CN108059690A - Initiation system containing alkyl trifluoroborate and its method for triggering monomer polymerization - Google Patents
Initiation system containing alkyl trifluoroborate and its method for triggering monomer polymerization Download PDFInfo
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- CN108059690A CN108059690A CN201711384737.8A CN201711384737A CN108059690A CN 108059690 A CN108059690 A CN 108059690A CN 201711384737 A CN201711384737 A CN 201711384737A CN 108059690 A CN108059690 A CN 108059690A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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Abstract
The invention discloses the initiation system containing alkyl trifluoroborate, the initiation system using alkyl trifluoroborate, silver oxide and water as Raolical polymerizable triggers the method for monomer polymerization, comprises the following steps：Step 1：The purifying of monomer；Step 2：Under conditions of alkyl trifluoroborate, silver oxide and water is the initiation systems of Raolical polymerizable, the monomer in step 1 after purification is subjected to polymerisation by mass polymerization or solution polymerization process；Step 3：The product tetrahydrofuran that step 2 is obtained or water dissolution, centrifuging and taking supernatant, purifying, then supernatant after purification is added drop-wise in methanol or petroleum ether, it precipitates, gained is precipitated and is dried in vacuo, gained is polymeric articles.The present invention has convincingly demonstrated alkyl trifluoroborate and has possessed condition as initiator, and polymerization time is short, and polymer is easily purified；The method of the present invention is easy, and alkyl trifluoroborate can effectively trigger monomer polymerization.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to a kind of primosome containing alkyl trifluoroborate
System, the invention further relates to a kind of methods that initiation system containing alkyl trifluoroborate triggers monomer polymerization.
Background technology
Free radical polymerization is that a kind of method of polymer is obtained by continuous sudden reaction, is pole in polymer science
Its important part and a kind of more thorough polymerisation is studied now.At present, the polymer more than more than half is
It is obtained by free radical polymerization, such as polyvinyl chloride, polystyrene, polymethyl methacrylate, polyacrylonitrile, nitrile rubber
With butadiene-styrene rubber etc..
The overall reaction of free radical polymerization is triggered by chain, chain growth, chain tra nsfer and four parts of chain termination form, and wherein chain draws
Hair is to control rate of polymerization and the committed step of molecular weight, and the initiator for playing initiation is exactly the core of initiation reaction.
As initiator, it should possess and easily resolve into the property of free radical, common initiator have azo, organic peroxide class and
Inorganic peroxygen species, in addition some oxidation-reduction trigger systems (such as Fe2+And H2O2Reaction can generate HO) also can
Generate free radicals and initiator in one kind.
Redox initiation system activation energy is low, has the advantages that trigger monomer polymerization at a lower temperature, by its dissolving
Property can be divided into water soluble oxidized-reduction initiating system and oil insoluble oxidation-reduction initiating system.Three fluoboric acid of alkyl in this patent
Salt, silver oxide and water can generate free radicals at room temperature[1]And trigger Raolical polymerizable, for the relatively low list of reactivity
Body styrene can also effectively trigger polymerization under heating condition, this provides a kind of new oxidation-also for free radical polymerization
Former initiation system.
The content of the invention
The object of the present invention is to provide a kind of initiation systems containing alkyl trifluoroborate, and the reaction system is at room temperature
Reaction is very fast, and polymer molecular weight is larger, the radical polymerization that alkyl trifluoroborate is participated in as radical polymerization initiator
The conjunction reactive polymeric time is short, and polymer is easily purified.
It is a further object to provide a kind of initiation systems containing alkyl trifluoroborate to trigger monomer polymerization
Method.
The technical solution adopted in the present invention is the initiation system containing alkyl trifluoroborate, with three fluoboric acid of alkyl
The initiation system of salt, silver oxide and water as Raolical polymerizable.
The features of the present invention also resides in：
The structural formula of alkyl trifluoroborate is：
In one kind.
