CN106699938A - Ligand-free atom transfer radical polymerization method under action of alkali - Google Patents
Ligand-free atom transfer radical polymerization method under action of alkali Download PDFInfo
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- CN106699938A CN106699938A CN201611069766.0A CN201611069766A CN106699938A CN 106699938 A CN106699938 A CN 106699938A CN 201611069766 A CN201611069766 A CN 201611069766A CN 106699938 A CN106699938 A CN 106699938A
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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
- 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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- 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
- C08F120/16—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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- C08F2/00—Processes of polymerisation
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- C08F2/06—Organic solvent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
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- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The invention discloses a ligand-free atom transfer radical polymerization method under the action of alkali. The method is characterized by comprising the following step: mixing reaction raw materials comprising a monomer, an initiator and a catalyst without using a ligand under the action of alkali, so that the monomer is subjected to atom transfer radical polymerization reaction to generate a corresponding polymer. The ligand-free atom transfer radical polymerization method improves the reaction raw materials adopted in the key atom transfer radical polymerization reaction, uses alkali to participate in the reaction, can further optimize components of an atom transfer radical polymerization system, overcomes defects that toxic and volatile organic compounds or polar solvents used by the atom transfer radical polymerization system as the ligands are expensive, highly toxic and volatile in the prior art, and reduces the degree of damage to the environment and the reaction cost.
Description
Technical field
The invention belongs to Polymer Synthesizing field, being shifted certainly without ligand atom under being acted on more particularly, to a kind of alkali
It is a kind of new practicable ways of atom transfer radical polymerization method by base polymerization.
Background technology
ATRP because its excellent controlling turn into most important " activity "/controllable polymerization method it
One, it is widely used in that synthetic molecular weight is controllable and polymer of narrow ditribution, while having good MOLECULE DESIGN function.Pass
The atom transfer radical polymerization method of system is required for addition organic compound (such as the compound containing P, N, organic acid, ionic liquid
Deng) as part and catalyst form complex to make system that there is greater activity, but these components it is expensive in itself and
With compared with high toxicity, can not meet the Green Development of polymerization and widely use requirement.
In order to overcome the shortcoming of conventional organic compounds part in conventional atom transferring free-radical polymerization, phosphinylidyne-containing amine group
Polar solvent (such as dimethylformamide, vinyl pyrrolidone, dimethyl-imidazolinone etc.) is introduced in atom transfer certainly
By in base polymerisation.Polymerization system shows preferable controllable reaction feature, but the volatilization of these polar solvents is serious, to people
Body and Environmental Health have very big harm.And appropriate inorganic base (sodium carbonate, NaOH, sodium acid carbonate, three oxidations two
Aluminium, aluminium hydroxide) it is usually used in ATRP, reaction rate can not only substantially accelerated, while keeping body
The controlling of system.If can only using alkali (inorganic base and organic base) act on Atom Transfer Radical Polymerization System and without this
A little poisonous and volatile organic compounds or polar solvent will greatly reduce reaction cost as part, promote greenization
The development of polymerization system, but up to the present, being had not been reported without ligand atom transfer radical polymerization method under alkali effect.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, it is an object of the invention to provide the nothing under a kind of effect of alkali
Ligand atom transfer radical polymerization method, wherein by the reaction used to its critical atoms transition free radical polymerization reaction
Raw material is improved, and participates in reacting using alkali, and the component of Atom Transfer Radical Polymerization System further can be optimized,
The organic compound or polar solvent that Atom Transfer Radical Polymerization System in the prior art is used are overcome (e.g., containing P, N chemical combination
Raw material of thing, organic acid, ionic liquid, and phosphinylidyne-containing amine group etc.) as the expensive, toxicity existing for part it is larger and
The shortcomings of volatility, reduce the extent of damage and reaction cost to environment.
To achieve the above object, it is proposed, according to the invention, poly- without ligand atom transferred free radical under being acted on there is provided a kind of alkali
Conjunction method, it is characterised in that the method is in the presence of alkali, under conditions of part is not used, to make to include monomer, initiator
And catalyst three mixes in interior reaction raw materials, so that the monomer carries out atom transition free radical polymerization reaction life
Into corresponding polymer.
