CN110563930A - Diazoacetate monomer activity controllable polymerization method - Google Patents
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- CN110563930A CN110563930A CN201910394617.9A CN201910394617A CN110563930A CN 110563930 A CN110563930 A CN 110563930A CN 201910394617 A CN201910394617 A CN 201910394617A CN 110563930 A CN110563930 A CN 110563930A
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Abstract
The invention discloses an activity-controllable polymerization method of diazoacetate monomers, which mainly utilizes allyl palladium (II) chloride dimer and chiral diphosphine ligand as a catalytic system to realize the activity-controllable polymerization of various diazoacetate monomers, and the obtained polymer has controllable molecular weight and narrower molecular weight distribution, and the polymerization process does not need strict anhydrous and anaerobic conditions, so that the reaction conditions are mild, and the monomers are simple to synthesize and have high yield. The new method for diazoacetate monomer activity controllable polymerization has great application space in organic synthesis, new material synthesis and material modification, and can be used for preparing materials which are widely applied in the fields of biology and high-tech application, such as biological probes, chiral separation materials, photosensitive materials and the like.
Description
Technical Field
The invention belongs to the field of polymer reaction, and particularly relates to a diazoacetate monomer activity controllable polymerization method.
background
diazo organic compounds are a class of organic compounds which can realize unique chemical conversion and have wide application value in organic synthesis. Compared with other compounds, most of themdiazo compounds are a relatively unstable class of compounds which are susceptible to loss of N2And a series of reactions occur following the formation of a carbene or metal carbene. Over the past century, diazo compounds have been favored by chemists. In particular diazoacetic acid esters, have attracted considerable interest because of their advantages over conventional olefin polymerizations.
researches in recent years show that the palladium complex can catalyze diazo compounds to generate novel reactions, the preparation of the polycarbocene from the diazoacetate monomers is a special polymerization, the generated main chain consists of C-C, each carbon of the main chain contains the polycarbocarbene with ester substituent, and the polymer has great application prospects in the biological field and the high-tech field, such as biological probes, chiral separation materials, photosensitive materials and the like.
Disclosure of Invention
The invention aims to provide a diazoacetate monomer activity controllable polymerization method, which takes allyl palladium (II) chloride dimer and diphosphine ligand as a catalytic system, researches the polymerization reaction kinetics of the diazoacetate monomer for the first time, designs the polymerization reaction and tracking reaction kinetics with different polymerization degrees, finds that the obtained polymer has controllable molecular weight and narrower molecular weight distribution, and finds that the reaction accords with the first-order reaction through the kinetic research. The traditional polymerization generally needs heating and anaerobic conditions, the invention does not need strict anhydrous and anaerobic conditions, and the reaction conditions are mild, so the diazoacetate monomer activity controllable polymerization method has great application space in organic synthesis, new material synthesis and material modification, and the method can be used for preparing widely applied materials in the fields of biology and high-tech application, such as biological probes, chiral separation materials, photosensitive materials and the like.
in order to achieve the purpose, the invention provides the following technical scheme:
a diazoacetate monomer activity controllable polymerization method comprises the following steps:
adding a palladium chloride catalytic system into a reaction bottle, adding a polymerization solvent, stirring for 2-3h, injecting a diazoacetate monomer, stirring at room temperature for reaction for 1-14h, adding n-hexane for quenching, precipitating a polymer, washing with n-hexane for 3-5 times, and centrifuging to obtain a yellow precipitate to obtain the poly-carbene L, wherein the palladium chloride catalytic system consists of an allyl palladium chloride (II) dimer and a diphosphine ligand, the catalyst is the allyl palladium chloride (II) dimer, and the structural formula of the palladium chloride catalytic system is as follows:
The structural formula of L is:
A diazoacetate monomer activity controllable polymerization method has a general formula as follows:
Wherein the polymerization degree n is 20-200, and the structure of R is as follows:
Preferably, the molar ratio of allyl palladium (II) chloride dimer to diazoacetate monomer is 1: (20-200).
preferably, the molar ratio of allyl palladium (II) chloride dimer to bisphosphine ligand is 1: 1.
when the dosage of diazoacetate monomer is 50-100mg, the dosage of tetrahydrofuran is 0.5-2 mL.
preferably, the polymerization solvent is tetrahydrofuran.
preferably, the bisphosphine ligand has the structural formula:
The invention has the beneficial effects that:
1. The invention takes allyl palladium (II) chloride dimer and diphosphine ligand as a catalytic system, researches the polymerization kinetics of diazoacetate monomer for the first time, designs polymerization reaction and tracking reaction kinetics with different polymerization degrees, finds that the obtained polymer has controllable molecular weight and narrower molecular weight distribution, and finds that the reaction accords with first-order reaction through kinetic research.