Another technical solution of the present invention is that the initiation system containing alkyl trifluoroborate triggers monomer to gather
The method of conjunction, comprises the following steps：
Step 1：The purifying of monomer；
Step 2：Under conditions of alkyl trifluoroborate, silver oxide and water is the initiation systems of Raolical polymerizable,
Monomer in step 1 after purification is subjected to polymerisation by mass polymerization or solution polymerization process；
Step 3：The product that step 2 is obtained is dissolved with solvent A, centrifuging and taking supernatant, purifying, then by supernatant after purification
Drop is added in solvent B, and gained is precipitated and is dried in vacuo by precipitation, and gained is polymeric articles.
The features of the present invention also resides in：
In step 1, the monomer is methoxypolyethylene glycol methacrylate, acrylamide, methyl methacrylate, third
One kind in e pioic acid methyl ester, butyl acrylate or styrene.
In step 2, the structural formula of the alkyl trifluoroborate is：
In one kind.
In step 3, the purification process of supernatant is：By monomer by connecting the neutrality of polyether sulfone or polytetrafluoroethylene (PTFE) filter
Aluminium oxide pillar is to get to the supernatant of purifying；The volume ratio of supernatant after purification and solvent B are 1:9；Gained precipitation is passed through
Be dried in vacuo 24 it is small when.
In step 3, the solvent A is tetrahydrofuran or water；The solvent B is methanol or petroleum ether.
In step 2, the process that the monomer in step 1 after purification is carried out to polymerisation by mass polymerization is：It will step
Rapid 1 monomer after purification is placed in reaction bulb, and alkyl trifluoroborate, silver oxide and water, sealing are then added in into reaction bulb
Deoxygenation after reaction bulb, inflated with nitrogen after deoxygenation, stirring.
In step 2, the process that the monomer in step 1 after purification is carried out to polymerisation by solution polymerization process is：It will step
Rapid 1 monomer after purification with etc. quality tetrahydrofuran or by the monomer of step 1 after purification with etc. the deionized waters of quality be placed in
In reaction bulb, alkyl trifluoroborate, silver oxide and water are then added in into reaction bulb, deoxygenation after reaction bulb is sealed, after deoxygenation
Inflated with nitrogen, stirring.
The molar ratio of monomer and alkyl trifluoroborate is 1:0.004~1:0.041；Alkyl trifluoroborate and silver oxide
Molar ratio be 1:0.8.
Initiation system of the present invention containing alkyl trifluoroborate and its beneficial outcomes of method of monomer polymerization are triggered to be：
(1) alkyl trifluoroborate, silver oxide and water can generate free radicals and trigger free radical polymerization anti-at room temperature
Should, for the relatively low monomer styrene of reactivity, it can also effectively trigger polymerization under heating condition, this is carried for free radical polymerization
A kind of new oxidation-reduction trigger system is supplied；
(2) using a kind of ten alkyl trifluoroborates, by the polymerisation of monomer, alkyl trifluoro boron has been convincingly demonstrated
Hydrochlorate possesses the condition as initiator, and polymerization time is short, and polymer is easily purified；
(3) the method for the present invention is easy, and alkyl trifluoroborate can not only effectively trigger monomer polymerization, can also will gather
End group different on object band is closed, this is just provided a convenient for the further modification of polymer.
Specific embodiment
The present invention is described in detail With reference to embodiment.
A kind of initiation system containing alkyl trifluoroborate of the present invention, with alkyl trifluoroborate, silver oxide and water
Initiation system as Raolical polymerizable.
