.Ann., 1826,6:369.).It is catalyzer that Japan in 1972 takes the lead in the 12-tungstosilicic acid, carries out the propylene hydration industrialization and succeeds; Nineteen eighty-two is a catalyzer with the 12-molybdophosphate, Methylacrylaldehyde gaseous oxidation system methacrylic acid; 1984 is catalyzer with 12-Molybdenum phosphoric acid, preparing tert-butanol from isobutylene by hydration; 1986 is catalyzer with the 12-tungstophosphoric acid, 8 project industrialization successes (referring to " Chemistry of Polyacids introduction ", Wang Enbo, Hu Changwen, Xu Linzhu, Chemical Industry Press) such as THF system polyoxy four methyne ethylene glycol.
Because the singularity of heteropolyacid (salt) structure, its application prospect is very extensive.Toxicologic study, the medical jurisprudence of the separation of medicine, evaluation, chemical toxicant identify and the analysis of biomaterial in, heteropoly compound is widely used as precipitation agent, oxygenant and developer.1979, people can be applied to fuel cell (such as H in searching
2-O
2Battery) find during new solid electrolyte in tungstophosphoric acid and molybdophosphate demonstrate high proton conductive (referring to Nakamura O, Kodama T, Ogino I, et al.Chem Lett, 1979,17:17).Heteropoly compound also has characteristics such as electric look, magnetic and nonlinear optics in addition, make that they can be at gel-sol inorganic materials additive (referring to Judeinstein P, Schmidt H.JSol-gel Sci Technol, 1994,3:189), organic non-conductive substrate additive (Suzuki T, Ozaki Y, JapanesePatent JP 63104027 A2,1988; Chem Abstr, 1988,109:119759), field such as recording materials obtains widespread use (referring to Lyman C.U S Patent 2895892,1959).Most important discovery is heteropolyanion [SiW
12O
40] antiviral activity (Raynaud M, Chermann J C, Plata F, et al.C R Acad Sci Ser D, 1971,272:347), [BW
12O
40]
4-, [P
2W
18O
62]
6-, [AsW
18O
62]
6-Show antiviral activity (referring to Schoenfeld B Deng heteropolyanion, Steinheider G, Glemser O.Z.Naturforsch, 1975,30b:959), a kind of HPA-23 heteropolyanion to the research that suppresses tumour (referring to Jasmin C, Chermann J C, Herve G, et al.J.Nat.Cancer Inst.1974,53:463) and have suppress the hiv virus reversed transcriptive enzyme effect (referring to Dormont D, Spire B, Barre-Sinousi F et al., Ann.Inst.Pasteur/Virol, 1985,136E; 75).These progress cause that the various countries scholar pays much attention to.
Polymkeric substance is contemporary the most widely used organic synthesis material, has numerous advantages such as easy processing.Radical polymerization is the important method of industrial production polymkeric substance, has that polymerisable monomer is many, the gentle easy control of reaction conditions, is easy to realize advantages such as industrialization, source of polymer more than 70% is arranged in the world approximately in radical polymerization.Active free radical polymerization (Living RadicalPolymerization) has and does not have termination, nothing shifts, trigger rate is far longer than characteristics such as rate of chain growth, with traditional radical polymerization mutually specific energy realize control better to molecular structure, be to realize molecular designing, syntheticly have an important means of ad hoc structure and functional polymer.In several active free radical polymerizations, atom transfer radical polymerization (Atom Transfer RadicalPolymerization, abbreviation ATRP) it is controlled to have the polymerization process activity, it is wide to adapt to the monomer scope, can synthesize low dispersity and definite molecular weight and molecular structure advantages such as polymkeric substance (referring to 1, Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T.Macromolecules 1995,28, and 1721; 2, Wang, J.S.; Matyjaszewski, K.J.Am.Chem.Soc.1995,117,5614.; 3, Matyjaszewski, K.; Wang, J.S.WO Pat.9630421, U.S.Pat.5 ,-763,548).More importantly advantage is end points or other position of initiating group being introduced a kind of polymkeric substance, can further cause another kind of monomer polymerization, thereby forms block, star, comb shape and hyperbranched polymer, has widened the use range of these polymkeric substance.
