CN111925280A - Novel bis-styrene polyether monomer and synthesis and application thereof - Google Patents
Novel bis-styrene polyether monomer and synthesis and application thereof Download PDFInfo
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Abstract
The invention provides a novel bis-styrene polyether monomer, synthesis thereof and application thereof in controllable preparation of a copolymer with a main chain containing a macrocyclic structure, belonging to the field of preparation and application of polymer monomers. The method is used for synthesizing the bis-styrene polyether monomer with the electron-rich structure, and the responsive cyclic polymer can be obtained through further maleic anhydride-assisted reversible fragmentation chain transfer cyclic polymerization, so that the electron-rich macrocyclic structure can be efficiently and quickly constructed, and the main properties of the cyclic polymer are further expanded.
Description
Technical Field
The invention belongs to the field of polymer monomer preparation and application, and particularly relates to a novel bis-styrene polyether monomer and synthesis and application thereof.
Background
In the 80's of the 20 th century, scientists reported a bis-phenyl 34 crown ether 10 compound with a structure similar to a diphenylene cycloalkane, which has a-pi electron-rich hydroquinone unit and can form a face-to-face complex with a-pi electron-deficient paraquat compound.
As shown in the formula 1, the compound of the diphenyl 34 crown ether 10 rich in the-pi electrons and the paraquat compound lacking the-pi electrons form a face-to-face compound mainly through the interaction of pi-pi stacking, and the formed compound has a special structure. The corresponding pseudorotaxanes can be obtained by rational molecular design [ Journal of the Chemical Society, Chemical Communications, 1991, (23): 1680.], rotaxanes, and catenes [ Journal of the American Chemical Society, 1992, 114 (1): 193-218, etc. For the construction of supramolecular machinery by further using bisphenyl 34 crown ether 10, there are documents [ Journal of the Chemical Society, Chemical Communications, 1992, (16): 1124.] reported the construction of a molecular shuttle that can achieve rapid oscillation of the bisphenyl 34 crown 10 ring structure on the end-capped linear molecule. Further references [ Chemistry-A European Journal, 2001, 7 (16): 3482 discloses a catenane-based bimodal molecular switch with a more complex structure, which provides the possibility for further development of molecular machines, especially for applications related to controlling unidirectional rotation of one ring relative to another ring in catenane. In the four and fifty years of the 20 th century, George Bergen Butler and its co-workers unexpectedly obtained linear soluble polymers in a single polymer crosslinking experiment, and further the concept of "Cyclopolymerization" (Cyclopolymerization) was proposed. With the continuous development of the chemistry of ring polymerization, not only can a thermodynamically stable five-membered or six-membered ring structure be prepared, but also a ring structure exceeding twenty-membered or even larger can be controllably prepared by using a ring polymerization method, so that the ring polymer can be used in the field of supramolecular chemistry.
There are recent documents [ Macromolecules, 2011, 44 (16): 6311-6317 ] reports a maleic anhydride-assisted reversible fragmentation chain transfer polymerization, as shown in formula 2, a controllable ring polymerization of a bis-styrene monomer can be realized to prepare a ring polymer. And can graft water-soluble polyethylene glycol chain on the main polymer chain through maleic anhydride ring-opening reaction, and can be used for adjusting the water solubility of the ring polymer.
By combining the research backgrounds, a stilbene monomer with an electron-rich structure is designed and synthesized, and a cyclic polymer with the electron-rich structure is constructed by a maleic anhydride-assisted RAFT (reversible addition fragmentation chain transfer) ring polymerization method, so that the interaction between the cyclic polymer and bipyridyl salt is further realized, and a foundation is provided for further constructing a novel supermolecule topological structure.
Disclosure of Invention
The invention provides a novel bis-styrene polyether monomer and a synthesis method thereof, the monomer can realize the controllable preparation of a copolymer with a main chain containing a large ring structure through maleic anhydride-assisted reversible fragmentation chain transfer polymerization, and further expands the application of the ring polymer in the field of supermolecules.