As present invention further optimization, including without ligand atom transfer radical polymerization method under the alkali effect
Following steps：
Under conditions of anhydrous and isolation oxygen, by the monomer, the alkali, the catalyst and the initiator four
Person mixes to form pre-reaction mixed liquor；Then the pre-reaction mixed liquor is heated into atom transferred free radical set in advance to gather
The reaction temperature of reaction is closed, the monomer is to proceed by atom transition free radical polymerization reaction to generate corresponding polymer；
The monomer is 200 with the mol ratio of both catalyst:1~500:1；
The monomer is 200 with the mol ratio of both initiators:1~500:1, both the alkali and described catalyst
Mol ratio be 0.2:1~4:1.
As present invention further optimization, the reaction raw materials also include solvent, the solvent be preferably benzene, toluene,
At least one in tetrahydrofuran, methyl phenyl ethers anisole, diphenyl ether, ethyl acetate.
As present invention further optimization, including without ligand atom transfer radical polymerization method under the alkali effect
Following steps：
Under conditions of anhydrous and isolation oxygen, by the monomer, the alkali, the catalyst, the solvent and institute
Initiator is stated to mix to form pre-reaction mixed liquor；Then the pre-reaction mixed liquor is heated into atom set in advance to turn
The reaction temperature of Raolical polymerizable is moved, the monomer is to proceed by atom transition free radical polymerization reaction generation accordingly
Polymer；
The monomer is 200 with the mol ratio of both catalyst:1~500:1；
The monomer is 200 with the mol ratio of both initiators:1~500:1, both the alkali and described catalyst
Mol ratio be 0.2:1~4:1；
The monomer is 1 with the volume ratio of both solvents:1~10:1.
Used as present invention further optimization, the monomer is methyl methacrylate, butyl methacrylate, acrylic acid
At least one in methyl esters, butyl acrylate, styrene, vinyl chloride, acrylic acid, acrylamide, acrylonitrile and vinylacetate；
The initiator is 2- Bromophenylacetic acids ethyl ester, 2- isobutyl ethyl bromides, 2- isobutyl bromides methyl esters, 2 bromopropionic acid second
Any one of ester and 2 bromoethyl benzene；
The alkali is at least one in inorganic base, organic base, wherein the inorganic base is sodium carbonate, sodium acid carbonate, carbon
At least one in sour potassium, saleratus, NaOH, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate, institute
It is at least one in monoethanolamine, ethylenediamine, triethylamine and urea to state organic base；
The catalyst is the catalyst containing metallic element, preferably ferrous bromide, cuprous bromide, ferric bromide and chlorination
Any one in iron.
Used as present invention further optimization, the pre-reaction mixed liquor is that mixing is stirred under conditions of protective gas
What 20min~30min was obtained；Preferably, the protective gas is nitrogen or inert gas.
As present invention further optimization, the reaction temperature of the atom transition free radical polymerization reaction set in advance
It is 30 DEG C~120 DEG C.
Used as present invention further optimization, the reaction time of the atom transition free radical polymerization reaction is small not less than 3
When；Preferably, the reaction time of the atom transition free radical polymerization reaction is 0~9 hour；
Preferably, the atom transition free radical polymerization reaction is terminated by cooling reaction system, generation it is described
Corresponding polymer is by removing catalyst described in the reaction system, the alkali and the unreacted monomer purification
Obtain.
By the contemplated above technical scheme of the present invention, compared with prior art, due to being carried out in the presence of alkali
Atom transition free radical polymerization reaction without part, overcomes what Atom Transfer Radical Polymerization System in the prior art used to have
Poison and volatile organic compound or polar solvent (compound containing P, N, organic acid, ionic liquid, and phosphinylidyne-containing amine group
Raw material etc.) as expensive, larger toxicity and volatility existing for part the shortcomings of, reduce the extent of damage to environment
And reaction cost.The present invention is (e.g., volatile without the part used in common atom transfer radical polymerization method
Organic polar solvent, toxicity it is larger containing N, P-compound or ionic liquid), specifically including 2 kinds of situations：The first situation
It is not use any ligand material but have the solvent (polytype solvent can be used in this case, these solvents are often
Cannot be coordinated in system and act only as solvent for forming polymerisation in solution), second situation is not use any part and solvent
(such case is polymerisation in bulk)；The present invention eliminates traditional original under the good controlling basis of ATRP
In sub- transition free radical polymerization reaction the shortcomings of the expensive of part presence, larger toxicity and volatility.Introduced in system
Cheap and easy to get, nontoxic alkali (inorganic base and organic base), can further regulate and control reaction speed by adjusting the species and consumption of alkali
Rate and product yield.The redox potential for being introduced into catalyst in the system of reducing of alkali so that electro transfer is easier hair
It is raw；Alkali can also directly facilitate the fracture of initiator carbon-halogen bond, accelerate the generation of living radical, improve reaction rate.The present invention
The use of the additional parts such as poisonous and volatile organic compound or polar solvent can be reduced, conventional atom is solved and is turned
The problem that cost of material is expensive, toxicity is larger of Raolical polymerizable is moved, atom transition free radical polymerization reaction is reduced
Cost of material, simplifies the last handling process of product so that system more environmental protection.Alkali needed for the present invention is inorganic base
And organic base, it is simple and easy to get.