2. The traditional polymerization generally needs heating and anaerobic conditions, the polymerization process of the diazoacetate monomer does not need strict anhydrous and anaerobic conditions, the reaction conditions are mild, the activity controllable polymerization method of the diazoacetate monomer has great application space in organic synthesis, new material synthesis and material modification, and materials which are widely applied in the biological field and the high-tech application field, such as biological probes, chiral separation materials, photosensitive materials and the like, can be prepared by the method.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of diazoacetate monomers 1 and 5 in examples 1 and 5 of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the polycarbonylpoly-1, poly-5 in examples 1, 5 of the present invention.
FIGS. 3(a) and (b) are graphs showing the relationship between the molecular weight of the polycarbonylpoly-1 and PDI in example 1 of the present invention; (c) and (d) are respectively the conversion rate and the first-order kinetic diagram of the diazoacetate monomers 1 and 5 in the examples 1 and 5.
FIGS. 4(a) and (b) are liquid phase diagrams of diazoacetate monomers 1 and 5 in examples 1 and 5, respectively, at different reaction times.
FIGS. 5(a) and (b) are graphs showing the relationship between the molecular weight of the polycarbonylpoly-2 and PDI in example 2 of the present invention; (c) and (d) is the conversion rate and first order kinetic diagram of diazoacetate monomer 2.
FIGS. 6(a) and (b) are graphs showing the molecular weight, PDI and degree of polymerization of the polycarbonylpoly-3 in example 3 of the present invention; (c) is a graph of the molecular weight and PDI of the polycarbonylpoly-3 as a function of conversion; (d) is the conversion rate and the first-order kinetic diagram of the diazoacetate monomer 3.
FIG. 7 is a nuclear magnetic hydrogen spectrum of diazoacetate monomer 2 of example 2 of the present invention.
FIG. 8 is a nuclear magnetic hydrogen spectrum of the polymer poly-2 obtained in example 2 of the present invention.
FIG. 9 is a nuclear magnetic hydrogen spectrum of diazoacetate monomer 3 of example 3 in the present invention.
FIG. 10 is a nuclear magnetic hydrogen spectrum of poly-3, a polymer obtained in example 3 of the present invention.
FIG. 11 is the nuclear magnetic hydrogen spectrum of diazoacetate monomer 4 of example 4 in the present invention
FIG. 12 is a nuclear magnetic hydrogen spectrum of the polymer poly-4 prepared in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The process for preparing the polycarbonylpoly with the polymerization degrees of 20, 40, 60, 80, 100, 120, 160 and 200 by catalyzing a target product III by using an allyl palladium (II) chloride dimer and a diphosphine system is as follows, and the amounts of the catalyst and the ligand required when the monomer is fed by 0.56mol are as follows:
adding 35mg of palladium catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
taking eight clean screw bottles, numbering the bottles firstly to eight, adding 0.56mol of diazoacetate monomer into the bottles respectively, taking 1.028mL, 0.514mL, 0.342mL, 0.258mL, 0.206mL, 0.171mL, 0.129mL and 0.102mL of catalyst solution by using a liquid transfer gun, sequentially adding the catalyst solution into the bottles firstly to eight screw bottles, and stirring the mixture at room temperature for reaction for 2 hours;
And (3) removing part of THF by spinning, precipitating the polymer by using n-hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the THF, precipitating the n-hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer.
