CN108059690B - Initiation system containing alkyl trifluoroborate and method for initiating monomer polymerization by using initiation system - Google Patents

Initiation system containing alkyl trifluoroborate and method for initiating monomer polymerization by using initiation system Download PDF

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CN108059690B
CN108059690B CN201711384737.8A CN201711384737A CN108059690B CN 108059690 B CN108059690 B CN 108059690B CN 201711384737 A CN201711384737 A CN 201711384737A CN 108059690 B CN108059690 B CN 108059690B
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alkyl trifluoroborate
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张乾
蒋云月
刘坤
齐菲
张佳妮
李鹏飞
丁思懿
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Xian University of Technology
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    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
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Abstract

The invention discloses an initiation system containing alkyl trifluoroborate, which takes alkyl trifluoroborate, silver oxide and water as the initiation system of free radical polymerization reaction, and a method for initiating monomer polymerization, comprising the following steps: step 1: purifying the monomer; step 2: under the condition that alkyl trifluoroborate, silver oxide and water are used as an initiating system of free radical polymerization reaction, carrying out polymerization reaction on the monomer purified in the step 1 by a bulk polymerization method or a solution polymerization method; and step 3: and (3) dissolving the product obtained in the step (2) with tetrahydrofuran or water, centrifuging to obtain a supernatant, purifying, dripping the purified supernatant into methanol or petroleum ether, precipitating, and vacuum-drying the obtained precipitate to obtain the polymer product. The invention powerfully proves that the alkyl trifluoroborate has the condition of being used as an initiator, the polymerization time is short, and the polymer is easy to purify; the method is simple and convenient, and the alkyl trifluoroborate can effectively initiate the polymerization of the monomers.

Description

Initiation system containing alkyl trifluoroborate and method for initiating monomer polymerization by using initiation system
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to an initiating system containing alkyl trifluoroborate, and a method for initiating monomer polymerization by using the initiating system containing alkyl trifluoroborate.
Background
Radical polymerization is a method for obtaining polymers by continuous addition polymerization, is an extremely important part of polymer science, and is also a polymerization reaction which is well studied nowadays. Currently, more than half of the polymers are obtained by free radical polymerization, such as polyvinyl chloride, polystyrene, polymethyl methacrylate, polyacrylonitrile, nitrile rubber, styrene butadiene rubber, and the like.
The total reaction of free radical polymerization consists of four parts, chain initiation, chain growth, chain transfer and chain termination, wherein the chain initiation is a key step for controlling the polymerization rate and molecular weight, and an initiator playing a role in initiation is the core of the initiation reaction. The initiator should have a property of being easily decomposed into radicals, and the common initiators include azo type initiators, organic peroxide initiators, inorganic peroxide initiators, and oxidation-reduction initiation systems (e.g., Fe)2+And H2O2The reaction is capable of producing HO) is also capable of producing free radicals, also of the type of initiator.
The redox initiation system has low activation energy and has the advantage of initiating the polymerization of monomers at a lower temperature, and can be divided into a water-soluble redox initiation system and an oil-soluble redox initiation system according to the solubility of the redox initiation system. In the patent, alkyl trifluoroborate, silver oxide and water can generate free radicals at room temperature[1]And initiating free radical polymerization reaction, and can effectively initiate polymerization under heating condition for monomer styrene with low reactivity, thereby providing a novel oxidation-reduction initiation system for free radical polymerization.
Disclosure of Invention
The invention aims to provide an initiation system containing alkyl trifluoroborate, the reaction system has fast reaction at room temperature, the molecular weight of the polymer is larger, the polymerization time of the free radical polymerization reaction in which the alkyl trifluoroborate participates as a free radical polymerization initiator is short, and the polymer is easy to purify.
It is another object of the present invention to provide a method for initiating polymerization of monomers using an initiation system comprising an alkyl trifluoroborate salt.
The technical scheme adopted by the invention is that an initiating system containing alkyl trifluoroborate takes the alkyl trifluoroborate, silver oxide and water as the initiating system for free radical polymerization reaction.