A novel bis-styrene polyether monomer has a structure shown in formula (I):
the bis-styrene polyether monomer obtained by the invention contains bis-styrene end groups, and can realize free radical copolymerization with maleic anhydride under the initiation of free radicals. By adjusting the proportion and concentration of the monomer and the maleic anhydride, the ring polymerization of the monomer can be realized, and the ring polymer containing a main chain macrocyclic structure can be obtained. The ring structure contains two-pi-rich hydroquinone structures, and can form a face-to-face complex with paraquat compounds lacking-pi electrons. The ring structure also contains a crown ether structure, and the pseudo-rotaxane compound can be realized with secondary ammonium salt.
A method for synthesizing a polystyrene-containing polyether monomer comprises the following steps:
(1) in a double-neck flask provided with a constant pressure dropping funnel and a magnetic stirrer, an aqueous solution of inorganic strong base is dropped into a tetrahydrofuran solution mixed by tetraethylene glycol and p-methylbenzenesulfonyl chloride under an argon atmosphere, and the mixture is stirred for 24 hours at room temperature. And carrying out post-treatment to obtain an intermediate M-1.
The structure of the tetraethylene glycol is shown as a formula (II)
The structure of the p-methyl benzene sulfonyl chloride is shown as a formula (III)
The structure of M-1 is shown as formula (IV)
(2) Under the atmosphere of argon, adding alkali, M-1 and hydroquinone into a double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer, dissolving in acetonitrile, and heating for reaction for 15 hours. And carrying out post-treatment to obtain an intermediate M-2.
The structure of the hydroquinone is shown as a formula (V)
The structure of M-2 is shown as formula (VI)
(3) Under argon atmosphere, adding alkali, p-hydroxybenzaldehyde and 1, 2-dibromoethane into a double-neck flask with a magnetic stirring bar, dissolving the mixture in acetonitrile, and reacting for 15 hours at room temperature. And carrying out post-treatment to obtain an intermediate M-3.
The structure of the hydroxybenzaldehyde is shown as a formula (VII)
The structure of the 1, 2-dibromoethane is shown as a formula (VIII)
The structure of M-3 is shown as formula (VIIII)
(4) Under the atmosphere of argon, adding alkali M-3 and M-2 into a double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer, dissolving in DMF, and heating for reaction for 15 h. And carrying out post-treatment to obtain an intermediate M-4.
The structure of M-4 is shown as the formula (X)
(5) Under the atmosphere of argon, in a double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer, adding sodium hydride into a tetrahydrofuran solution of a wittig reagent in batches, refluxing for 1h, dropwise adding an M-4 tetrahydrofuran solution, and continuing to perform reflux reaction for 12 h. After-treatment, the bis-styrene polyether monomer is obtained.
Preferably, the monomer is linear and is end-capped with styryl groups at both ends.
The inorganic strong base in the preferable step (1) is potassium hydroxide.
Preferably, the base used in steps (2), (3) and (4) is potassium carbonate.
The heating temperature in the preferable step (2) is 80 ℃.
Preferably, the heating temperature in the step (4) is 130 ℃.
The wittig reagent in the preferable step (5) is triphenylphosphonium bromomethane.
Compared with the prior art, the invention has the beneficial effects that: the synthesis of a novel bis-styrene polyether monomer is realized for the first time, the controllable ring polymerization of the monomer can be realized by using maleic anhydride-assisted reversible fragmentation chain transfer polymerization, and the obtained ring polymer can realize the host-object recognition effect of various objects, thereby laying a foundation for further expanding the application of the ring polymerization in the supermolecule field.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a monomer, and FIG. 2 is a hydrogen nuclear magnetic spectrum of a cyclic polymer.