The structural formula of alkyl trifluoroborate is R1~R11In any one, R1~R11Successively shown in following structural formula：
The method that a kind of above-mentioned initiation system containing alkyl trifluoroborate triggers monomer polymerization, including following step
Suddenly：
Step 1：The purifying of monomer；
In step 1, monomer is methoxypolyethylene glycol methacrylate, acrylamide, methyl methacrylate, acrylic acid
One kind in methyl esters, butyl acrylate or styrene；
Step 2：Under conditions of alkyl trifluoroborate, silver oxide and water is the initiation systems of Raolical polymerizable,
Monomer in step 1 after purification is subjected to polymerisation by mass polymerization or solution polymerization process；
In step 2, the structural formula of alkyl trifluoroborate is：
In one kind；
In step 2, the process that the monomer in step 1 after purification is carried out to polymerisation by mass polymerization is：It will step
Rapid 1 monomer after purification is placed in reaction bulb, and alkyl trifluoroborate, silver oxide and water, sealing are then added in into reaction bulb
Deoxygenation after reaction bulb, inflated with nitrogen after deoxygenation, stirring；
In step 2, the process that the monomer in step 1 after purification is carried out to polymerisation by solution polymerization process is：It will step
Rapid 1 monomer after purification with etc. quality tetrahydrofuran or by the monomer of step 1 after purification with etc. the deionized waters of quality be placed in
In reaction bulb, alkyl trifluoroborate, silver oxide and water are then added in into reaction bulb, deoxygenation after reaction bulb is sealed, after deoxygenation
Inflated with nitrogen, stirring；
Wherein, the molar ratio of monomer and alkyl trifluoroborate is 1:0.004~1:0.041；Alkyl trifluoroborate and
The molar ratio of silver oxide is 1:0.8；
Step 3：The product that step 2 is obtained is dissolved with solvent A, centrifuging and taking supernatant, purifying, then by supernatant after purification
Drop is added in solvent B, and gained is precipitated and is dried in vacuo by precipitation, and gained is polymeric articles；
In step 3, the purification process of supernatant is：By monomer by connecting the neutrality of polyether sulfone or polytetrafluoroethylene (PTFE) filter
Aluminium oxide pillar is to get to the supernatant of purifying；The volume ratio of supernatant after purification and solvent B are 1:9；Gained precipitation is passed through
Be dried in vacuo 24 it is small when；
In step 3, the solvent A is tetrahydrofuran or water；The solvent B is methanol or petroleum ether.
Initiation system containing alkyl trifluoroborate triggers the reaction principle of monomer polymerization to be：By containing, there are many alkyl
The initiation system of trifluoroborate compound triggers monomer polymerization, and specific function is introduced in polymer end using initiator fragment
Property end group；The alkyl trifluoroborate of different end group is connected to, the initiated polymerization in the presence of silver oxide and water contains alkyl
The structural formula of trifluoroborate and its process of generation reactive species are：
Embodiment 1：
Styrene by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter is purified, measures purifying
(0.442mL, 3.841mmol, 1.000eq.) styrene monomer afterwards, places it in Shi Lanke bottles, sequentially adds
(19.0mg, 0.024eq.) R1, (17.0mg, 0.019eq.) Ag2O and 40 μ L deionized waters, with rubber stopper seal, by three times
- method the deoxygenation of dissolving circulation is freezed-vacuumized, nitrogen is filled with after deoxygenation, is protected from light and is stirred to react at 90 DEG C, is stopped after 4h anti-
Should, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying the neutral alumina of polyether sulfone filter
Aluminium pillar, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, it is solid that centrifugation obtains white
Body places it in drying in vacuum drying oven and for 24 hours, obtains the polystyrene of white, reaction
Formula is as follows：
Embodiment 2：
By methoxypolyethylene glycol methacrylate by connecting the alkalescence or neutral alumina column of polytetrafluoroethylene (PTFE) filter
Son is purified, and is measured (0.952mL, 9.988mmol, 1.000eq.) monomer after purification, is placed it in Shi Lanke bottles, according to
Secondary addition (10.0mg, 0.005eq.) R1, (9.0mg, 0.004eq.) Ag2O and 1.000mL deionized waters, with rubber stopper seal,
By freezing-vacuumizing-method deoxygenation of dissolving circulation three times, nitrogen is filled with after deoxygenation, is protected from light is stirred to react at room temperature, is reacted
Start substantially to observe that viscosity becomes larger, magneton, which is fixed up, after 30min stops reaction.Mixture after reaction is molten with THF
Solution, centrifugation removal precipitation, by solution by carrying the neutral alumina pillar of polytetrafluoroethylene (PTFE) filter, it is molten to obtain water white transparency
Liquid.Solution is instilled dropwise in the petroleum ether that stirred, precipitated three times, centrifugation obtains transparent solid.