Yet realize that for inorganic heteropolyacid-organic polymer hybrid segmented copolymer and application of active radical polymerization the preparation of this hybridized segmented copolymer does not appear in the newspapers yet.
The inorganic heteropoly compound is subjected to very paying close attention to widely owing to its brilliance is functional, in all many-sides such as medicine, biology, the energy, catalysis, materials huge potential application foreground is arranged all.But because still there are many problem demanding prompt solutions in actual applications in this body structure of heteropoly compound and inherent nature.For example, the application need on medicine, biology is introduced organic group to strengthen or to improve its biological activity; In the application of aspects such as the energy, catalysis, material, the inorganic heteropoly compound easily runs off, and easily lumps, and specific surface area is little, poor heat stability, and to the impurity sensitivity in the industrial raw material, easy inactivation, work-ing life is short, is difficult for reclaiming; Particularly it is in organic solvent, and the inorganic heteropoly compound is stable and poorly soluble.These shortcomings have greatly limited the application of inorganic heteropoly compound.
(3) summary of the invention
The objective of the invention is at the problems referred to above, provide a kind of simple and practical, with low cost and be easy to realize the inorganic heteropoly compound-organic polymer hybrid segmented copolymer and the preparation method of suitability for industrialized production.
Technical scheme of the present invention:
A kind of inorganic heteropoly compound-organic polymer hybrid segmented copolymer, it is characterized in that: inorganic heteropoly compound and organic polymer are connected and composed by covalent linkage by organic link molecule, thereby keep the relatively independent performance separately that keeps on the molecular scale.
Described inorganic heteropoly compound be a class can with the inorganic heteropoly compound of organic compound reaction.
Described organic link molecule be a class can with the organic compound of inorganic heteropoly compound reaction.
The described organic link molecule that is connected the inorganic heteropoly compound contains the organic monomer polymeric functional group that initiation comprises carbon-carbon double bond.
Described organic polymer is the organic polymer that a class can generate from the functional group initiated polymerization of organic link molecule of being connected the inorganic heteropoly compound.
The heteropoly compound section can conversion mutually between the form of acid and salt in described inorganic heteropoly compound-organic polymer hybrid segmented copolymer.
The preparation method of a kind of inorganic heteropoly compound-organic polymer hybrid segmented copolymer, it is characterized in that: at first inorganic heteropoly compound and small molecules initiator are prepared into inorganic heteropoly compound macromole evocating agent by link molecule, further trigger monomer polymerization obtains inorganic heteropoly compound-organic polymer hybrid segmented copolymer.
Described inorganic heteropoly compound be all can with the heteropoly compound of hydroxyl reaction.
Described small molecules initiator is all small molecules initiators that contain ester group and can be used to cause atom transfer radical polymerization.
Described link molecule is that hydroxyl and amino molecule are contained in all two ends.
Described inorganic heteropoly compound macromole evocating agent is that the hydroxyl terminal by link molecule links to each other by esterification with heteropoly compound, and aminoterminal and the small molecules initiator ammonolysis reaction by ester links to each other and constitutes.
Described monomer is all monomers that can be used for atom transfer radical polymerization.
Described organic polymer is the organic polymer that obtains by chain polymerization.
Inorganic heteropoly compound-organic polymer hybrid segmented copolymer that described preparation has definite molecular weight and molecular weight distribution is to realize by the time of controlled polymerization reaction.