Detailed Description
Example 1
M-1: in a 150mL two-necked flask equipped with a constant pressure dropping funnel and a magnetic stirrer, an aqueous solution (5mL) of KOH (2.24g, 40mmol) was added dropwise to a THF solution (25mL) of a mixture of tetraethylene glycol (1.94g, 10mmol) and p-toluenesulfonyl chloride (4.77g, 25mmol) under an argon atmosphere, and stirred at room temperature for 24 hours. Suction filtration, spin-drying, addition of 50mL of distilled water, extraction with dichloromethane (150mL × 3), combination of organic phases, drying over anhydrous magnesium sulfate, filtration, spin-drying, and purification by column chromatography (PE: EA ═ 1: 2) gave M-1(3.14g, 62%) as a colorless oil.
M-2: under argon atmosphere, K is added into a 100mL double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer2CO3(1.45g, 10.5mmol), M-1(2.5g, 5mmol), hydroquinone (5.5g, 50mmol) in acetonitrile (25mL) was heated to 80 ℃ for 15 h. Acetonitrile was removed under reduced pressure, and 50mL of distilled water was added, extracted with dichloromethane (50mL × 3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, dried, and purified by column chromatography (EA: DCM ═ 1: 2) to give M-2(1.19g, 63%) as a colorless oil.
M-3: in a 100mL two-necked flask equipped with a magnetic stirrer, K was added under an argon atmosphere2CO3(1.38g, 10mmol), p-hydroxybenzaldehyde (0.61g, 5mmol), 1, 2-dibromoethane (2.02g, 1.1mL, 10mmol) and dissolved in acetonitrile (15mL) and reacted at room temperature for 15 h. Acetonitrile was removed under reduced pressure, 50mL of distilled water was added, dichloromethane extraction (50mL × 3) was performed, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spun-dried, and purified by column chromatography (PE: EA ═ 3: 1) to give M-3(0.79g, 65%) as a colorless oil.
M-4: under the argon atmosphere, constant pressure drop is providedAdding K into a 100mL double-neck flask with a liquid funnel, a spherical condenser and a magnetic stirrer2CO3(277mg, 2mmol), M-3(252mg, 1.1mmol), M-2(189mg, 0.5mmol) in DMF (3mL) and heated to 130 ℃ for 15 h. DMF was removed under reduced pressure, 15mL of distilled water was added, dichloromethane extraction (25mL × 3) was performed, organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spun-dried, and purified by column chromatography (EA: DCM ═ 1: 1) to give M-4(260mg, 77%) as a pale yellow solid.
M: NaH (45.25mg, 1.125mmol, 60% in mineral oil) was added portionwise to a THF solution (3mL) of triphenylphosphonium bromomethane (186mg, 1.05mmol) under an argon atmosphere in a 100mL two-necked flask equipped with a constant pressure dropping funnel, a spherical condenser and a magnetic stirrer, refluxed for 1 hour to turn the system yellow, and then a THF solution (3mL) of M-4(295mg, 0.44mmol) was added dropwise to continue the reflux reaction for 12 hours. After completion of the reaction, THF was removed under reduced pressure, 15mL of distilled water was added, dichloromethane was extracted (25mL × 3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spin-dried, and purified by column chromatography (EA: DCM ═ 1: 10) to obtain M (175mg, 60%) as a white solid.
Example 2
M-1: in a 250mL two-necked flask equipped with a constant pressure dropping funnel and a magnetic stirrer, an aqueous solution (10mL) of KOH (4.48g, 80mmol) was added dropwise to a THF solution (50mL) of a mixture of tetraethylene glycol (3.88g, 20mmol) and p-toluenesulfonyl chloride (9.53g, 50mmol) under an argon atmosphere, and stirred at room temperature for 24 hours. Suction filtration, spin-drying, addition of 100mL of distilled water, extraction with dichloromethane (150mL × 3), combination of organic phases, drying over anhydrous magnesium sulfate, filtration, spin-drying, and purification by column chromatography (PE: EA ═ 1: 2) gave M-1(5.969g, 59%) as a colorless oil.