In the present invention alkali effect under without ligand atom transfer radical polymerization method, it is adaptable to the polymerization of all kinds of monomers,
Such as methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, vinyl chloride, acrylic acid, third
Acrylamide, acrylonitrile and vinylacetate；The alkali of use both can be inorganic base (such as sodium carbonate, sodium acid carbonate, potassium carbonate, carbon
Potassium hydrogen phthalate, NaOH, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate), or organic base (e.g., ethanol
Amine, ethylenediamine, triethylamine, urea).
The present invention is preferably controlled by by monomer in atom transition free radical polymerization reaction with the mol ratio of both catalyst
200:1~500:1st, the mol ratio of both monomer and initiator is preferably controlled to 200:1~500:1, both alkali and catalyst
Mol ratio be preferably controlled to 0.2:1~4:1；Monomer is preferably controlled to 1 with the volume ratio of both solvents:1~10:1；By control
The ratio (the especially adding proportion of alkali) of each reaction raw materials, and the overall co-ordination for passing through each reaction condition are made, can be true
Protect effective generation of atom transition free radical polymerization reaction, it is ensured that appropriate reaction rate, product yield and polymerization control
Property.Additionally, the present invention is preferably 30 DEG C~120 DEG C, during reaction by by the reaction temperature of atom transition free radical polymerization reaction
Between be preferably more than 3 hours (or 0~9 hour), it can be ensured that generate specific subject polymer product.
In the present invention, the introducing of alkali in the case of without any extra ligand, can change the oxygen of metallic catalyst
Change reduction potential, the redox potential of catalyst in reduction system so that electro transfer is easier to be occurred；And alkali can be with
The fracture of initiator carbon-halogen bond is directly facilitated, accelerates the generation of living radical, improve reaction rate and conversion ratio.
The present invention combines alkali and ATRP without part, good in ATRP
On the basis of good controlling, further optimization is reacted atom transferred free radical by the introducing of alkali and the exclusion of part, accelerated
Reaction process, reduces cost of material, simplifies last handling process, for the development of environmental protection Atom Transfer Radical Polymerization System
With great directive significance.
Brief description of the drawings
Fig. 1 a are polymerization system [methyl methacrylate] in embodiment 30:[2- Bromophenylacetic acids ethyl ester]0:[protobromide
Iron]0:[alkali]0=200:1:1:2 in 60 DEG C of kinetics of polymerization curves of reaction；
Fig. 1 b are molecular weight and molecualr weight distribution corresponding with kinetics of polymerization curve in embodiment 3 with the change of alkali content
Change curve.
Fig. 2 is the catalyst system and catalyzing applied in embodiment 7, the effect that alkali is probed into by cyclic voltammetric method change catalyst and
The redox potential size of initiator.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method
Not constituting conflict each other can just be mutually combined.
In the present invention alkali effect under without ligand atom transfer radical polymerization method, the method is in alkali operative condition
Under, do not use poisonous and volatile organic compound or polar solvent in usual atom transfer radical polymerization method to make
Be part, will monomer, catalyst and initiator mix after carry out ATRP, and by adjust alkali species and
Consumption regulates and controls reaction rate and product yield, obtains required polymerizate.