Advantage of the present invention is: the first Application active free radical polymerization has been realized the block copolymerization of heteropoly compound and polymkeric substance, heteropoly compound specific surface area after the load increases, because segmented copolymer relies on covalent linkage to connect, therefore load is firm, is difficult for running off, and stability improves, from system, reclaim easily after the reaction, can reuse, save industrial cost greatly, reduce the environmental pollution degree; Secondly, in inorganic heteropoly compound-organic polymer hybrid segmented copolymer, it is relatively independent that inorganic heteropoly compound and organic polymer keep on the yardstick of whole molecule, but connect by chemical bond at regional area, their original separately functions have all been kept to a great extent, organic polymer has also kept their original rerum naturas, make inorganic heteropoly compound-organic polymer hybrid segmented copolymer can be dissolved in the more organic solvent, greatly strengthen its stability and thermostability, and can carry out melt-processed; Can effectively solve and improve the problem that heteropoly compound exists in industrial application, further widen the range of application and the prospect of function heteropoly compound, and the preparation method is simple and practical, with low cost and be easy to realize suitability for industrialized production.
(4) embodiment
Embodiment 1:
The inorganic heteropoly compound is Dawson structure phosphorus tungsten vanadium heteropolyacid organic ammonium salt [(n-C
4H
9) N]
5[H
4P
2V
3W
15O
62], the small molecules initiator is that bromo acid hydroxy methacrylate, link molecule are Tutofusin tris, to adopt atom transfer radical polymerization, monomer be vinylbenzene, the preparation molecular weight is 97, inorganic heteropoly compound-organic polymer hybrid segmented copolymer of 000, its preparation method is as follows:
1) the heteropoly compound macromole evocating agent is synthetic
1. synthetic (the first step reaction in the synthetic route) of small molecules initiator (bromo acid hydroxy methacrylate):, cool off in the moisture eliminator with 2 mouthfuls of bottles dry 4h under 120 ℃.Add 43g ethylene glycol, 8.4g triethylamine, 250ml methylene dichloride; argon shield is dissolved in 15g bromo isobutyl acylbromide in the 50ml methylene dichloride in advance with the slow dropping of 2h under ice-water bath and intense stirring condition, room temperature continues reaction 24h; filter insolubles, solvent is spin-dried for, obtain thick liquid.
2. the purification of small molecules initiator: the previous step product is washed layering, 3 times repeatedly with the 100ml distillation, obtain water layer and oil reservoir, combining water layer is used 100ml chloroform extraction 3 times, merges trichloromethane phase and oil reservoir, anhydrous magnesium sulfate drying spends the night, the filtration drying agent is spin-dried for solvent, the underpressure distillation product, obtain initiator 8.7g, productive rate is 60%.
3. the introducing of linking group on the small molecules initiator (reaction of the step of second in the synthetic route): become in flask, the 1.147g Tutofusin tris to be dissolved in 7.9ml N; in the dinethylformamide; add initiator 2g, salt of wormwood 1.417g, argon shield; 25 ℃ of reaction 24h; the elimination insolubles is spin-dried for product, uses ethyl acetate: the eluent of sherwood oil=2: 1 is crossed silicagel column; be spin-dried for solution and obtain white crystal 1.58g, productive rate is 61.8%.
4. synthetic (three-step reaction in the synthetic route) of heteropoly compound macromole evocating agent: in flask with 1g[(n-C
4H
9) N]
5[H
4P
2V
3W
15O
62] be dissolved in 13.5ml N, in the dinethylformamide, add 0.0625g previous step products therefrom; argon shield; 70 ℃ the reaction 7 days, splash in the 120ml ether and precipitate, with resolution of precipitate in minimum DMF; in 5 times of ether, precipitate; redissolve, precipitation process 2 times, suction filtration, 50 ℃ of vacuum-drying 2d; obtain yellow powder shape heteropolyacid salt macromole evocating agent 0.89g, productive rate is 85.4%.