example 1
the process for preparing the polycarbonylpoly-1 with the polymerization degree of 20 by catalyzing a target product III by using an allyl palladium (II) chloride dimer and a diphosphine system is as follows:
Adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
taking another clean screw bottle, adding 107mg of diazoacetate monomer 1, taking 1.028mL of allyl palladium (II) chloride dimer catalyst solution by using a pipette, sequentially adding the solution into the screw bottle, and stirring at room temperature for reaction for 2 hours;
and (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using n-hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the n-hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-1.
the diazoacetate monomer has the following kinetic steps:
107mg of diazoacetate monomer 1(0.56mol) and 14mg of p-1, 4-dimethoxyether are weighed in a screw bottle, 1.8mL of tetrahydrofuran solvent is added, sampling is carried out after uniform stirring to measure a liquid phase, allyl palladium (II) chloride dimer/diphosphine ligand (0.0056mol) is dissolved in 0.2mL of tetrahydrofuran and added into the screw bottle, polymerization reaction is carried out under stirring, and sampling is carried out at 0min, 10min, 30min, 60min, 90min and 120min to measure HPLC. The test calculates the conversion of monomer 1 based on the internal standard versus dimethyl terephthalate calibration curve and the peak area corresponding to unreacted monomer 1, and the Mn and Mw/Mn are estimated by SEC-which is reported as corresponding to the PSt standard.
the route for preparing the polymer poly-1 by catalyzing the diazoacetate monomer 1 is as follows:
the structural formula of the palladium chloride catalytic system is as follows:
Example 2
The process for preparing the polycarbonylpoly-2 with the polymerization degree of 40 by catalyzing a target product III by using an allyl palladium (II) chloride dimer and a diphosphine system is as follows:
Adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
another clean screw bottle is taken, 99mg of diazoacetate monomer 2 is added into each bottle, 0.514mL of allyl palladium (II) chloride dimer catalyst solution is taken by a pipette and added into the second screw bottle in sequence, and the mixture is stirred and reacts for 2 hours at room temperature;
and (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-2.
The diazoacetate monomer dynamic test process is as follows:
Diazoacetate monomer 2(0.56mol) and 14mg of p-1, 4-dimethoxyether were weighed in a screw bottle, 1.8mL of tetrahydrofuran as a solvent was added, and after stirring uniformly, a liquid phase was sampled, allyl palladium (II) chloride dimer/bisphosphine ligand (0.0056mol) was dissolved in 0.2mL of tetrahydrofuran and added to the above screw bottle, polymerization was stirred, and HPLC was measured by sampling at 60s, 90s, 120s, 180s, 240s, and the like. The test calculates the conversion of monomer 2 based on the internal standard versus dimethyl terephthalate calibration curve and the peak area corresponding to unreacted monomer 2, the Mn and Mw/Mn being estimated by SEC as corresponding to the PSt standard.
the kinetic procedures of monomers 3-8 were carried out in accordance with this method, with samples taken at various times to test the kinetics of diazoacetate monomers, and are not described in detail in the examples below.
Example 3
the process for preparing the polycarbonylpoly-3 with the polymerization degree of 60 by catalyzing the target product III by the allyl palladium (II) chloride dimer and the diphosphine system is as follows:
adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
Another clean screw bottle is taken, 95mg of diazoacetate monomer 3 is added into each bottle, 0.342mL of allyl palladium (II) chloride dimer catalyst solution is taken by a pipette and added into the second screw bottle in sequence, and the mixture is stirred and reacts for 2 hours at room temperature;
and (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-3.
example 4
the process for preparing the polycarbonylpoly-4 with the polymerization degree of 80 by catalyzing the target product III by the allyl palladium (II) chloride dimer and the diphosphine system is as follows:
Adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
Another clean screw bottle is taken, 130mg of diazoacetate monomer 4 is added into each bottle, 0.258mL of allyl palladium (II) chloride dimer catalyst solution is taken by a pipette and added into the second screw bottle in sequence, and the mixture is stirred and reacts for 2 hours at room temperature;
And (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-4.
Example 5
the process for preparing the polycarbonylpoly-5 with the polymerization degree of 100 by catalyzing the target product III by the allyl palladium (II) chloride dimer and the diphosphine system is as follows:
adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
taking another clean screw bottle, adding 107mg of diazoacetate monomer 5, taking 0.206mL of allyl palladium (II) chloride dimer catalyst solution by using a pipette, sequentially adding the solution into the second screw bottle, and stirring at room temperature for reacting for 2 hours;
And (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-5.