M-2: under argon atmosphere, K is added into a 100mL double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer2CO3(2.9g, 21mmol), M-1(5.03g, 10mmol), hydroquinone (11g, 100mmol) in acetonitrile (50mL) was heated to 80 ℃ for 15 h. Acetonitrile was removed under reduced pressure, 50mL of distilled water was added, dichloromethane extraction (100mL × 3) was performed, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spin-dried, and purified by column chromatography (EA: DCM ═ 1: 2) to obtainM-2(2.27g, 60%) as a colorless oil.
M-3: in a 100mL two-necked flask equipped with a magnetic stirrer, K was added under an argon atmosphere2CO3(2.76g, 20mmol), p-hydroxybenzaldehyde (1.22g, 10mmol), 1, 2-dibromoethane (4.04g, 2.2mL, 20mmol) and dissolved in acetonitrile (30mL) and reacted at room temperature for 15 h. Acetonitrile was removed under reduced pressure, 50mL of distilled water was added, dichloromethane extraction (100mL × 3) was performed, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spun-dried, and purified by column chromatography (PE: EA ═ 3: 1) to give M-3(1.56g, 64%) as a colorless oil.
M-4: under argon atmosphere, K is added into a 100mL double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer2CO3(553mg, 4mmol), M-3(504mg, 2.2mmol), M-2(378mg, 1mmol) in DMF (5mL) and heated to 130 ℃ for 15 h. DMF was removed under reduced pressure, 15mL of distilled water was added, dichloromethane extraction (50mL × 3) was performed, organic phases were combined, dried over anhydrous magnesium sulfate, filtered, dried and purified by column chromatography (EA: DCM ═ 1: 1) to obtain M-4(499mg, 74%) as a pale yellow solid.
M: NaH (90.5mg, 2.25mmol, 60% in mineral oil) was added portionwise to a THF solution (5mL) of triphenylphosphonium bromomethane (372mg, 2.1mmol) under an argon atmosphere in a 100mL two-necked flask equipped with a constant pressure dropping funnel, a spherical condenser and a magnetic stirrer, and after refluxing for 1 hour and the system became yellow, a THF solution (5mL) of M-4(589mg, 0.87mmol) was added dropwise and the reaction was continued for further refluxing for 12 hours. After completion of the reaction, THF was removed under reduced pressure, 50mL of distilled water was added, and extraction was carried out three times with ethyl acetate (3X 100 mL). Suction filtration, spin-drying, addition of 15mL of distilled water, extraction with dichloromethane (25mL × 3), combination of organic phases, drying over anhydrous magnesium sulfate, filtration, spin-drying, and purification by column chromatography (EA: DCM ═ 1: 10) gave M (350mg, 60%) as a white solid.
Example 3
M-1: in a 250mL two-necked flask equipped with a constant pressure dropping funnel and a magnetic stirrer, an aqueous solution (20mL) of KOH (8.96g, 160mmol) was added dropwise to a THF solution (100mL) of a mixture of tetraethylene glycol (7.76g, 40mmol) and p-toluenesulfonyl chloride (19.06g, 100mmol) under an argon atmosphere, and stirred at room temperature for 24 hours. Suction filtration, spin-drying, addition of 100mL of distilled water, extraction with dichloromethane (150mL × 3), combination of organic phases, drying over anhydrous magnesium sulfate, filtration, spin-drying, and purification by column chromatography (PE: EA ═ 1: 2) gave M-1(12.14g, 60%) as a colorless oil.
M-2: under argon atmosphere, K is added into a 250mL double-mouth flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer2CO3(5.8g, 42mmol), M-1(10.06g, 20mmol), hydroquinone (22g, 200mmol) in acetonitrile (80mL) was heated to 80 ℃ for 15 h. Acetonitrile was removed under reduced pressure, and 100mL of distilled water was added, extracted with dichloromethane (100mL × 3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, dried, and purified by column chromatography (EA: DCM ═ 1: 2) to give M-2(4.54g, 60%) as a colorless oil.