The invention is also characterized in that:
the alkyl trifluoroborate has the structural formula:
Figure BDA0001516387530000021
Figure BDA0001516387530000022
one kind of (1).
The invention adopts another technical scheme that the method for initiating the monomer polymerization by the initiation system containing the alkyl trifluoroborate comprises the following steps:
step 1: purifying the monomer;
step 2: under the condition that alkyl trifluoroborate, silver oxide and water are used as an initiating system of free radical polymerization reaction, carrying out polymerization reaction on the monomer purified in the step 1 by a bulk polymerization method or a solution polymerization method;
and step 3: and (3) dissolving the product obtained in the step (2) by using a solvent A, centrifuging to obtain a supernatant, purifying, dropwise adding the purified supernatant into a solvent B, precipitating, and vacuum-drying the obtained precipitate to obtain the polymer product.
The invention is also characterized in that:
in the step 1, the monomer is one of polyethylene glycol methyl ether methacrylate, acrylamide, methyl methacrylate, methyl acrylate, butyl acrylate or styrene.
In step 2, the structural formula of the alkyl trifluoroborate is as follows:
Figure BDA0001516387530000031
Figure BDA0001516387530000032
Figure BDA0001516387530000033
one kind of (1).
In step 3, the purification process of the supernatant is as follows: passing the monomer through a neutral alumina column connected with a polyethersulfone or polytetrafluoroethylene filter head to obtain purified supernatant; the volume ratio of the purified supernatant to the solvent B is 1: 9; the resulting precipitate was dried under vacuum for 24 hours.
In the step 3, the solvent A is tetrahydrofuran or water; the solvent B is methanol or petroleum ether.
In step 2, the process of polymerizing the monomer purified in step 1 by a bulk polymerization method is as follows: and (2) placing the monomer purified in the step (1) into a reaction bottle, then adding alkyl trifluoroborate, silver oxide and water into the reaction bottle, sealing the reaction bottle, removing oxygen, filling nitrogen after removing oxygen, and stirring.
In step 2, the process of polymerizing the monomer purified in step 1 by a solution polymerization method is as follows: putting the monomer purified in the step 1 and tetrahydrofuran with equal mass or putting the monomer purified in the step 1 and deionized water with equal mass into a reaction bottle, then adding alkyl trifluoroborate, silver oxide and water into the reaction bottle, sealing the reaction bottle, removing oxygen, filling nitrogen after removing oxygen, and stirring.
The molar ratio of the monomer to the alkyl trifluoroborate is 1: 0.004-1: 0.041; the molar ratio of the alkyl trifluoroborate to the silver oxide was 1: 0.8.
The beneficial results of the initiation system containing alkyl trifluoroborate and the method for initiating the polymerization of the monomer of the initiation system are as follows:
(1) the alkyl trifluoroborate, the silver oxide and the water can generate free radicals at room temperature and initiate free radical polymerization reaction, and can effectively initiate polymerization under heating condition for monomer styrene with lower reactivity, so that a novel oxidation-reduction initiation system is provided for the free radical polymerization;
(2) the adoption of the undecyl trifluoroborate strongly proves that the alkyltrifluoroborate has the condition as an initiator through the polymerization reaction of the monomers, the polymerization time is short, and the polymer is easy to purify;
(3) the method is simple and convenient, and the alkyl trifluoroborate can not only effectively initiate the polymerization of the monomer, but also bring different end groups to the polymer, thereby providing convenience for further modification of the polymer.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to an initiation system containing alkyl trifluoroborate, which takes the alkyl trifluoroborate, silver oxide and water as the initiation system of free radical polymerization.