Specifically may comprise steps of：
(1) it is anhydrous and isolation Oxygen Condition under prepare bulk polymerization component, in polymerisation component, monomer with draw
The mol ratio for sending out agent is 200:1~500:1, alkali is 0.2 with the mol ratio of catalyst:1~4:1；
(2) the polymerisation component and solvent obtained by step (1) are mixed to form solution, monomer is with the volume ratio of solvent
1:1~10:1；
(3) the polymerisation component obtained by step (1) or (2) is placed in the reactor full of protective gas and is stirred at room temperature
20~30min, makes the components such as catalyst fully dispersed in monomer and dissolves, and is then placed on polymerization in heater, leads to
Cross change reaction temperature, initiator type, the species of alkali, the consumption of alkali and reaction time telo merization process；
(4) after polymerisation reaches predetermined reaction time interval, a certain amount of reactant mixture is taken out from reactor,
Cooling stops reaction, to obtain the polymer of differentiated yields；
(5) after removing unreacted monomer, catalyst and alkali, it is dried to obtain pure polymerizate.
The monomer be methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene,
One kind in vinyl chloride, acrylic acid, acrylamide, acrylonitrile and vinylacetate；
The initiator is 2- Bromophenylacetic acids ethyl ester, 2- isobutyl ethyl bromides, 2- isobutyl bromides methyl esters, 2 bromopropionic acid second
One kind of ester and 2 bromoethyl benzene；
The alkali can be inorganic bases sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus, NaOH, potassium hydroxide,
One kind, or organic base monoethanolamine, ethylenediamine, triethylamine and urine in sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate
One kind in element；Wherein described catalyst is using the one kind in ferrous bromide, cuprous bromide, ferric bromide and iron chloride；
The solvent is the one kind in benzene, toluene, tetrahydrofuran, methyl phenyl ethers anisole, diphenyl ether, ethyl acetate.
Preferably, reaction temperature may depend on the species of monomer described in step (3), and scope control is in general controllable polymerization
In the range of, 30~120 DEG C；Protective gas described in step (3) is the one kind in inert gas or nitrogen；Step (3) is described
Reaction time depending on purpose, studies kinetics, and the time is 0~9 hour, prepares specific polymer product, and the time is 3
More than hour.
It is optional step to (2) the step of solvent is added in reaction system, that is to say, that can be without in reaction system
Solvent.
It is below specific embodiment：
Embodiment 1：
By methyl methacrylate monomer, solvent, (solvent is respectively toluene, benzene, tetrahydrofuran, methyl phenyl ethers anisole, diphenyl ether, second
Acetoacetic ester), 2- isobutyl ethyl bromides initiator and sodium phosphate after purification, carry out polymerisation component preparation, methyl methacrylate
Ester, 2- isobutyl ethyl bromides, ferrous bromide (lower valency transition-metal catalyst) and sodium phosphate mol ratio are 200:1:1:2, first
The volume ratio of base methyl acrylate and solvent is 1:1.Process for preparation is：Weighed in glove box 0.061 gram of ferrous bromide and
0.0928 gram of sodium phosphate is put into eggplant-shape bottle, takes 6 milliliters of methyl methacrylate monomers and 6 milliliters of solvents are added to eggplant-shape bottle
In, magnetic agitation adds 37.7 microlitres of 2- isobutyl ethyl bromides after 20 minutes, continues to stir 2 minutes, obtains pre-reaction mixing
Liquid.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 60 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Remove unreacted monomer, catalyst and alkali, calculate conversion ratio, dissolved product with 2~5 milliliters of tetrahydrofurans, by 200~
The neutral alumina pillar of 300 mesh removes catalyst, is dried to obtain polymethyl methacrylate product.
Embodiment 2：
By methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl esters initiator, sodium acid carbonate and stannous octoate after purification,
Carry out reductive polymerization reactive component preparation (wherein stannous octoate is as reducing agent), methyl methacrylate, 2- bromophenyl second
Acetoacetic ester, ferric bromide (or iron chloride) (high-valence state transition-metal catalyst), sodium carbonate and stannous octoate mol ratio are 200:1:
1:2:3.Process for preparation is：0.0459 gram of ferric bromide (or iron chloride) is weighed in glove box and 0.0476 gram of sodium acid carbonate is put into
In eggplant-shape bottle, take 6 milliliters of methyl methacrylate monomers and 0.275 milliliter of stannous octoate is added in eggplant-shape bottle, magnetic agitation
After 20 minutes, 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters are added, continue to stir 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 60 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Unreacted monomer, catalyst and alkali is gone to calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolving, by 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain polymethyl methacrylate product.
Being reacted without ligand polymer under alkali effect is carried out by using the transition-metal catalyst and reducing agent of high-valence state
Process.
