CN109251282B - Temperature-redox dual stimulus response type polymer and preparation method and application thereof - Google Patents
Temperature-redox dual stimulus response type polymer and preparation method and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 230000009977 dual effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000004044 response Effects 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 23
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
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- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention provides a temperature-redox dual stimulus-responsive polymer shown as a formula (I) and a preparation method and application thereof, the invention utilizes a RAFT active polymerization method to prepare a temperature-sensitive polymer with controllable molecular weight, and then oxidizes the temperature-sensitive polymer to prepare the TEMPO nitroxide free radical-containing temperature-redox dual stimulus-responsive polymer which can be used as a recovery catalyst for the catalytic oxidation reaction of alcohol; the preparation process of the temperature-redox dual stimulus response type polymer is simple, in addition, the polymer is endowed with controllable preparation by RAFT active polymerization, meanwhile, a temperature sensitive group (NIPAM) is introduced, and the amphiphilic polymer is provided with a redox response type group (nitroxide free radical) through oxidation;
Description
(I) technical field
The invention relates to a temperature-redox dual stimulus-responsive polymer, and a preparation method and application thereof.
(II) background of the invention
The stimulus-responsive polymer can make corresponding physical or chemical property changes due to the change of external environment (such as temperature, pH value, oxidation reduction, light, salt, sugar and carbon dioxide), so that the stimulus-responsive polymer has important research significance in the aspects of nanotechnology, drug controlled release, gene transfer systems, recoverable catalysts, shape memory materials and the like (chem.Rev.,2010,110, 146-177).
Among the stimulus-responsive polymers, redox-responsive polymers are of great interest due to their promising application prospects in catalysis, energy storage, controlled release, and the like. Many researchers have worked on the construction of redox stimulus responsive polymers. For example, disulfide bonds are implanted into the polymer backbone as redox sensitive groups (poly. chem.,2016,7, 6330-6339); the disassembly and self-assembly of amphiphilic polymer molecules with diselenides in redox environments has also been reported (macromol. rapid Commun.,2016,37, 865-871); supramolecular gels with redox self-healing due to host-guest interactions have also been reported (Nature chem.,2011,2, 511-516). However, these examples mainly report the introduction of redox-sensitive groups (such as disulfide bonds, diselenide, ferrocene, etc.) in the polymer chain, however the construction and introduction of redox groups is relatively complex. Therefore, it is of theoretical and practical interest to find a simple construction of an amphiphilic molecule with redox properties.
Nitroxides, such as 2,2,6, 6-tetramethylpiperidine nitroxide (TEMPO), are a stable free radical at room temperature. It can be reversibly oxidized and reduced under mild conditions. This property imparts TEMPO properties as an organic catalyst, a nuclear magnetic resonance developer and a battery material (Science,2002,35, 774-; Doi. org/10.1002/ange.201801009; Angew. chem. int. Ed.2017,57, 231-. However, to the best of our knowledge, redox stimulus responsive polymers prepared by covalently bonding TEMPO redox groups to amphiphilic polymers have been rarely reported.
In addition, a multi-responsive polymer is capable of responding to two or more stimulus signals, as opposed to a single-responsive polymer, which changes in properties to varying degrees when different stimulus-responsive signals are applied. Since poly-N-isopropylacrylamide (PNIPAM) has the lowest critical phase transition temperature (LCST) and the LCST of a polymer can be changed by adding a functional group, PNIPAM is currently the most hot material to be studied. Due to this property, the polymer material has temperature-redox dual responsiveness by introducing a TEMPO group in PNIPAM, so that the temperature sensitivity of the polymer can be adjusted by a redox reagent (vitamin C).
Disclosure of the invention
The invention aims to provide a temperature-redox dual stimulus-responsive polymer, and a preparation method and application thereof. The polymer can be used as a recovery catalyst for catalytic oxidation reaction of alcohol.
The technical scheme of the invention is as follows:
a temperature-redox dual stimulus-responsive polymer of formula (I):
in the formula (I), the compound is shown in the specification,
m is the polymerization degree of 2,2,6, 6-tetramethyl piperidine oxynitride, and m is an integer of 10-40;
n is the polymerization degree of the N-isopropyl acrylamide, and N is an integer of 60-90.