Example 6
the process for preparing the polycarbonylpoly-6 with the polymerization degree of 120 by catalyzing the target product III by the allyl palladium (II) chloride dimer and the diphosphine system is as follows:
Adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
another clean screw bottle is taken, 91mg of diazoacetate monomer 6 is added, 0.171mL of allyl palladium (II) chloride dimer catalyst solution is taken by a pipette and sequentially added into the second screw bottle, and the mixture is stirred and reacts for 2 hours at room temperature;
and (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-6.
example 7
the process for preparing the poly-carbene-poly-7 with the polymerization degree of 160 by catalyzing the target product III by the allyl palladium (II) chloride dimer and the diphosphine system is as follows:
Adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
Adding 136mg of diazoacetate monomer 7 into another clean screw bottle, taking 0.129mL of allyl palladium (II) chloride dimer catalyst solution by using a pipette, sequentially adding into the second screw bottle, and stirring at room temperature for reacting for 2 h;
And (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-7.
Example 8
the process for preparing the polycarbonylpoly-8 with the polymerization degree of 200 by catalyzing a target product III by using an allyl palladium (II) chloride dimer and a diphosphine system is as follows:
Adding 35mg of allyl palladium (II) chloride dimer catalyst and 55.3mg of diphosphine ligand into a screw bottle, adding 3.5mL of tetrahydrofuran, and stirring for 2-3 h;
adding 142mg of diazoacetate monomer 8 into another clean screw bottle, taking 0.102mL of allyl palladium (II) chloride dimer catalyst solution by using a pipette, sequentially adding the solution into the second screw bottle, and stirring at room temperature for reacting for 2 hours;
And (3) removing part of tetrahydrofuran by spinning, precipitating the polymer by using normal hexane, centrifuging to remove supernatant, dissolving the obtained solid by using the tetrahydrofuran, precipitating the normal hexane, repeating the steps for 3-4 times, and pumping the obtained solid to obtain the polymer poly-8.
In summary, the general polymerization reaction is as follows:
In the formula (I), the compound is shown in the specification,
wherein the polymerization degree n is 20-200, and the structure of R is as follows:
the structural formula of the diphosphine ligand is as follows:
a small amount of polymer with different polymerization degrees was dissolved in tetrahydrofuran to obtain a gel chromatogram, as shown in FIG. 3.
1-8 diazoacetate monomers can be fed by using the catalyst system according to the molar ratio to realize the activity controllable polymerization of the diazoacetate monomers.
FIG. 1 is a nuclear magnetic hydrogen spectrum of diazoacetate monomer 1 in example 1 of the present invention; in the figure, the unique sum of the benzene ring and the side chain hydrogen is identical with the structural formula, and the purity of the synthesized monomer has no influence on the polymerization.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the polycarbonylpoly-1 in example 1 of the present invention; the positions of the various hydrogens in the figure are almost unchanged, and the peaks are changed into peaks of wrapping and no monomer, which shows that the monomer polymerization in the air is rapid and thorough, and the allyl palladium (II) chloride dimer and diphosphine ligand catalyst system is relatively stable, mild and efficient.
FIGS. 3(a) and (b) are graphs showing the relationship between the molecular weight and the degree of polymerization of the polycarbonylpoly-1 and the molecular weight distribution in example 1 of the present invention; the molecular weight is linearly increased along with the increase of the polymerization degree, and the molecular weight distribution is narrower, so that the controllable polymerization is realized. (c) And (d) are respectively the conversion rate of the diazoacetate monomers 1 and 5 in the examples 1 and 5 along with the time and the corresponding first-order kinetic diagram; it can be seen from the figure that the diazoacetate monomer is polymerized according to the first-order kinetic process, and belongs to living polymerization.
FIGS. 4(a) and (b) are liquid phase diagrams of diazoacetate monomers 1 and 5 in examples 1 and 5, respectively, at different reaction times; under the condition of adding the internal standard, the internal standard does not participate in the reaction in the polymerization process, and the volume of the monomer which does not participate in the reaction is integrated.