2) realize synthetic (four-step reaction in the synthetic route) of inorganic heteropoly compound-organic polymer hybrid segmented copolymer by ATRP: will react the eggplant bottle and dry by the fire 4h for 160 ℃, cool off in the moisture eliminator, cuprous bromide 5.34mg packs into, cupric bromide 0.267mg, heteropoly compound macromole evocating agent 0.2424g vacuumizes, applying argon gas 3 times repeatedly, add vinylbenzene 4.6456g in the argon gas stream, pentamethyl-diethyl triamine 6.4mg, N, dinethylformamide 5ml, the sealed reaction bottle, liquid nitrogen freezing, bleed, thaw 110 ℃ of reaction 12h, logical atmosphere 3 times repeatedly, the ice-water bath cooling, cross the aluminium sesquioxide post, precipitate in the methyl alcohol, oven dry, get final product, molecular weight 97,000, transformation efficiency are 71.8%.
3) the mutual conversion between heteropoly compound section acid in inorganic heteropoly compound-organic polymer hybrid segmented copolymer, the salt form.
1. H
+The pre-treatment of type ion exchange resin: the strongly acidic styrene type cation exchange resin of getting the commercially available 001*7 of 10ml, distilled water flushing is for several times until colourless, the NaOH solution soaking of 20ml 5% 1 day, distilled water is washed till neutrality, the HCl solution soaking of 30ml5% 1 day, deionized water is washed till neutrality, 80 ℃ of oven dry.
2. [Bu
4N]
+The pre-treatment of type ion exchange resin: get the strongly acidic styrene type cation exchange resin of the commercially available 001*7 of 60ml, distilled water flushing is for several times until colourless, the HCl solution soaking of 120ml 5% 1 day, and distilled water is washed till neutrality, 25% the Bu of 100ml
4NOH solution soaking 1 day, deionized water is washed till neutrality, 80 ℃ of oven dry.
3. in the hybridized segmented copolymer inorganic heteropoly compound section heteropolyacid salt to the conversion of heteropolyacid: get 100mg step 2) the inorganic heteropoly compound-organic polymer hybrid segmented copolymer of preparation, be dissolved in the N of 50ml, in the dinethylformamide, add the good H of 10ml pre-treatment
+Type ion exchange resin, the solution feculence, 70 ℃ are stirred 6h, and the deionizing exchange resin is spin-dried for turbid liquid, and vacuum-drying promptly gets the hybrid segmented copolymer of heteropolyacid form.
4. in the hybridized segmented copolymer inorganic heteropoly compound section heteropolyacid to the conversion of heteropolyacid salt: get the hybrid segmented copolymer of the heteropolyacid form of 100mg previous step preparation, be dissolved in the N of 50ml, in the dinethylformamide, add the good [Bu of 10ml pre-treatment
4N]
+Type ion exchange resin, 70 ℃ are stirred 6h, and the deionizing exchange resin is spin-dried for solution, and vacuum-drying promptly obtains the inorganic heteropoly compound-organic polymer hybrid thing segmented copolymer of heteropolyacid salt form again.
Inorganic heteropoly compound-organic polymer hybrid segmented copolymer the synthetic route and the principle of embodiment 1 preparation are expressed as follows:
Embodiment 2:
Raw materials used identical with embodiment 1, the preparation molecular weight is inorganic heteropoly compound-organic polymer hybrid segmented copolymer of 36,000, and its preparation method is as follows:
1) the heteropoly compound macromole evocating agent is synthetic
Among this embodiment, the synthetic method of heteropoly compound macromole evocating agent and step are all identical with embodiment 1.
2) realize the synthetic of inorganic heteropoly compound-organic polymer hybrid segmented copolymer by ATRP: with the difference of embodiment 1 under 110 ℃ of conditions, reacting 4.5h, control the molecular weight of segmented copolymer by controlling reaction time, dry final product, molecular weight 36,000, transformation efficiency 37.8%.
3) the heteropoly compound section can be changed between the form of acid and salt mutually in inorganic heteropoly compound-organic polymer hybrid segmented copolymer, and the method for conversion and step are all identical with embodiment 1.