A preparation method of a temperature-redox dual stimulus-responsive polymer shown as a formula (I) comprises the following steps:
(1) mixing a compound (polyethylene glycol monomethyl ether, M) shown as a formula (II)n2000, written mPEG), 4-Dimethylaminopyridine (DMAP), a compound of formula (III) (4-cyano-4- (dodecylthiocarbonylthio) sulfonylpentanoic acid, written CDP), dichloromethane a to obtain a system a; mixing 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride (EDC) and dichloromethane B to obtain a system B; dropwise adding the system B into the system A under an ice bath condition, reacting at room temperature (20-30 ℃) for 16-24 hours after dropwise adding is finished, and then carrying out post-treatment on reaction liquid to obtain a compound (a macromolecular RAFT reagent, recorded as mPEG-CDP) shown in the formula (IV);
the amount ratio of the compound shown in the formula (II) to the substances of 4-dimethylamino pyridine, the compound shown in the formula (III) and 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride is 1: 0.5-2: 1-3: 1-3, preferably 1: 1: 2: 2;
the volume dosage of the dichloromethane A is 40-60 mL/g based on the mass of the compound shown in the formula (II); the volume dosage of the dichloromethane B is 60-80 mL/g calculated by the mass of 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride; the terms "dichloromethane a" and "dichloromethane B" have no special meaning and refer to the solvent dichloromethane in the general sense, and the labels "a" and "B" are used only to distinguish dichloromethane used in the different process steps;
the post-treatment method comprises the following steps: after the reaction is finished, precipitating the reaction solution by diethyl ether, centrifugally collecting the precipitate, and drying to obtain a compound shown as a formula (IV), wherein the compound is a light yellow solid;
(2) under the protection of inert gas (such as nitrogen), mixing a compound shown as a formula (IV), Azobisisobutyronitrile (AIBN), N-isopropylacrylamide (NIPAM), 2,6, 6-tetramethylpiperidinol ester (TMPM) and dioxane, reacting at 60-70 ℃ for 16-24 h, and then carrying out aftertreatment on reaction liquid to obtain a polymer shown as a formula (V) (marked as PEG-b-P (TMPM-co-NIPAM) and a temperature-sensitive amphiphilic polymer);
the mass ratio of the compound shown in the formula (IV) to the substances of azodiisobutyronitrile, 2,6, 6-tetramethylpiperidinol ester and N-isopropylacrylamide is 1: 0.25-0.4: 10-40: 60-90, preferably 1: 0.33: 20: 80;
the volume dosage of the dioxane is 20-50 mL/g based on the mass of the compound shown in the formula (IV);
the post-treatment method comprises the following steps: after the reaction is finished, precipitating the reaction solution by petroleum ether, centrifugally collecting the precipitate, and drying to obtain a polymer shown as a formula (V), wherein the polymer is white powder;
(3) dissolving the polymer of formula (V) in tetrahydrofuran, and adding Na2WO4·2H2O and Ethylene Diamine Tetraacetic Acid (EDTA), stirring for 20-40 min at room temperature, then heating to 50-60 ℃, and adding H2O2Continue to turn overReacting for 18-24 h, and then carrying out post-treatment on the reaction solution to obtain a polymer (marked as PEG-b-P (TMA-co-NIPAM)) shown in the formula (I);
the polymer shown in the formula (V) contains secondary amine groups, ethylene diamine tetraacetic acid and Na2WO4·2H2O、H2O2The ratio of the amounts of substances (1): 0.1-0.2: 0.2-0.4: 5-15, preferably 1: 0.15: 0.3: 10; the amount of the substance of the secondary amine group contained in the polymer of formula (V) can be determined by nmr analysis, a test means known in the art;
the volume consumption of the tetrahydrofuran is 10-20 mL/g based on the mass of the polymer shown in the formula (V);
the post-treatment method of the reaction liquid comprises the following steps: after the reaction is finished, filtering the reaction solution, precipitating the filtrate by petroleum ether, centrifuging, collecting the precipitate, and drying in vacuum to obtain a polymer shown as a formula (I), wherein the polymer is orange yellow powder;
in the formula (V), m and n are as defined in the formula (I).
The temperature-redox dual stimulus-responsive polymer shown in the formula (I) can be used as a recovery catalyst for catalytic oxidation reaction of alcohol.
Specifically, for example, the application method is as follows: mixing the polymer shown in the formula (I), benzyl alcohol, 4-dimethylaminopyridine, cuprous chloride and deionized water, carrying out catalytic oxidation reaction at room temperature (20-30 ℃), and monitoring by HPLC (high performance liquid chromatography) until the reaction is finished;
the mass ratio of the polymer shown in the formula (I), the benzyl alcohol, the 4-dimethylamino pyridine and the cuprous chloride is 1: 5-6: 0.5-0.6: 0.2 to 0.3, preferably 1: 5.4: 0.56: 0.25;
the volume consumption of the deionized water is 40-50 mL/g based on the mass of the benzyl alcohol.