FIGS. 5(a) and (b) are graphs of the molecular weight of polycarbonylpoly-2 as a function of time and PDI in example 2 of the present invention; the molecular weight is linearly increased along with the increase of time, the molecular weight distribution is narrow, and the controllable polymerization characteristic is realized; (c) and (d) respectively shows the conversion rate and a first-order kinetic diagram of the diazoacetate monomer 2: it can be seen from the figure that the diazoacetate monomer is polymerized and conforms to the first order kinetic process, and the polymerization activity is controllable.
FIGS. 6(a) and (b) are graphs of the molecular weight of polycarbonylpoly-3 as a function of time and PDI in example 3 of the present invention; the molecular weight is linearly increased along with the increase of time, the molecular weight distribution is narrow, and the controllable polymerization characteristic is realized; (c) and (d) respectively shows the conversion rate and a first-order kinetic diagram of the diazoacetate monomer 2: it can be seen from the figure that the diazoacetate monomer 2 polymerizes and follows a first order kinetic process, and is living polymerization.
FIGS. 7 and 8 are nuclear magnetic hydrogen spectrograms of diazoacetate monomer 2 and the corresponding polymer, respectively. It can be seen that the monomer is polymerized efficiently and rapidly under the catalyst system of allyl palladium (II) chloride dimer and diphosphine ligand.
FIGS. 9 and 10 are the nuclear magnetic hydrogen spectrum of diazoacetate monomer 3 and the nuclear magnetic hydrogen spectrum of the corresponding polymer, respectively.
FIGS. 11 and 12 are the nuclear magnetic hydrogen spectrum of diazoacetate monomer 4 and the nuclear magnetic hydrogen spectrum of the corresponding polymer, respectively.
The foregoing is merely exemplary and illustrative of the present invention, and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
Claims (7)
1. A diazoacetate monomer activity-controllable polymerization method is characterized by comprising the following steps:
adding a palladium chloride catalytic system into a reaction bottle, adding a polymerization solvent, stirring for 2-3h, injecting a diazoacetate monomer, stirring at room temperature for reaction for 1-14h, adding n-hexane for quenching, precipitating a polymer, washing with n-hexane for 3-5 times, and centrifuging to obtain a yellow precipitate to obtain the poly-carbene L, wherein the palladium chloride catalytic system consists of an allyl palladium chloride (II) dimer and a diphosphine ligand, the catalyst is the allyl palladium chloride (II) dimer, and the structural formula of the palladium chloride catalytic system is as follows:
The structural formula of L is:
2. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the polymerization reaction has the general formula:
wherein the polymerization degree n is 20-200, and the structure of R is as follows:
3. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the molar ratio of allyl palladium (II) chloride dimer to diazoacetate monomers is 1: (20-200).
4. the method for the activity-controlled polymerization of diazoacetate monomers as claimed in claim 1, wherein the molar ratio of allyl palladium (II) chloride dimer to diphosphine ligand is 1: 1.
5. The method for the controlled polymerization of diazoacetate monomer activity as claimed in claim 1, wherein when the amount of diazoacetate monomer is 50-100mg, the amount of tetrahydrofuran added is 0.5-2 mL.
6. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the polymerization solvent is tetrahydrofuran.
7. The method for the controlled-activity polymerization of diazoacetate monomers as claimed in claim 1, wherein the diphosphine ligand has the structural formula:
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| CN115558087A (en) * | 2022-11-09 | 2023-01-03 | 合肥工业大学 | Optically active spiral polycarbobin, preparation method thereof and post-polymerization modification method |
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| JP2008031304A (en) * | 2006-07-28 | 2008-02-14 | Fujifilm Corp | Film by using norbornene copolymer, polarizing plate, liquid crystal display, and norbornene copolymer |
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| JP2008031304A (en) * | 2006-07-28 | 2008-02-14 | Fujifilm Corp | Film by using norbornene copolymer, polarizing plate, liquid crystal display, and norbornene copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115558087A (en) * | 2022-11-09 | 2023-01-03 | 合肥工业大学 | Optically active spiral polycarbobin, preparation method thereof and post-polymerization modification method |
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Application publication date: 20191213 |