Embodiment 3：
By methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiators and sodium carbonate after purification, carry out being polymerized instead
Component is answered to prepare, methyl methacrylate, 2- Bromophenylacetic acids ethyl ester, ferrous bromide (lower valency transition-metal catalyst) and alkali
Mol ratio is 200:1:1:2.Process for preparation is：0.061 gram of ferrous bromide is weighed in glove box and respective amount alkali is put into eggplant shape
In bottle, take 6 milliliters of methyl methacrylate monomers and be added in eggplant-shape bottle, magnetic agitation adds 49.5 microlitres after 20 minutes
2- Bromophenylacetic acid ethyl esters, continue to stir 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 60 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Unreacted monomer, catalyst and alkali is gone to calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolving, by 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain polymethyl methacrylate product.
Rate of polymerization and controllability are adjusted by changing the species of alkali, sodium carbonate, sodium acid carbonate, carbonic acid are used respectively
Potassium, saleratus, NaOH, potassium hydroxide, repeat the preparation of foregoing pre-reaction mixed liquor and the polymerisation mistake without part
Journey.
The change in concentration of Fig. 1 a displaying monomers and time (ln [M]0/ ln [M]-t) it is linear, under the conditions of showing this
Polymerisation is first order kinetics course of reaction.Fig. 1 b are that the corresponding molecular weight and molecualr weight distribution of kinetics of polymerization curve exists
With the change curve of conversion ratio under different alkali contents.
Embodiment 4：
By n-BMA monomer, 2- Bromophenylacetic acid ethyl ester initiators and sodium carbonate after purification, it is polymerized
Reactive component is prepared, n-BMA, 2- Bromophenylacetic acids ethyl ester, ferrous bromide (lower valency transition-metal catalyst)
It is 200 with sodium carbonate mol ratio:1:1:2.Process for preparation is：0.061 gram of ferrous bromide and 0.06 gram of carbon are weighed in glove box
Sour sodium is put into eggplant-shape bottle, is taken 8 milliliters of n-BMA monomers and is added in eggplant-shape bottle, and magnetic agitation is after 20 minutes,
49.5 microlitres of 2- Bromophenylacetic acid ethyl esters are added, continues to stir 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 80 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Unreacted monomer, catalyst and alkali is gone to calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolving, by 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain Vinalac 5920 product.
Embodiment 5：
By Butyl Acrylate Monomer, benzyl chloride initiator and sodium carbonate after purification, polymerisation component preparation, propylene are carried out
Acid butyl ester, benzyl chloride, frerrous chloride (lower valency transition-metal catalyst) and sodium carbonate mol ratio are 200:1:1:2.Prepared
Cheng Wei：Weigh 0.0267 gram of frerrous chloride in glove box and during 0.06 gram of sodium carbonate is put into eggplant-shape bottle, take 6 milliliters of acrylic acid fourths
Ester monomer is added in eggplant-shape bottle, and magnetic agitation adds 7.2 microlitres of benzyl chlorides after 20 minutes, continues to stir 2 minutes, is obtained
Pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 60 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Unreacted monomer, catalyst and alkali is gone to calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolving, by 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain butyl polyacrylate product.
Embodiment 6：
By methyl methacrylate monomer, polymethyl methacrylate macromole evocating agent, sodium carbonate after purification, gathered
Close reactive component to prepare, methyl methacrylate, polymethyl methacrylate macromole evocating agent, ferrous bromide (lower valency mistake
Cross metallic catalyst) and sodium carbonate mol ratio be 500:1:1:2.Process for preparation is：0.061 gram of protobromide is weighed in glove box
Iron, 0.06 gram of sodium carbonate and 1.5 grams of polymethyl methacrylate macromole evocating agents are put into eggplant-shape bottle, take 6 milliliters of methyl-props
E pioic acid methyl ester monomer is added in eggplant-shape bottle, and magnetic agitation obtains pre-reaction mixed liquor after 20 minutes.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 60 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Unreacted monomer, catalyst and alkali calculating conversion ratio, predetermined reaction time is gone to be sampled after being spaced, with 2~5 milliliters of tetrahydrochysene furans
Mutter and remove catalyst by product dissolving, by the neutral alumina pillar of 200~300 mesh, be dried to obtain poly-methyl methacrylate
Ester products.
