CN107056976B - A kind of reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect - Google Patents
A kind of reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect Download PDFInfo
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- CN107056976B CN107056976B CN201710396014.3A CN201710396014A CN107056976B CN 107056976 B CN107056976 B CN 107056976B CN 201710396014 A CN201710396014 A CN 201710396014A CN 107056976 B CN107056976 B CN 107056976B
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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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- 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
- C08F120/16—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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- 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
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
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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
- C08F4/06—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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- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The present invention provides a kind of reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect, the polymerization does not use organic ligand and radical initiator, polymerization system includes vinyl monomer, halogenated hydrocarbons, alkali and high-valence state transition-metal catalyst, so that monomer is carried out reverse atom transfer radical polymerization reaction by activation of the alkali to halogenated hydrocarbons and generates the polymer with Narrow Molecular Weight Distribution.The polymerization avoids the use of the lower valency transition-metal catalyst of radical initiator and water oxygen sensitivity, while overcoming existing atom transfer radical polymerization method and using toxic, volatile organic compound as expensive existing for ligand, environmental pollution defect.
Description
Technical field
The invention belongs to Polymer Synthesizing fields, and in particular, to a kind of reversed atom turn of alkali activation halogenated hydrocarbons effect
Free radical polymerisation process is moved, is a kind of new controllable free radical polymerization process.
Background technique
Atom transfer radical polymerization method is because its suitable monomers type is more, MOLECULE DESIGN is strong, molecular weight of product distribution
The advantages that narrow, becomes most important " activity "/controllable free radical polymerization process.Traditional atom transfer radical polymerization method makes
Body is assigned with lower valency transition-metal catalyst and organic ligand (such as the compound containing P, N, organic acid, ionic liquid etc.) effect
It is greater activity.However lower valency transition metal is easier to be oxidized, to moisture, air-sensitive；Organic ligand component is expensive,
It is more toxic；The disadvantages of catalyst/ligand system dosage is big, and polymerizate post-processing step is cumbersome, at high cost limits the party
The application of method and industrialization development.
To overcome in conventional atom transfer radical polymerization method using lower valency catalyst and organic compound ligand
The reverse atom transfer radical polymerization method that the metal catalyst complex of disadvantage, radical initiator and high-valence state uses is mentioned
Out.The polymerization reaction need to be in polar solvent (such as dimethylformamide, vinyl pyrrolidone, dimethyl containing amide group
Imidazolone etc.) in carry out, show preferable controllable reaction feature.But the polar solvent volatilization that this method uses is serious,
There is very big harm to human health and environment.Reverse atom transfer radical polymerization method is needed using tradition freely simultaneously
Base initiator, stability is poor, and homopolymer is easily formed during preparing block copolymer.These defects also constrain
The Green Development direction of reversed atomic radicals polymerization.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of alkali to activate halogenated hydrocarbons
The reverse atom transfer radical polymerization new method of effect promotes carbon-halogen bond fracture to the activation of halogenated hydrocarbons by alkali, without making
With the lower valency transition-metal catalyst of radical initiator and water oxygen sensitivity, the reversed atom transfer of polymerized monomer is realized certainly
By the controllable polymerization of base, while overcoming existing atom transfer radical polymerization method and using toxic, volatile organic compound
Object (such as the compound containing P, N, organic acid, ionic liquid and the raw material of phosphinylidyne-containing amine group etc.) is high as price existing for ligand
Expensive, environmental pollution defect.
According to one aspect of the present invention, the reversed atom transferred free radical for providing a kind of alkali activation halogenated hydrocarbons effect is poly-
Conjunction method, the polymerization do not use organic ligand and radical initiator, polymerization system include vinyl monomer, halogenated hydrocarbons,
Alkali and high-valence state transition-metal catalyst carry out the vinyl monomer by activation of the alkali to halogenated hydrocarbons reversed former
Sub- transition free radical polymerization reaction generates the polymer with Narrow Molecular Weight Distribution.