M-3: in a 100mL two-necked flask equipped with a magnetic stirrer, K was added under an argon atmosphere2CO3(5.52g, 40mmol), p-hydroxybenzaldehyde (2.44g, 20mmol), 1, 2-dibromoethane (8.08g, 4.4mL, 40mmol) and dissolved in acetonitrile (50mL) and reacted at room temperature for 15 h. Acetonitrile was removed under reduced pressure, 50mL of distilled water was added, dichloromethane extraction (100mL × 3) was performed, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spun-dried, and purified by column chromatography (PE: EA ═ 3: 1) to give M-3(2.97g, 61%) as a colorless oil.
M-4: under argon atmosphere, K is added into a 100mL double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer2CO3(1.11mg, 8mmol), M-3(1.01mg, 4.4mmol), M-2(756mg, 2mmol) in DMF (10mL) and heated to 130 ℃ for 15 h. DMF was removed under reduced pressure, 15mL of distilled water was added, dichloromethane extraction (50mL × 3) was performed, organic phases were combined, dried over anhydrous magnesium sulfate, filtered, dried and purified by column chromatography (EA: DCM ═ 1: 1) to obtain M-4(944mg, 70%) as a pale yellow solid.
M: NaH (181mg, 4.5mmol, 60% in mineral oil) was added in portions to a THF solution (10mL) of triphenylphosphorbromomethane (744mg, 4.2mmol) under an argon atmosphere in a 100mL two-necked flask equipped with a constant pressure dropping funnel, a spherical condenser and a magnetic stirrer, refluxed for 1 hour to turn yellow, and then a THF solution (10mL) of M-4(1.18mg, 1.74mmol) was added dropwise to continue the reflux reaction for 12 hours. After completion of the reaction, THF was removed under reduced pressure, 15mL of distilled water was added, dichloromethane was extracted (25mL × 3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, spin-dried, and purified by column chromatography (EA: DCM ═ 1: 10), to give M (709mg, 60%) as a white solid.
Application example 1
Maleic anhydride (980mg, 10mmol), monomer M (671mg, 1mmol), benzyl dithiobenzoate as a chain transfer reagent (13mg, 0.053mmol), and AIBN (3mg, 0.018mmol) as an initiator were added in this order to a 200mL polymerization tube equipped with a magnetic stirrer under an argon atmosphere, and the polymerization tube was sealed. A freeze-pump-thaw degassing operation was carried out three times to remove residual oxygen. Finally, after thawing, the polymerization tube was placed in an oil bath preheated to 60 ℃. Polymerizing for 48h, taking a small amount of crude product, removing the solvent, and dissolving in CDCl3In the middle, in1H NMR was used to monitor the conversion of monomer M1 (> 99%, alkenyl signal completely disappeared), followed by cooling to room temperature, quenching, removing solvent under reduced pressure, dissolving the crude product in about 10mL of dichloromethane, reprecipitating in 80mL of anhydrous ether, repeating the procedure three times, and vacuum drying after suction filtration to give pink solid cyclic polymer P (772mg, 89%).