The structural formula of the alkyl trifluoroborate is R1～R11Any one of (1), R1～R11The following structural formula is shown in sequence:
Figure BDA0001516387530000051
the method for initiating the polymerization of the monomer by using the initiating system containing the alkyl trifluoroborate comprises the following steps:
step 1: purifying the monomer;
in the step 1, the monomer is one of polyethylene glycol methyl ether methacrylate, acrylamide, methyl methacrylate, methyl acrylate, butyl acrylate or styrene;
step 2: under the condition that alkyl trifluoroborate, silver oxide and water are used as an initiating system of free radical polymerization reaction, carrying out polymerization reaction on the monomer purified in the step 1 by a bulk polymerization method or a solution polymerization method;
in step 2, the alkyl trifluoroborate has the structural formula:
Figure BDA0001516387530000061
Figure BDA0001516387530000062
one of (1);
in step 2, the process of polymerizing the monomer purified in step 1 by a bulk polymerization method is as follows: placing the monomer purified in the step 1 into a reaction bottle, then adding alkyl trifluoroborate, silver oxide and water into the reaction bottle, sealing the reaction bottle, deoxidizing, filling nitrogen after deoxidizing, and stirring;
in step 2, the process of polymerizing the monomer purified in step 1 by a solution polymerization method is as follows: putting the monomer purified in the step 1 and tetrahydrofuran with equal mass or putting the monomer purified in the step 1 and deionized water with equal mass into a reaction bottle, then adding alkyl trifluoroborate, silver oxide and water into the reaction bottle, sealing the reaction bottle, removing oxygen, filling nitrogen after removing oxygen, and stirring;
wherein the molar ratio of the monomer to the alkyl trifluoroborate is 1: 0.004-1: 0.041; the molar ratio of the alkyl trifluoroborate to the silver oxide is 1: 0.8;
and step 3: dissolving the product obtained in the step 2 by using a solvent A, centrifuging to obtain a supernatant, purifying, dropwise adding the purified supernatant into a solvent B, precipitating, and vacuum-drying the obtained precipitate to obtain a polymer product;
in step 3, the purification process of the supernatant is as follows: passing the monomer through a neutral alumina column connected with a polyethersulfone or polytetrafluoroethylene filter head to obtain purified supernatant; the volume ratio of the purified supernatant to the solvent B is 1: 9; the obtained precipitate is dried in vacuum for 24 hours;
in the step 3, the solvent A is tetrahydrofuran or water; the solvent B is methanol or petroleum ether.
The reaction principle of initiating the monomer polymerization by an initiating system containing the alkyl trifluoroborate is as follows: initiating monomer polymerization by an initiation system containing a plurality of alkyl trifluoroborate compounds, and introducing a specific functional end group at a polymer end by utilizing initiator fragments; alkyl trifluoroborate connected with different end groups initiates polymerization reaction in the presence of silver oxide and water, and the structural formula of the alkyl trifluoroborate and the process for generating active species are as follows:
Figure BDA0001516387530000071
example 1:
purifying styrene by passing through basic or neutral alumina column connected with polytetrafluoroethylene filter head, measuring purified (0.442mL, 3.841mmol, 1.000eq.) styrene monomer, and purifyingIt was placed in a Schlenk bottle and (19.0mg, 0.024eq.) R was added sequentially1、(17.0mg，0.019eq.)Ag2O and 40 mu L of deionized water are sealed by a rubber plug, oxygen is removed by a three-time freezing-vacuumizing-dissolving circulation method, nitrogen is filled after oxygen is removed, the reaction is stirred in the dark at 90 ℃, the reaction is stopped after 4 hours, the mixture after the reaction is dissolved by THF, the precipitate is removed by centrifugation, and the solution passes through a neutral alumina column with a polyether sulfone filter head to obtain colorless transparent solution. Dripping the solution into stirred methanol dropwise for precipitation for three times, centrifuging to obtain white solid, drying in a vacuum oven for 24h to obtain white polystyrene, and reacting
The formula is as follows:
Figure BDA0001516387530000072
example 2:
purifying polyethylene glycol methyl ether methacrylate by an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring a purified (0.952mL, 9.988mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and sequentially adding (10.0mg, 0.005eq.) R1、(9.0mg，0.004eq.) Ag2O and 1.000mL of deionized water are sealed by a rubber plug, oxygen is removed by a three-time freezing-vacuumizing-dissolving circulation method, nitrogen is filled after oxygen is removed, the reaction is stirred at room temperature in a dark place, the viscosity is obviously increased at the beginning of the reaction, and the reaction is stopped after 30min when magnetons are not stirred. The reacted mixture was dissolved in THF, the precipitate was removed by centrifugation, and the solution was passed through a neutral alumina column with a Teflon filter to give a colorless transparent solution. The solution is dripped into petroleum ether which is stirred, and the solution is precipitated for three times and centrifuged to obtain transparent solid.