Embodiment 7：
By acetonitrile, 2- Bromophenylacetic acid ethyl ester initiators and sodium carbonate after purification, volt-ampere fractions tested is circulated to prepare,
2- Bromophenylacetic acids ethyl ester and sodium carbonate mol ratio are 1:2.Process for preparation is：1.6116 grams of tetrabutyl bromines are weighed in glove box
Change ammonium and 0.0127 gram of sodium carbonate is put into eggplant-shape bottle, take 50 milliliters of acetonitriles and 10.5 microlitres of 2- Bromophenylacetic acid ethyl esters are added to
In four-hole bottle, magnetic agitation after 20 minutes static 2min obtain cyclic voltammetry mixed liquor.
Four-hole bottle mixed liquor is transferred in heater, controlling reaction temperature is 60 DEG C, three electrodes is accessed, in 0.01V/
It is scanned under the sweep speed of s, 0.02V/s, 0.05V/s, monitors cyclic voltammetry curve.
Fig. 2 is the redox potential size of the effect change initiator that cyclic voltammetric method probes into alkali.Alkali of the present invention is made
Any additional part, reactant can not be used without ligand atom transfer radical polymerization method, in its course of reaction under
System still has good controlling, and another aspect reaction mechanism can not be explained with the system mechanism containing part, because
This, the present invention has used calculating chemical simulation method and the cyclic voltammetric technology to carry out reaction mechanism in terms of study mechanism
Explore to solve this problem.
Embodiment 8：
By methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiators and organic base after purification, carry out being polymerized instead
Answer component to prepare, methyl methacrylate, 2- Bromophenylacetic acids ethyl ester, ferrous bromide (lower valency transition-metal catalyst) and have
Machine alkali mol ratio is 200:1:1:2.Process for preparation is：0.061 gram of ferrous bromide is weighed in glove box and respective amount alkali is put into
In eggplant-shape bottle, take 6 milliliters of methyl methacrylate monomers and be added in eggplant-shape bottle, magnetic agitation adds 49.5 after 20 minutes
Microlitre 2- Bromophenylacetic acid ethyl esters, continue to stir 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heater, controlling reaction temperature is 60 DEG C；Polymerisation
After reaching predetermined reaction time interval, a certain amount of mixture is taken out from reactor pour into flask cooling and stop reaction, remove
Unreacted monomer, catalyst and alkali is gone to calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolving, by 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain polymethyl methacrylate product.
Rate of polymerization and controllability are adjusted by changing the species of alkali, monoethanolamine, urea, ethylenediamine and three are used respectively
Ethamine, repeats the preparation of foregoing pre-reaction mixed liquor and the polymerization process without part.
In addition to specific monomeric species in above-described embodiment, the applicable monomeric species of the present invention can also be methacrylic acid
Methyl esters, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, vinyl chloride, acrylic acid, acrylamide, propylene
Any one in nitrile and vinylacetate；Polymerisation both can be the homopolymerization that a kind of monomer is participated in, or many
Plant the copolyreaction that monomer is participated in；Corresponding initiator, catalyst, can also use existing conventional initiator, catalyst, can root
It is adjusted flexibly according to specific monomeric species.
In addition to the solvent employed in above-described embodiment, the present invention in alkali effect under without ligand atom transferred free radical
The solvent that polymerization can be used is at least one in benzene, toluene, tetrahydrofuran, methyl phenyl ethers anisole, diphenyl ether, ethyl acetate,
Can be adjusted flexibly according to monomeric species.Except the specific reaction that atom transition free radical polymerization reaction in above-described embodiment is used
Outside temperature and time, reaction temperature can be adjusted flexibly with the reaction time；Reaction temperature depends on the species of monomer, scope control
Make in the range of general controllable polymerization, such as 30~120 DEG C；Reaction time depending on purpose, studies kinetics, then react
Time is 0~9 hour, prepares specific polymer product, then the reaction time is more than 3 hours.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (8)
1. under a kind of effect of alkali without ligand atom transfer radical polymerization method, it is characterised in that the method is the work in alkali
Under, under conditions of part is not used, make mutually to be mixed including the reaction raw materials including monomer, initiator and catalyst three
Close, so that the monomer carries out atom transition free radical polymerization reaction generates corresponding polymer.