Embodiment 3：
(0.200g, 2.814mmol, 1.000eq.) acrylamide is measured, is placed in Shi Lanke bottles, sequentially adds
(8.3mg, 0.014eq.) R1, (7.4mg, 0.011eq.) Ag2O and 0.200mL deionized waters, with rubber stopper seal, by three times
- method the deoxygenation of dissolving circulation is freezed-vacuumized, nitrogen is filled with after deoxygenation, is protected from light is stirred to react at room temperature, reacts viscosity after 1h
It is larger, stop reaction after 2h.By the mixture water dissolution after reaction, centrifugation removal precipitation, by solution by carrying polyether sulfone
The neutral alumina pillar of filter, obtains colourless transparent solution.Solution is instilled dropwise in the petroleum ether that stirred and precipitated three times,
Centrifugation obtains white solid.
Embodiment 4：
Butyl acrylate by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter is purified, is measured
(1.119mL, 7.802mmol, 1.000eq.) monomer after purification, places it in Shi Lanke bottles, sequentially add (23.0mg,
0.014eq.)R1, (20.6mg, 0.011eq.) Ag2O, (1.126mL) tetrahydrofuran and 100 μ L deionized waters, it is close with rubber stopper
Envelope by freezing-vacuumize-method deoxygenation of dissolving circulation three times, is filled with nitrogen, is protected from light is stirred to react at room temperature after deoxygenation,
Stop reaction after 4h, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying polytetrafluoroethylene (PTFE)
The neutral alumina pillar of filter, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, from
Gains in depth of comprehension place it in drying in vacuum drying oven and for 24 hours, obtain the butyl polyacrylate of water white transparency to transparent solid.Reaction equation is such as
Under：
Embodiment 5：
Methacrylate monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.524mL, 5.808mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(16.7mg, 0.015eq.) R2, (16.2mg, 0.011eq.) Ag2O, (0.563mL) tetrahydrofuran and 50 μ L deionized waters are used
Rubber stopper seal by freezing-vacuumizing-method deoxygenation of dissolving circulation three times, is filled with nitrogen, is protected from light stirs at room temperature after deoxygenation
Reaction is mixed, stops reaction after 2h11min, the mixture after reaction is dissolved with THF, solution is passed through band by centrifugation removal precipitation
There is the neutral alumina pillar of polyether sulfone filter, obtain colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and sunk
It forms sediment three times, centrifugation obtains transparent solid, places it in drying in vacuum drying oven and for 24 hours, obtains the polymethyl acrylate of water white transparency.
Reaction equation is as follows：
Embodiment 6：
Butyl Acrylate Monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.559mL, 3.901mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(8.7mg, 0.015eq.) R3, (10.9mg, 0.012eq.) Ag2O and 50 μ L deionized waters, with rubber stopper seal, by three times
- method the deoxygenation of dissolving circulation is freezed-vacuumized, nitrogen is filled with after deoxygenation, is protected from light is stirred to react at room temperature, is stopped after 4h anti-
Should, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying the neutrality of polytetrafluoroethylene (PTFE) filter
Aluminium oxide pillar, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, centrifugation obtains transparent
Solid places it in drying in vacuum drying oven and for 24 hours, obtains the butyl polyacrylate of water white transparency.