Example 3:
acrylamide (0.200g, 2.814mmol, 1.000eq.) was measured, placed in a Schlenk bottle, and R (8.3mg, 0.014eq.) was added sequentially1、(7.4mg，0.011eq.)Ag2O and 0.200mL of deionized water are sealed by a rubber plug, oxygen is removed by a method of three times of freezing-vacuumizing-dissolving circulation, nitrogen is filled after oxygen is removed, the reaction is stirred at room temperature in a dark place and is carried out for 1 hourThe viscosity was higher after the reaction, and the reaction was stopped after 2 hours. The reacted mixture was dissolved in water, the precipitate was removed by centrifugation, and the solution was passed through a neutral alumina column with a polyethersulfone filter head to give a colorless transparent solution. The solution was dropwise added to petroleum ether under stirring to precipitate three times, and the mixture was centrifuged to obtain a white solid.
Example 4:
butyl acrylate was purified by passing it through an alkaline or neutral alumina column attached to a polytetrafluoroethylene frit, the purified (1.119mL, 7.802mmol, 1.000eq.) monomer was weighed out, placed in a Schlenk flask, and (23.0mg, 0.014eq.) R was added sequentially1、(20.6mg，0.011eq.)Ag2O, (1.126mL) tetrahydrofuran and 100 μ L deionized water, sealed by a rubber plug, deoxygenated by three cycles of freezing, vacuumizing and dissolving, filled with nitrogen after deoxygenation, stirred at room temperature in the dark for reaction, stopped after 4h, the reacted mixture was dissolved with THF, the precipitate was removed by centrifugation, and the solution was passed through a neutral alumina column with a Teflon filter to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless and transparent polybutyl acrylate. The reaction formula is as follows:
Figure BDA0001516387530000091
example 5:
the methyl acrylate monomer was purified by passing through an alkaline or neutral alumina column connected to a polytetrafluoroethylene filter head, and the purified (0.524mL, 5.808mmol, 1.000eq.) monomer was measured and placed in a Schlenk bottle, and (16.7mg, 0.015eq.) R was added in order2、(16.2mg，0.011eq.)Ag2O, (0.563mL) tetrahydrofuran and 50 μ L deionized water, sealed with a rubber plug, deoxygenated by three freezing-vacuum-dissolving cycles, charged with nitrogen after deoxygenation, stirred and reacted at room temperature in the dark, stopped after 2h11min, the reacted mixture was dissolved with THF, centrifuged to remove the precipitate, and the solution was passed through a neutral alumina column with a polyethersulfone filter to obtain a colorless clear solutionAnd (4) clear solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless and transparent polymethyl acrylate. The reaction formula is as follows:
Figure BDA0001516387530000092
example 6:
purifying butyl acrylate monomer through an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.559mL, 3.901mmol, 1.000eq.) monomer, placing the monomer into a Schlenk bottle, and sequentially adding (8.7mg, 0.015eq.) R3、(10.9mg，0.012eq.)Ag2O and 50 mu L of deionized water are sealed by a rubber plug, oxygen is removed by a three-time freezing-vacuumizing-dissolving circulation method, nitrogen is filled after oxygen is removed, the reaction is stirred at room temperature in the dark, the reaction is stopped after 4 hours, the mixture after the reaction is dissolved by THF, the precipitate is removed by centrifugation, and the solution passes through a neutral alumina column with a polytetrafluoroethylene filter head to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless and transparent polybutyl acrylate.