Further, after the catalytic oxidation reaction is finished, the method for recovering the polymer shown in the catalyst formula (I) comprises the following steps: after the reaction is finished, the reaction system is placed at 50 ℃ for 10min, and the catalyst is recovered by filtration.
Compared with the prior art, the invention has the beneficial effects that: the preparation process of the temperature-redox dual stimulus response type polymer is simple, in addition, the polymer is endowed with controllable preparation by RAFT active polymerization, meanwhile, a temperature sensitive group (NIPAM) is introduced, and the amphiphilic polymer is provided with a redox response type group (nitroxide free radical) through oxidation.
(IV) description of the drawings
FIG. 1 is a hydrogen spectrum of mPEG-CDP (IV);
FIG. 2 is a hydrogen spectrum of PEG-b-P (TMPM-co-NIPAM) (V);
FIG. 3 is a hydrogen spectrum of PEG-b-P (TMA-co-NIPAM) (I);
FIG. 4 is a cyclic voltammogram of PEG-b-P (TMA-co-NIPAM) (I);
FIG. 5 is a graph showing the effect of catalytic oxidation of PEG-b-P (TMA-co-NIPAM) (I);
FIG. 6 shows the temperature sensitive recovery of PEG-b-P (TMA-co-NIPAM) (I).
(V) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Example 1: preparation of mPEG-CDP (IV)
Reacting mPEG (II) (M)n2000,2.0g,1mmol), cdp (iii) (0.8g, 2mmol), DMAP (0.122g,1mmol), added to 100ml dichloromethane; EDC (0.4g, 2mmol) is dissolved in 30mL dichloromethane, and the solution is dripped into the system under an ice bath environment to react for 18 hours at room temperature, after the reaction is finished, part of solvent is evaporated, the residual liquid is dripped into cold ether to wash the precipitate, after the washing is repeated for 3 times, the precipitate is put into a vacuum drying oven and is kept overnight at 40 ℃, and 2.11g of macromolecule RAFT reagent mPEG-CDP (IV) is obtained, and the yield is 87%.
Example 2: preparation of PEG-b-P (TMPM-co-NIPAM) (V)
To a 50mL single-neck round-bottom flask were added mPEG-CDP (IV) (0.24g,0.1mmol), AIBN (5.5mg,0.0335mmol), NIPAM (0.904g,8mmol), TMPM (0.45g,2mmol), and 6.37mL dioxane, respectively. General formula (N)2 3After 0min, the reaction was carried out at 70 ℃ for 24h, the liquid obtained by the reaction was precipitated with petroleum ether, and the precipitate was placed in a vacuum oven and dried overnight at 40 ℃ to obtain 1.51g of polymer PEG-b-P (TMPM-co-NIPAM) (V) with a yield of 95%.
Example 3: preparation of redox stimulus responsive Polymer PEG-b-P (TMA-co-NIPAM) (I)
Into a 50mL single-neck round-bottom flask were charged the polymers PEG-b-P (TMPM-co-NIPAM) (V) (1.0g, 1.26mmol of secondary amine group was detected), and Na2WO4·2H2O (0.1040g,0.32mmol), EDTA (0.0552g,0.19mmol), THF 16mL, stirred at room temperature for 30min, then transferred to a 60 ℃ oil bath, and H was added slowly2O2(1.3mL,12.6mmol), reacted for 24h, the liquid obtained from the reaction was precipitated with petroleum ether, and the precipitate was dried in a vacuum oven at 40 ℃ overnight to give 0.85g of polymer PEG-b-P (TMA-co-NIPAM) (I) in 84% yield.
Example 4: temperature-redox stimulus responsive polymer PEG-b-P (TMA-co-NIPAM) for alcohol catalytic oxidation
0.0224g of 4-dimethylaminopyridine, 0.01g of cuprous chloride, 0.216g of benzyl alcohol, 10ml of deionized water and 0.04g of PEG-b-P (TMA-co-NIPAM) are sequentially added into a 50ml flask and reacted for 5 hours at the temperature of 20 ℃, and the product is benzaldehyde with the yield of 99 percent; the conversion of the raw materials in the reaction process is shown in fig. 5;
example 5: recovery of temperature-redox stimulus responsive polymer PEG-b-P (TMA-co-NIPAM catalyst)
After the catalytic reaction is finished, the reaction solution is placed at 50 ℃ for ten minutes and filtered to obtain the PEG-b-P (TMA-co-NIPAM) catalyst. The temperature-sensitive property of the polymer can be endowed with the property of recycling under heating. As shown in fig. 6.
Claims (10)
1. A temperature-redox dual stimulus-responsive polymer of formula (I):
in the formula (I), the compound is shown in the specification,
m is an integer of 10-40;
n is an integer of 60 to 90.