Embodiment 7：
Methacrylate monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.336mL, 3.485mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(11.5mg, 0.015eq.) R4, (9.8mg, 0.012eq.) Ag2O, (0.338mL) tetrahydrofuran and 30 μ L deionized waters, use rubber
Rubber plug seals, and by freezing-vacuumizing-method deoxygenation of dissolving circulation three times, nitrogen is filled with after deoxygenation, is protected from light stirring at room temperature
It reacts, stops reaction after 6h11min, the mixture after reaction is dissolved with THF, centrifugation removal precipitates, by solution by carrying
The neutral alumina pillar of polyether sulfone filter, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated
Three times, centrifugation obtains transparent solid, places it in drying in vacuum drying oven and for 24 hours, obtains the polymethyl acrylate of water white transparency.
Embodiment 8：
Methyl methacrylate monomer is carried out by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter
Purifying, measures (0.213mL, 1.998mmol, 1.000eq.) monomer after purification, places it in Shi Lanke bottles, sequentially add
(6.6mg, 0.015eq.) R4, (5.6mg, 0.012eq.) Ag2O and 20 μ L deionized waters, with rubber stopper seal, by cold three times
Freeze-vacuumize-method deoxygenation of dissolving circulation, nitrogen is filled with after deoxygenation, is protected from light is stirred to react at room temperature, stop after 70min anti-
Should, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying the neutrality of polytetrafluoroethylene (PTFE) filter
Aluminium oxide pillar, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, centrifugation obtains white
Solid places it in drying in vacuum drying oven and for 24 hours, obtains the polymethyl methacrylate of white.Reaction equation is as follows：
Embodiment 9：
Butyl Acrylate Monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.560mL, 3.901mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(21.6mg, 0.015eq.) R5, (10.9mg, 0.012eq.) Ag2O, (0.563mL) tetrahydrofuran and 50 μ L deionized waters are used
Rubber stopper seal by freezing-vacuumizing-method deoxygenation of dissolving circulation three times, is filled with nitrogen, is protected from light stirs at room temperature after deoxygenation
Reaction is mixed, stops reaction after 5h, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying polyethers
The neutral alumina pillar of sulfone filter, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times,
Centrifugation obtains water white transparency solid, places it in drying in vacuum drying oven and for 24 hours, obtains the butyl polyacrylate of water white transparency.
Embodiment 10：
Butyl Acrylate Monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.560mL, 3.901mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(12.0mg, 0.015eq.) R6, (11.1mg, 0.012eq.) Ag2O and 50 μ L deionized waters, with rubber stopper seal, by three times
Freeze-pump-thaw cycle deoxygenations, are filled with nitrogen after deoxygenation, be protected from light be stirred to react at room temperature, stop reaction after 4.5h,
Mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying the neutral alumina column of polyether sulfone filter
Son obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, centrifugation obtains water white transparency and consolidates
Body places it in drying in vacuum drying oven and for 24 hours, obtains the butyl polyacrylate of water white transparency.
Embodiment 11：
Methyl methacrylate monomer is carried out by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter
Purifying, measures (0.532mL, 4.994mmol, 1.000eq.) monomer after purification, places it in Shi Lanke bottles, sequentially add
(73.0mg, 0.051eq.) R7, (47.0mg, 0.041eq.) Ag2O and 50 μ L deionized waters, with rubber stopper seal, by three times
- method the deoxygenation of dissolving circulation is freezed-vacuumized, nitrogen is filled with after deoxygenation, is protected from light is stirred to react at room temperature, is stopped after 3.5h anti-
Should, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying the neutrality of polytetrafluoroethylene (PTFE) filter
Aluminium oxide pillar, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, centrifugation obtains white
Solid places it in drying in vacuum drying oven and for 24 hours, obtains the polymethyl methacrylate of white.