Example 7:
the methyl acrylate monomer was purified by passing through an alkaline or neutral alumina column connected to a polytetrafluoroethylene filter head, and the purified (0.336mL, 3.485mmol, 1.000eq.) monomer was measured and placed in a Schlenk bottle, and (11.5mg, 0.015eq.) R was added in order4、(9.8mg，0.012eq.)Ag2O, (0.338mL) tetrahydrofuran and 30 μ L deionized water, sealed by a rubber plug, deoxygenated by a three-time freezing-vacuumizing-dissolving cycle method, filled with nitrogen after deoxygenation, stirred and reacted at room temperature in the dark, stopped after 6h and 11min, the reacted mixture was dissolved by THF, and the precipitate was removed by centrifugation, and the solution was passed through a neutral alumina column with a polyethersulfone filter to obtain a colorless transparent solution. Dripping the solution into stirred methanol dropwise for precipitation for three times, centrifuging to obtain transparent solid, and placing in a vacuum ovenDrying for 24h to obtain colorless transparent polymethyl acrylate.
Example 8:
purifying methyl methacrylate monomer by an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.213mL, 1.998mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and adding (6.6mg, 0.015eq.) R in turn4、(5.6mg，0.012eq.) Ag2O and 20 mu L of deionized water are sealed by a rubber plug, oxygen is removed by a three-time freezing-vacuumizing-dissolving circulation method, nitrogen is filled after oxygen is removed, the reaction is stirred at room temperature in the dark, the reaction is stopped after 70min, the mixture after the reaction is dissolved by THF, the precipitate is removed by centrifugation, and the solution passes through a neutral alumina column with a polytetrafluoroethylene filter head to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a white solid, and drying in a vacuum oven for 24 hours to obtain white polymethyl methacrylate. The reaction formula is as follows:
Figure BDA0001516387530000111
example 9:
purifying butyl acrylate monomer through an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.560mL, 3.901mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and sequentially adding (21.6mg, 0.015eq.) R5、(10.9mg，0.012eq.)Ag2O, (0.563mL) tetrahydrofuran and 50. mu.L of deionized water were sealed with a rubber stopper, deoxygenated by three cycles of freezing, vacuum-pumping and dissolution, and then nitrogen was introduced after deoxygenation, the reaction was stopped after 5 hours with stirring at room temperature in the dark, the reacted mixture was dissolved with THF, the precipitate was removed by centrifugation, and the solution was passed through a neutral alumina column with a polyethersulfone filter to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a colorless transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless transparent polybutyl acrylate.
Example 10:
purifying butyl acrylate monomer through an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.560mL, 3.901mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and sequentially adding (12.0mg, 0.015eq.) R6、(11.1mg，0.012eq.)Ag2O and 50 mu L of deionized water are sealed by a rubber plug, oxygen is removed by three times of Freeze-pump-thaw cycles, nitrogen is filled after oxygen removal, the reaction is stirred at room temperature in the dark, the reaction is stopped after 4.5h, the mixture after the reaction is dissolved by THF, the precipitate is removed by centrifugation, and the solution passes through a neutral alumina column with a polyether sulfone filter head to obtain colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a colorless transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless transparent polybutyl acrylate.
Example 11:
purifying methyl methacrylate monomer by an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.532mL, 4.994mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and adding (73.0mg, 0.051eq.) R in turn7、(47.0mg，0.041eq.) Ag2O and 50 mu L of deionized water are sealed by a rubber plug, oxygen is removed by a three-time freezing-vacuumizing-dissolving circulation method, nitrogen is filled after oxygen removal, the reaction is stirred at room temperature in the dark, the reaction is stopped after 3.5h, the mixture after the reaction is dissolved by THF, the precipitate is removed by centrifugation, and the solution passes through a neutral alumina column with a polytetrafluoroethylene filter head to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a white solid, and drying in a vacuum oven for 24 hours to obtain white polymethyl methacrylate.