2. under alkali as claimed in claim 1 effect without ligand atom transfer radical polymerization method, it is characterised in that the alkali
Being comprised the following steps without ligand atom transfer radical polymerization method under effect：
Under conditions of anhydrous and isolation oxygen, by the monomer, the alkali, the catalyst and the initiator phase
It is mixed to form pre-reaction mixed liquor；Then the pre-reaction mixed liquor is heated to ATRP set in advance anti-
The reaction temperature answered, the monomer is to proceed by atom transition free radical polymerization reaction to generate corresponding polymer；
The monomer is 200 with the mol ratio of both catalyst:1~500:1；
The monomer is 200 with the mol ratio of both initiators:1~500:1, the alkali rubs with both catalyst
You are than being 0.2:1~4:1.
3. alkali as claimed in claim 1 effect it is lower without ligand atom transfer radical polymerization method, it is characterised in that it is described instead
Answering raw material also includes solvent, and the solvent is preferably in benzene, toluene, tetrahydrofuran, methyl phenyl ethers anisole, diphenyl ether, ethyl acetate extremely
Few one kind.
4. under alkali as claimed in claim 3 effect without ligand atom transfer radical polymerization method, it is characterised in that the alkali
Being comprised the following steps without ligand atom transfer radical polymerization method under effect：
Under conditions of anhydrous and isolation oxygen, by the monomer, the alkali, the catalyst, the solvent and described draw
Hair agent mixes to form pre-reaction mixed liquor；Then the pre-reaction mixed liquor is heated to atom transfer set in advance certainly
By the reaction temperature of base polymerisation, the monomer is to proceed by the corresponding polymerization of atom transition free radical polymerization reaction generation
Thing；
The monomer is 200 with the mol ratio of both catalyst:1~500:1；
The monomer is 200 with the mol ratio of both initiators:1~500:1, the alkali rubs with both catalyst
You are than being 0.2:1~4:1；
The monomer is 1 with the volume ratio of both solvents:1~10:1.
5. as described in claim 2 or 4 alkali effect under without ligand atom transfer radical polymerization method, it is characterised in that institute
Monomer is stated for methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, vinyl chloride, third
At least one in olefin(e) acid, acrylamide, acrylonitrile and vinylacetate；
The initiator be 2- Bromophenylacetic acids ethyl ester, 2- isobutyl ethyl bromides, 2- isobutyl bromides methyl esters, 2 bromopropionic acid ethyl ester and
Any one of 2 bromoethyl benzene；
The alkali be inorganic base, organic base at least one, wherein the inorganic base be sodium carbonate, sodium acid carbonate, potassium carbonate,
At least one in saleratus, NaOH, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate, it is described organic
Alkali is at least one in monoethanolamine, ethylenediamine, triethylamine and urea；
The catalyst is the catalyst containing metallic element, preferably in ferrous bromide, cuprous bromide, ferric bromide and iron chloride
Any one.
6. as described in claim 2 or 4 alkali effect under without ligand atom transfer radical polymerization method, it is characterised in that institute
State pre-reaction mixed liquor stirred under conditions of protective gas mixing 20min~30min obtain；Preferably, the guarantor
Shield property gas is nitrogen or inert gas.
7. as described in claim 2 or 4 alkali effect under without ligand atom transfer radical polymerization method, it is characterised in that institute
The reaction temperature for stating atom transition free radical polymerization reaction set in advance is 30 DEG C~120 DEG C.
8. as described in claim 2 or 4 alkali effect under without ligand atom transfer radical polymerization method, it is characterised in that institute
The reaction time for stating atom transition free radical polymerization reaction is not less than 3 hours；Preferably, the ATRP is anti-
The reaction time answered is 0~9 hour；
Preferably, the atom transition free radical polymerization reaction is terminated by cooling reaction system, generation it is described corresponding
Polymer be to be obtained by removing catalyst described in the reaction system, the alkali and the unreacted monomer purification
's.
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| CN108752543A (en) * | 2018-05-03 | 2018-11-06 | 华中科技大学 | A kind of synthetic method of polyethylene glycol group block copolymer |
| CN108752510A (en) * | 2018-05-17 | 2018-11-06 | 安徽工程大学 | Without iron catalysis AGET ATRP systems and polymerization under the conditions of ligand in a kind of biomass-based solvent |
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| CN111559816A (en) * | 2019-02-13 | 2020-08-21 | 中国石油天然气股份有限公司 | Method for treating wastewater of methyl methacrylate device |
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