Embodiment 12：
Methacrylate monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.314mL, 3.485mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(10.0mg, 0.015eq.) R8, (9.8mg, 0.012eq.) Ag2O and 30 μ L deionized waters, with rubber stopper seal, by three times
- method the deoxygenation of dissolving circulation is freezed-vacuumized, nitrogen is filled with after deoxygenation, is protected from light is stirred to react at room temperature, stop after 3h50min
It only reacts, the mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying polytetrafluoroethylene (PTFE) filter
Neutral alumina pillar, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, centrifugation obtains
Water white transparency solid places it in drying in vacuum drying oven and for 24 hours, obtains the polymethyl acrylate of water white transparency.
Embodiment 13：
Butyl Acrylate Monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.336mL, 2.341mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(9.0mg, 0.015eq.) R9, (6.6mg, 0.012eq.) Ag2O, (0.338mL) tetrahydrofuran and 30 μ L deionized waters, use rubber
Rubber plug seals, and by freezing-vacuumizing-method deoxygenation of dissolving circulation three times, nitrogen is filled with after deoxygenation, is protected from light stirring at room temperature
It reacts, stops reaction after 2h, the mixture after reaction is dissolved with THF, centrifugation removal precipitates, by solution by carrying polyether sulfone
The neutral alumina pillar of filter, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, from
Gains in depth of comprehension place it in dry 24 h in vacuum drying oven, obtain the butyl polyacrylate of water white transparency to water white transparency solid.
Embodiment 14：
Monomer by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter is purified, is measured after purification
(0.190mL, 1.998mmol, 1.000eq.) monomer, place it in Shi Lanke bottles, sequentially add (6.6mg,
0.015eq.)R10, (5.4mg, 0.012eq.) Ag2O and 200 μ L deionized waters, with rubber stopper seal, by freezing-taking out three times
The method deoxygenation of vacuum-dissolving circulation, is filled with nitrogen after deoxygenation, be protected from light be stirred to react at room temperature, observes and increasingly glues,
Stop reaction after 10min.Mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying polytetrafluoroethyl-ne
The neutral alumina pillar of alkene filter, obtains colourless transparent solution.Solution is instilled dropwise in the petroleum ether that stirred and precipitate three
Time, centrifugation obtains water white transparency solid.
Embodiment 15：
Methacrylate monomer is purified by the alkalescence or neutral alumina pillar for connecting polytetrafluoroethylene (PTFE) filter,
(0.319mL, 3.485mmol, 1.000eq.) monomer after purification is measured, places it in Shi Lanke bottles, sequentially adds
(25.3mg, 0.033eq.) R11, (21.4mg, 0.026eq.) Ag2O and 30 μ L deionized waters, with rubber stopper seal, pass through three
Secondary Freeze-pump-thaw cycle deoxygenations, are filled with nitrogen after deoxygenation, be protected from light be stirred to react at room temperature, stop reaction after 6h,
Mixture after reaction is dissolved with THF, centrifugation removal precipitation, by solution by carrying the neutral alumina of polytetrafluoroethylene (PTFE) filter
Aluminium pillar, obtains colourless transparent solution.Solution is instilled dropwise in the methanol that stirred and precipitated three times, centrifugation obtains water white transparency
Solid places it in drying in vacuum drying oven and for 24 hours, obtains the polymethyl acrylate of water white transparency.
It is an advantage of the invention that：
(1) alkyl trifluoroborate, silver oxide and water can generate free radicals at room temperature[1]And trigger free radical polymerization
Reaction for the relatively low monomer styrene of reactivity, can also effectively trigger polymerization, this is free radical polymerization under heating condition
Provide a kind of new oxidation-reduction trigger system；
(2) using a kind of ten alkyl trifluoroborates, by the polymerisation of monomer, alkyl trifluoro boron has been convincingly demonstrated
Hydrochlorate possesses the condition as initiator, and polymerization time is short, and polymer is easily purified；
(3) the method for the present invention is easy, and alkyl trifluoroborate can not only effectively trigger monomer polymerization, can also will gather
End group different on object band is closed, this is just provided a convenient for the further modification of polymer.Bibliography
[1]Ding S,Xu L,Li P.Copper-Catalyzed Boron-Selective C(sp2)–C(sp3)
Oxidative Cross-Coupling of Arylboronic Acids and Alkyltrifluoroborates
Involving a Single-Electron Transmetalation Process[J].Acs Catalysis,2016。
Claims (10)
1. the initiation system containing alkyl trifluoroborate, which is characterized in that using alkyl trifluoroborate, silver oxide and water as
The initiation system of Raolical polymerizable.