Example 12:
purifying methyl acrylate monomer through an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.314mL, 3.485mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and sequentially adding (10.0mg, 0.015eq.) R8、(9.8mg，0.012eq.)Ag2O and 30. mu.L of deionized water, with rubberSealing the plug, removing oxygen by a three-time freezing-vacuumizing-dissolving circulation method, introducing nitrogen after oxygen removal, stirring and reacting at room temperature in a dark place, stopping the reaction after 3h50min, dissolving the mixture after the reaction by using THF, centrifuging to remove precipitates, and passing the solution through a neutral alumina column with a polytetrafluoroethylene filter head to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a colorless transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless transparent polymethyl acrylate.
Example 13:
purifying butyl acrylate monomer through an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.336mL, 2.341mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and sequentially adding (9.0mg, 0.015eq.) R9、(6.6mg，0.012eq.)Ag2O, (0.338mL) tetrahydrofuran and 30 μ L deionized water, sealed by a rubber plug, deoxygenated by three freezing-vacuumizing-dissolving cycles, charged with nitrogen after deoxygenation, stirred at room temperature in the dark for reaction, stopped after 2h, the reacted mixture was dissolved with THF, the precipitate was removed by centrifugation, and the solution was passed through a neutral alumina column with a polyethersulfone filter to obtain a colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a colorless transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless transparent polybutyl acrylate.
Example 14:
purifying the monomer by passing through an alkaline or neutral alumina column connected with a polytetrafluoroethylene filter head, measuring the purified (0.190mL, 1.998mmol, 1.000eq.) monomer, placing the monomer in a Schlenk bottle, and adding (6.6mg, 0.015eq.) R in turn10、(5.4mg，0.012eq.)Ag2O and 200 mu L of deionized water are sealed by a rubber plug, oxygen is removed by a three-time freezing-vacuumizing-dissolving circulation method, nitrogen is filled after oxygen is removed, the reaction is stirred at room temperature in a dark place, the reaction is observed to be increasingly sticky, and the reaction is stopped after 10 min. Dissolving the reacted mixture with THF, centrifuging to remove precipitate, and passing the solution through neutral alumina column with polytetrafluoroethylene filter head to obtain the final productA color clear solution. The solution is dripped into petroleum ether which is stirred to precipitate for three times, and the colorless transparent solid is obtained after centrifugation.
Example 15:
the methyl acrylate monomer was purified by passing through an alkaline or neutral alumina column connected to a polytetrafluoroethylene filter head, and the purified (0.319mL, 3.485mmol, 1.000eq.) monomer was measured and placed in a Schlenk bottle, and (25.3mg, 0.033eq.) R was added in order11、(21.4mg，0.026eq.)Ag2O and 30 mu L of deionized water are sealed by a rubber plug, oxygen is removed by three times of Freeze-pump-thaw cycles, nitrogen is filled after oxygen removal, the reaction is stirred at room temperature in the dark, the reaction is stopped after 6h, the mixture after the reaction is dissolved by THF, the precipitate is removed by centrifugation, and the solution passes through a neutral alumina column with a polytetrafluoroethylene filter head to obtain colorless transparent solution. And dropwise adding the solution into stirred methanol to precipitate for three times, centrifuging to obtain a colorless transparent solid, and drying in a vacuum oven for 24 hours to obtain colorless transparent polymethyl acrylate.