Claims (8)
1. A novel bis-styrene polyether monomer is characterized in that the structure is shown as formula (I):
2. the method for synthesizing a bis-styrene-containing polyether monomer according to claim 1, comprising the steps of synthesis and post-treatment, wherein the method comprises the following steps:
(1) dripping aqueous solution of inorganic strong base into tetrahydrofuran solution mixed by tetraethylene glycol and p-methyl benzene sulfonyl chloride in a double-neck flask provided with a constant pressure dropping funnel and a magnetic stirring rod under the argon atmosphere, stirring for 24 hours at room temperature, and carrying out post-treatment to obtain an intermediate M-1;
the structure of the tetraethylene glycol is shown as a formula (II)
The structure of the p-methyl benzene sulfonyl chloride is shown as a formula (III)
The structure of M-1 is shown as formula (IV)
(2) Under the atmosphere of argon, adding alkali, M-1 and hydroquinone into a double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer, dissolving in acetonitrile, heating for reacting for 15h, and carrying out post-treatment to obtain an intermediate M-2;
the structure of the hydroquinone is shown as a formula (V)
The structure of M-2 is shown as formula (VI)
(3) Under the atmosphere of argon, adding alkali, p-hydroxybenzaldehyde and 1, 2-dibromoethane into a double-mouth flask with a magnetic stirrer, dissolving the mixture in acetonitrile, reacting for 15 hours at room temperature, and performing post-treatment to obtain an intermediate M-3;
the structure of the hydroxybenzaldehyde is shown as a formula (VII)
The structure of the 1, 2-dibromoethane is shown as a formula (VIII)
The structure of M-3 is shown as formula (VIIII)
(4) Under the atmosphere of argon, adding alkali M-3 and M-2 into a double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer, dissolving in DMF, heating for reacting for 15h, and carrying out post-treatment to obtain an intermediate M-4;
the structure of M-4 is shown as the formula (X)
(5) Under the atmosphere of argon, in a double-neck flask provided with a constant-pressure dropping funnel, a spherical condenser tube and a magnetic stirrer, adding sodium hydride into a tetrahydrofuran solution of a wittig reagent in batches, refluxing for 1h, dropwise adding an M-4 tetrahydrofuran solution, continuing reflux reaction for 12h, and performing post-treatment to obtain the bis-styrene polyether monomer.
3. The method of claim 2, wherein the monomer is linear and has styrene end-caps at both ends.
4. The method for synthesizing a bis-styryl-containing polyether monomer according to claim 2, wherein the inorganic strong base in the step (1) is potassium hydroxide, and the base in the steps (2), (3) and (4) is potassium carbonate.
5. The method of claim 2, wherein the heating temperature in step (2) is 80 ℃.
6. The method of claim 2, wherein the heating temperature in step (4) is 130 ℃.
7. The method for synthesizing a bis-styryl-containing polyether monomer as claimed in claim 2, wherein the wittig reagent in the step (5) is triphenylphosphorobromomethane.
8. The use of the bisphenylvinyl polyether containing monomer as claimed in claim 1, wherein the controlled preparation of the copolymer whose backbone contains macrocyclic structure is achieved by maleic anhydride-assisted reversible scission chain transfer polymerization.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786522A (en) * | 2012-07-17 | 2012-11-21 | 广西大学 | Matrine derivative, its preparation method and application |
| CN102977341A (en) * | 2012-11-15 | 2013-03-20 | 南京邮电大学 | Preparation method and application of multiblock conjugated polymer containing phenylene ethylene skeleton |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786522A (en) * | 2012-07-17 | 2012-11-21 | 广西大学 | Matrine derivative, its preparation method and application |
| CN102977341A (en) * | 2012-11-15 | 2013-03-20 | 南京邮电大学 | Preparation method and application of multiblock conjugated polymer containing phenylene ethylene skeleton |
Non-Patent Citations (3)
| Title |
|---|
| GUANGCHEN SUN 等: "Supramolecular Assembly-Driven Color-Tuning and White-Light Emission Based on Crown-Ether-Functionalized Dihydrophenazine", 《ACS APPL. MATER. INTERFACES》 * |
| MICHEL P. L. WERTS 等: "Mechanically Linked Polyrotaxanes: A Stepwise Approach", 《MACROMOLECULES》 * |
| YONG-GUANG JIA 等: "Crown Ether Cavity-Containing Copolymers via Controlled Alternating Cyclocopolymerization", 《MACROMOLECULES》 * |
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