2. the initiation system according to claim 1 containing alkyl trifluoroborate, which is characterized in that the alkyl trifluoro
The structural formula of borate is：
In one kind.
3. the method that the initiation system containing alkyl trifluoroborate triggers monomer polymerization, which is characterized in that comprise the following steps：
Step 1：The purifying of monomer；
Step 2：Under conditions of alkyl trifluoroborate, silver oxide and water is the initiation systems of Raolical polymerizable, it will walk
Monomer in rapid 1 after purification carries out polymerisation by mass polymerization or solution polymerization process；
Step 3：The product that step 2 is obtained is dissolved with solvent A, centrifuging and taking supernatant, purifying, then by supernatant drop after purification
It is added in solvent B, precipitates, gained is precipitated and is dried in vacuo, gained is polymeric articles.
4. the method that the initiation system according to claim 3 containing alkyl trifluoroborate triggers monomer polymerization, special
Sign is, in step 1, the monomer is methoxypolyethylene glycol methacrylate, acrylamide, methyl methacrylate, third
One kind in e pioic acid methyl ester, butyl acrylate or styrene.
5. the method that the initiation system according to claim 3 containing alkyl trifluoroborate triggers monomer polymerization, special
Sign is, in step 2, the structural formula of the alkyl trifluoroborate is：
In one kind.
6. the method that the initiation system according to claim 3 containing alkyl trifluoroborate triggers monomer polymerization, special
Sign is, in step 3, the purification process of supernatant is：By monomer by connecting the neutrality of polyether sulfone or polytetrafluoroethylene (PTFE) filter
Aluminium oxide pillar is to get to the supernatant of purifying；The volume ratio of supernatant after purification and solvent B are 1:9；Gained precipitation is passed through
Be dried in vacuo 24 it is small when.
7. the method that the initiation system according to claim 3 containing alkyl trifluoroborate triggers monomer polymerization, special
Sign is, in step 3, the solvent A is tetrahydrofuran or water；The solvent B is methanol or petroleum ether.
8. the method that the initiation system according to claim 3 containing alkyl trifluoroborate triggers monomer polymerization, special
Sign is, in step 2, the process that the monomer in step 1 after purification is carried out to polymerisation by mass polymerization is：By step
1 monomer after purification is placed in reaction bulb, and alkyl trifluoroborate, silver oxide and water are then added in into reaction bulb, and sealing is anti-
Answer deoxygenation after bottle, inflated with nitrogen after deoxygenation, stirring.
9. the method that the initiation system according to claim 3 containing alkyl trifluoroborate triggers monomer polymerization, special
Sign is, in step 2, the process that the monomer in step 1 after purification is carried out to polymerisation by solution polymerization process is：By step
1 monomer after purification with etc. the tetrahydrofuran of quality or by the monomer of step 1 after purification with etc. the deionized waters of quality be placed in instead
It answers in bottle, alkyl trifluoroborate, silver oxide and water is then added in into reaction bulb, seal deoxygenation after reaction bulb, filled after deoxygenation
Nitrogen, stirring.
10. the method that the initiation system containing alkyl trifluoroborate according to claim 8 or claim 9 triggers monomer polymerization,
It is characterized in that, the molar ratio of monomer and alkyl trifluoroborate is 1:0.004~1:0.041；Alkyl trifluoroborate and oxygen
The molar ratio for changing silver is 1:0.8.
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