The invention has the advantages that:
(1) the alkyl trifluoroborate, the silver oxide and the water can generate free radicals at room temperature[1]And initiating free radical polymerization reaction, and effectively initiating polymerization under heating condition for monomer styrene with low reactivity, thereby providing a novel oxidation-reduction initiation system for free radical polymerization;
(2) the adoption of the undecyl trifluoroborate strongly proves that the alkyltrifluoroborate has the condition as an initiator through the polymerization reaction of the monomers, the polymerization time is short, and the polymer is easy to purify;
(3) the method is simple and convenient, and the alkyl trifluoroborate can not only effectively initiate the polymerization of the monomer, but also bring different end groups to the polymer, thereby providing convenience for further modification of the polymer. Reference to the literature
[1]Ding S,Xu L,Li P.Copper-Catalyzed Boron-Selective C(sp2)–C(sp3)Oxidative Cross-Coupling of Arylboronic Acids and AlkyltrifluoroboratesInvolving a Single-Electron Transmetalation Process[J].Acs Catalysis,2016。

Claims (8)

1. A method for initiating the polymerization of monomers by using an initiation system containing an alkyl trifluoroborate, wherein the initiation system containing the alkyl trifluoroborate takes the alkyl trifluoroborate, silver oxide and water as the initiation system of free radical polymerization, and is characterized by comprising the following steps:
step 1: purifying the monomer;
step 2: under the condition that alkyl trifluoroborate, silver oxide and water are used as an initiating system of free radical polymerization reaction, carrying out polymerization reaction on the monomer purified in the step 1 by a bulk polymerization method or a solution polymerization method;
and step 3: and (3) dissolving the product obtained in the step (2) by using a solvent A, centrifuging to obtain a supernatant, purifying, dropwise adding the purified supernatant into a solvent B, precipitating, and vacuum-drying the obtained precipitate to obtain the polymer product.
2. The method for initiating the polymerization of a monomer by using an initiation system containing an alkyl trifluoroborate according to claim 1, wherein in step 1, the monomer is one of polyethylene glycol methyl ether methacrylate, acrylamide, methyl methacrylate, methyl acrylate, butyl acrylate or styrene.
3. The method for initiating polymerization of monomers using an initiation system comprising an alkyltrifluoroborate according to claim 1, wherein in step 2, the alkyltrifluoroborate has the formula:
Figure FDA0002253665400000011
Figure FDA0002253665400000021
Figure FDA0002253665400000022
one kind of (1).
4. The method for initiating the polymerization of monomers by using the initiation system containing the alkyl trifluoroborate according to claim 1, wherein the purification process of the supernatant in the step 3 is as follows: passing the monomer through a neutral alumina column connected with a polyethersulfone or polytetrafluoroethylene filter head to obtain purified supernatant; the volume ratio of the purified supernatant to the solvent B is 1: 9; the resulting precipitate was dried under vacuum for 24 hours.
5. The method for initiating the polymerization of monomers by using the initiation system containing the alkyl trifluoroborate according to claim 1, wherein the solvent A is tetrahydrofuran or water in the step 3; the solvent B is methanol or petroleum ether.
6. The method for initiating the polymerization of monomers by using the initiation system containing the alkyl trifluoroborate according to claim 1, wherein the step 2 comprises the following steps of polymerizing the monomers purified in the step 1 by a bulk polymerization method: and (2) placing the monomer purified in the step (1) into a reaction bottle, then adding alkyl trifluoroborate, silver oxide and water into the reaction bottle, sealing the reaction bottle, removing oxygen, filling nitrogen after removing oxygen, and stirring.
7. The method for initiating the polymerization of monomers by using the initiation system containing the alkyl trifluoroborate according to claim 1, wherein the step 2 of polymerizing the monomers purified in the step 1 by the solution polymerization method comprises the following steps: putting the monomer purified in the step 1 and tetrahydrofuran with equal mass or putting the monomer purified in the step 1 and deionized water with equal mass into a reaction bottle, then adding alkyl trifluoroborate, silver oxide and water into the reaction bottle, sealing the reaction bottle, removing oxygen, filling nitrogen after removing oxygen, and stirring.
8. The method for initiating the polymerization of the monomer by using the initiation system containing the alkyl trifluoroborate according to claim 6 or 7, wherein the molar ratio of the monomer to the alkyl trifluoroborate is 1: 0.004-1: 0.041; the molar ratio of the alkyl trifluoroborate to the silver oxide was 1: 0.8.
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