Embodiment 3:
The inorganic heteropoly compound is Dawson structure phosphorus tungsten vanadium heteropolyacid organic ammonium salt [(n-C
4H
9) N]
5[H
4P
2V
3W
15O
62], the small molecules initiator is that bromo acid hydroxy methacrylate, link molecule are Tutofusin tris, to adopt atom transfer radical polymerization, monomer be methyl methacrylate, the preparation molecular weight is 49, inorganic heteropoly compound-organic polymer hybrid segmented copolymer of 000, its preparation method is as follows:
1) the heteropoly compound macromole evocating agent is synthetic
Among this embodiment, the synthetic method of heteropoly compound macromole evocating agent and step are all identical with embodiment 1.
2) realize the synthetic of inorganic heteropoly compound-organic polymer hybrid segmented copolymer by ATRP: will react 160 ℃ of bakings of eggplant bottle 4h, cool off in the moisture eliminator, the cuprous chloride 3.08mg that packs into, heteropoly compound macromole evocating agent 0.2424g vacuumizes, applying argon gas 3 times repeatedly, add methyl methacrylate 3.2254g in the argon gas stream, pentamethyl-diethyl triamine 6.4mg, N, dinethylformamide 5ml, the sealed reaction bottle, liquid nitrogen freezing, bleed, thaw 30 ℃ of reaction 14h, logical atmosphere 3 times repeatedly, precipitate in the methyl alcohol, oven dry gets final product, molecular weight 49,000, transformation efficiency is 55%.
3) the heteropoly compound section can be changed between the form of acid and salt mutually in inorganic heteropoly compound-organic polymer hybrid segmented copolymer, and the method for conversion and step are all identical with embodiment 1.
Embodiment 4:
The inorganic heteropoly compound is Anderson structure heteropolyacid salt [N (C
4H
9)
4]
3[MnMo
6O
18{ (OCH
2)
3CNH
2}
2], the small molecules initiator is that bromo acid hydroxy methacrylate, link molecule are Tutofusin tris, to adopt atom transfer radical polymerization, monomer be vinylbenzene, the preparation molecular weight is 25, inorganic heteropoly compound-organic polymer hybrid segmented copolymer of 000, its preparation method is as follows:
1) the heteropoly compound macromole evocating agent is synthetic
Among this embodiment, the synthesis step of heteropoly compound macromole evocating agent 1., 2., 3. all identical with embodiment 1
4. synthetic (three-step reaction in the synthetic route) of heteropoly compound macromole evocating agent: in flask with 8g[N (C
4H
9)
4]
4[α-Mo
8O
26], 1.49gMn (CH
3COO)
3H
2O is dissolved in the 150ml acetonitrile, adds 3.46g previous step products therefrom; argon shield, backflow 16h is cooled to room temperature; elimination black insolubles, ether diffusion 2h, elimination white insolubles; continue to spread a couple of days; leach orange crystal, with minor amounts of acetonitrile, ether washing, vacuum-drying 2d; obtain heteropolyacid salt macromole evocating agent 9.77g, productive rate is 80%.
2) realize synthetic (four-step reaction in the synthetic route) of inorganic heteropoly compound-organic polymer hybrid segmented copolymer by ATRP: will react the eggplant bottle and dry by the fire 4h for 160 ℃, and cool off in the moisture eliminator, cuprous bromide 5.34mg packs into, cupric bromide 0.267mg, heteropolyacid macromole evocating agent 0.0879g vacuumizes, applying argon gas 3 times repeatedly adds vinylbenzene 4.6456g in the argon gas stream, pentamethyl-diethyl triamine 6.4mg, N, dinethylformamide 5ml, sealing, liquid nitrogen freezing, bleed, thaw 3 times repeatedly, 110 ℃ of reaction 2h, logical atmosphere, ice-water bath cooling, cross the aluminium sesquioxide post, precipitate in the methyl alcohol, dry final product, molecular weight 25,000, transformation efficiency 25%.
3) the heteropoly compound section can conversion mutually between the form of acid and salt in inorganic heteropoly compound-organic polymer hybrid segmented copolymer.The method and the step of conversion are all identical with embodiment 1.