2. The method for preparing the temperature-redox dual stimuli-responsive polymer of formula (I) according to claim 1, wherein the method comprises:
(1) mixing a compound shown in a formula (II), 4-dimethylamino pyridine, a compound shown in a formula (III) and dichloromethane A to obtain a system A; mixing 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride and dichloromethane B to obtain a system B; under the ice bath condition, dropwise adding the system B into the system A, reacting at room temperature for 16-24 h after dropwise adding, and then carrying out post-treatment on the reaction liquid to obtain a compound shown in a formula (IV);
the amount ratio of the compound shown in the formula (II) to the substances of 4-dimethylamino pyridine, the compound shown in the formula (III) and 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride is 1: 0.5-2: 1-3: 1-3;
(2) under the protection of inert gas, mixing a compound shown as a formula (IV), azodiisobutyronitrile, N-isopropyl acrylamide, 2,6, 6-tetramethyl piperidinol ester and dioxane, reacting for 16-24 h at 60-70 ℃, and then carrying out aftertreatment on reaction liquid to obtain a polymer shown as a formula (V);
the mass ratio of the compound shown in the formula (IV) to the substances of azodiisobutyronitrile, 2,6, 6-tetramethylpiperidinol ester and N-isopropylacrylamide is 1: 0.25-0.4: 10-40: 60-90;
(3) dissolving the polymer of formula (V) in tetrahydrofuran, and adding Na2WO4·2H2O and ethylene diamine tetraacetic acid, stirring for 20-40 min at room temperature, then heating to 50-60 ℃, and adding H2O2Continuing to react for 18-24 h, and then carrying out post-treatment on the reaction solution to obtain a polymer shown in the formula (I);
the polymer shown in the formula (V) contains secondary amine groups, ethylene diamine tetraacetic acid and Na2WO4·2H2O、H2O2The ratio of the amounts of substances (1): 0.1-0.2: 0.2E &0.4：5～15；
In the formula (V), m and n are as defined in the formula (I).
3. The preparation method according to claim 2, wherein in the step (1), the volume of the dichloromethane A is 40 to 60mL/g based on the mass of the compound represented by the formula (II); the volume dosage of the dichloromethane B is 60-80 mL/g based on the mass of the 1-ethyl-3- (3- (dimethylamino) propyl) carbodiimide hydrochloride.
4. The method of claim 2, wherein in the step (1), the post-treatment is carried out by: after the reaction is finished, the reaction solution is precipitated by ether, centrifugally collected and dried to obtain the compound shown in the formula (IV).
5. The method according to claim 2, wherein in the step (2), the volume of the dioxane is 20 to 50mL/g based on the mass of the compound represented by the formula (IV).
6. The method according to claim 2, wherein in the step (2), the post-treatment is carried out by: after the reaction is finished, the reaction solution is precipitated by petroleum ether, centrifugally collected, precipitated and dried to obtain the polymer shown in the formula (V).
7. The method according to claim 2, wherein in the step (3), the volume of the tetrahydrofuran is 10 to 20mL/g based on the mass of the polymer represented by the formula (V).
8. The method according to claim 2, wherein in the step (3), the reaction solution is post-treated by: after the reaction is finished, filtering the reaction solution, precipitating the filtrate by petroleum ether, centrifuging, collecting the precipitate, and drying in vacuum to obtain the polymer shown in the formula (I).
9. Use of a temperature-redox dual stimuli-responsive polymer of formula (I) according to claim 1 as a regenerative catalyst in the catalytic oxidation of alcohols.
10. The application of claim 9, wherein the method of applying is:
mixing the polymer shown in the formula (I), benzyl alcohol, 4-dimethylamino pyridine, cuprous chloride and deionized water, carrying out catalytic oxidation reaction at room temperature, and monitoring by HPLC (high performance liquid chromatography) until the reaction is finished;
the mass ratio of the polymer shown in the formula (I), the benzyl alcohol, the 4-dimethylamino pyridine and the cuprous chloride is 1: 5-6: 0.5-0.6: 0.2 to 0.3;
the volume consumption of the deionized water is 40-50 mL/g based on the mass of the benzyl alcohol.
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| "Catalytic oxidation of cellulose with a novel amphiphilic nitroxide block copolymer as a recoverable catalyst";Shaojie Liu et al.;《Cellulose》;20170619;第24卷(第9期);3635–3644 * |
| "Thermoresponsive and Redox Behaviors of Poly(N-isopropylacrylamide)-Based Block Copolymers Having TEMPO Groups as Their Side Chains";Toru Uemukai et al.;《International Journal of Polymer Science》;20131231;第2013卷;1-9 * |
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