Inorganic heteropoly compound-organic polymer hybrid segmented copolymer the synthetic route and the principle of embodiment 4 preparations are expressed as follows:
Claims (14)
1. inorganic heteropoly compound-organic polymer hybrid segmented copolymer, it is characterized in that: inorganic heteropoly compound and organic polymer are connected and composed by covalent linkage by link molecule, thereby keep the relatively independent performance separately that keeps on the molecular scale.
2. inorganic heteropoly compound according to claim 1-organic polymer hybrid segmented copolymer is characterized in that: described inorganic heteropoly compound be a class can with the inorganic heteropoly compound of organic compound reaction.
3. inorganic heteropoly compound according to claim 1-organic polymer hybrid segmented copolymer is characterized in that: described organic link molecule be a class can with the organic compound of inorganic heteropoly compound reaction.
4. inorganic heteropoly compound according to claim 1-organic polymer hybrid segmented copolymer is characterized in that: the described organic link molecule that is connected the inorganic heteropoly compound contains the organic monomer polymeric functional group that initiation comprises carbon-carbon double bond.
5. inorganic heteropoly compound according to claim 1-organic polymer hybrid segmented copolymer is characterized in that: described organic polymer is the organic polymer that a class can generate from the functional group initiated polymerization of organic link molecule of being connected the inorganic heteropoly compound.
6. inorganic heteropoly compound according to claim 1-organic polymer hybrid segmented copolymer is characterized in that: the heteropoly compound section can conversion mutually between the form of acid and salt in described inorganic heteropoly compound-organic polymer hybrid segmented copolymer.
7. the preparation method of inorganic heteropoly compound-organic polymer hybrid segmented copolymer, it is characterized in that: at first inorganic heteropoly compound and small molecules initiator are prepared into inorganic heteropoly compound macromole evocating agent by link molecule, further trigger monomer polymerization obtains inorganic heteropoly compound-organic polymer hybrid segmented copolymer.
8. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer is characterized in that: described inorganic heteropoly compound be all can with the heteropoly compound of hydroxyl reaction.
9. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer is characterized in that: described small molecules initiator is all small molecules initiators that contain ester group and can be used to cause atom transfer radical polymerization.
10. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer is characterized in that: described link molecule is that hydroxyl and amino molecule are contained in all two ends.
11. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer, it is characterized in that: described inorganic heteropoly compound macromole evocating agent is that the hydroxyl terminal by link molecule links to each other by esterification with heteropoly compound, and aminoterminal and the small molecules initiator ammonolysis reaction by ester links to each other and constitutes.
12. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer is characterized in that: described monomer is all monomers that can be used for atom transfer radical polymerization.
13. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer is characterized in that: described organic polymer is the organic polymer that obtains by chain polymerization.
14. the preparation method of inorganic heteropoly compound according to claim 7-organic polymer hybrid segmented copolymer is characterized in that: inorganic heteropoly compound-organic polymer hybrid segmented copolymer that described preparation has definite molecular weight and molecular weight distribution is to realize by the time of controlled polymerization reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914191A (en) * | 2010-07-05 | 2010-12-15 | 南开大学 | Preparation method of polyoxometallate-polymer hybridized segmented copolymer nanotube |
| CN102659851A (en) * | 2012-05-04 | 2012-09-12 | 南开大学 | Polyoxometallate-silsesquioxane hybrid compound and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914191A (en) * | 2010-07-05 | 2010-12-15 | 南开大学 | Preparation method of polyoxometallate-polymer hybridized segmented copolymer nanotube |
| CN102659851A (en) * | 2012-05-04 | 2012-09-12 | 南开大学 | Polyoxometallate-silsesquioxane hybrid compound and preparation method |
| CN102659851B (en) * | 2012-05-04 | 2016-01-20 | 南开大学 | Polyoxometallate-silhybridoxane hybridoxane compound and preparation method |
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