Preferably, the reverse atom transfer radical polymerization method of the alkali activation halogenated hydrocarbons effect, specifically includes following
Step:
(1) under conditions of anhydrous and isolation oxygen, by the vinyl monomer, alkali, high-valence state transition-metal catalyst
And halogenated hydrocarbons is uniformly mixed and forms pre-reaction mixed liquor；
Wherein, the molar ratio of the vinyl monomer and high-valence state transition-metal catalyst is 200:1~500:1；It is described
The molar ratio of vinyl monomer and the halogenated hydrocarbons is 200:1~500:1；The alkali and the high-valence state transition-metal catalyst
Molar ratio be 0.2:1~4:1；
(2) the pre-reaction mixed liquor of step (1) is placed under scheduled reaction temperature and is reacted, the vinyl monomer is opened
Begin to carry out the polymer that reverse atom transfer radical polymerization reaction generation has Narrow Molecular Weight Distribution.
Preferably, the reaction radical initiator is azo-initiator or peroxide type initiators.
Preferably, the vinyl monomer is methyl methacrylate, butyl methacrylate, methyl acrylate, propylene
At least one of acid butyl ester, styrene, vinyl chloride, acrylic acid, acrylamide, acrylonitrile and vinylacetate；
The halogenated hydrocarbons is 2- Bromophenylacetic acid ethyl ester, 2- isobutyl ethyl bromide, 2- isobutyl bromide methyl esters, 2 bromopropionic acid second
Any one in ester, 2 bromoethyl benzene, ethyl chloroacetate, 2- chloroethyl nitrile and 2- bromopropionitrile；
The alkali is at least one of inorganic base or organic base, wherein the inorganic base is sodium carbonate, sodium bicarbonate, carbon
Sour potassium, saleratus, sodium hydroxide, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium thiosulfate, hydrogen-oxygen
Change at least one of iron and basic alumina；The organic base be potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, butyl lithium,
Dibutyl magnesium, butylmagnesium chloride, ethanol amine, ethylenediamine, in 11 carbon -7- alkene of triethylamine, imidazoles and 1,8- diazabicylo extremely
Few one kind；
The high-valence state transition-metal catalyst is high-valence state metal halide, preferably ferric bromide, copper bromide, iron chloride
At least one of with ferric chloride hexahydrate.
Preferably, step (1) the pre-reaction mixed liquor is that 20~30 points are stirred under the atmosphere of protective gas
What clock obtained.
Preferably, the protective gas is nitrogen or inert gas.
Preferably, step (2) the predetermined reaction temperature is 50 DEG C~120 DEG C.
Preferably, step (2) the reverse atom transfer radical polymerization reaction time is no less than 3 hours.
Preferably, the reverse atom transfer radical polymerization reaction time is 3~15 hours.
Preferably, the reverse atom transfer radical polymerization reaction of the alkali activation halogenated hydrocarbons effect is reacted by cooling
What system terminated, the polymer with Narrow Molecular Weight Distribution of generation be by remove catalyst in the reaction system,
What alkali and unreacted vinyl monomer purified.
Preferably, the molecular weight distributing index of step (2) described narrow molecular weight distribution polymer is 1.07~1.25.
Contemplated above technical scheme through the invention, compared with prior art, have it is below the utility model has the advantages that
Reverse atom transfer radical polymerization reaction of the invention due to be carried out under alkali activation halogenated hydrocarbons effect it is anti-
To atom transition free radical polymerization reaction, azo or peroxy type free radical initiator are avoided
(e.g., azodiisobutyronitrile, azobisisoheptonitrile, the different heptonitrile of azo dimethoxy, dibenzoyl peroxide and peroxide
Change two diethyl hexylcarbonates) and water oxygen sensitivity lower valency transition-metal catalyst use, while overcoming in the prior art
Atom Transfer Radical Polymerization System organic compound or polar solvent (such as the compound containing P, N, organic acid, ionic liquid, and
The raw material etc. of phosphinylidyne-containing amine group) as it is expensive present in ligand, be more toxic and the disadvantages of volatility, reduce to environment
The extent of damage and reaction cost.
The present invention introduces cheap and easy to get, nontoxic alkali (inorganic base and organic base) in system, can pass through the kind of adjusting alkali
Class and dosage further regulate and control reaction rate and product yield.The carbon-halogen bond of the introducing direct activation halogenated hydrocarbons of alkali, promotes
The generation of living radical, thus by high-valence state transition metal reduction make reverse atom transfer radical polymerization reaction be able into
Row.
The present invention can be avoided azo, peroxy type free radical initiator and organic compound or polar solvent etc. are additional matches
The use of body proposes a kind of new polymerization implementation method, solve the raw material of conventional atom transition free radical polymerization reaction at
This valuableness, the problem of being more toxic, reduce the cost of material of atom transition free radical polymerization reaction, so that system is more green
Environmental protection.Alkali needed for the present invention be inorganic base and organic base, it is simple and easy to get.
The reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect, is suitable for all kinds of vinyl in the present invention
The polymerization of monomer, such as methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, chloroethene
Alkene, acrylic acid, acrylamide, acrylonitrile and vinylacetate；The alkali of use is either inorganic base (such as sodium carbonate, bicarbonate
Sodium, potassium carbonate, saleratus, sodium hydroxide, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate etc.), it is also possible to
Organic base (such as ethanol amine, ethylenediamine, triethylamine, imidazoles).
The present invention is excellent by the molar ratio that reverse atom transfer radical polymerization is reacted medium vinyl monomer and catalyst
Selected control system is preferably controlled to 200:1~500:1 in the molar ratio of 200:1~500:1, vinyl monomer and halogenated hydrocarbons, alkali with urge
The molar ratio of agent is preferably controlled to 0.2:1~4:1；By ratio (the especially addition ratio of alkali for controlling each reaction raw materials
Example), and pass through the overall co-ordination of each reaction condition, it can be ensured that effective hair of reverse atom transfer radical polymerization reaction
It is raw, guarantee reaction rate, product yield and polymerization controlling appropriate.In addition, the present invention is by shifting certainly reversed son
Reaction temperature by base polymerization reaction is preferably 50 DEG C~120 DEG C, and the reaction time is preferably 3 hours or more (or 3~15 hours),
Specific subject polymer product can be ensured to generate.
In the present invention, the introducing of alkali can be in the case where not adding any extra ligand, and alkali can be halogenated with direct activation
The carbon-halogen bond of hydrocarbon reduces the redox potential of halogenated hydrocarbons, accelerates the generation of living radical, so that electronics transfer is easier to send out
It is raw, so that high-valence state transition-metal catalyst be restored and reverse atom transfer radical polymerization reaction occurs.
The present invention combines alkali and atom transfer radical polymerization method, well controls in atom transfer radical polymerization
On the basis of property processed, by the introducing of alkali, a kind of no ligand and the reversed atom transfer freedom without radical initiator are constructed
Base polymerize new method, accelerates existing reaction process, reduces cost of material, simplifies last handling process, for environmentally protective atom
The development of transferring free-radical polymerization system has great directive significance.
Detailed description of the invention
Fig. 1 is polymerization system [methyl methacrylate] in embodiment 20: [2- Bromophenylacetic acid ethyl ester]0: [ferric bromide]0:
[sodium hydroxide]0The kinetics of polymerization curve that=200:1:1:2 is reacted at 60 DEG C and 90 DEG C respectively；
Fig. 2 is polymerization system [methyl methacrylate] in embodiment 30: [2- Bromophenylacetic acid ethyl ester]0: [ferric bromide]0:
[sodium carbonate]0The molecular weight and molecualr weight distribution curve that=200:1:1:4 is reacted at 60 DEG C；
Fig. 3 is the halogenated hydrocarbons system applied in embodiment 7, changes halogenated hydrocarbons by the effect that cyclic voltammetric method probes into alkali
Redox potential size.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
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 in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect in the present invention, this method are not use to have
Machine ligand and radical initiator, polymerization system include that vinyl monomer, halogenated hydrocarbons, alkali and high-valence state are transition metal-catalyzed
Agent makes the vinyl monomer carry out reverse atom transfer radical polymerization reaction by activation of the alkali to halogenated hydrocarbons, and
Regulate and control reaction rate and product yield by the type and dosage that adjust alkali, obtains the polymer with Narrow Molecular Weight Distribution.
Specifically includes the following steps:
(1) under conditions of anhydrous and isolation oxygen, vinyl monomer, alkali, catalyst and halogenated hydrocarbons are uniformly mixed shape
At pre-reaction mixed liquor, the molar ratio of vinyl monomer and halogenated hydrocarbons is 200:1~500:1, and the molar ratio of alkali and catalyst is
0.2:1~4:1；
(2) the resulting pre-reaction mixed liquor of step (1) is placed in the reactor full of protective gas and is stirred at room temperature 20~
30 minutes, keeps the components such as catalyst fully dispersed in vinyl monomer and dissolve, then place it in predetermined reaction temperature
It polymerize in heating device, it is poly- by changing reaction temperature, halogenated hydrocarbons type, the type of alkali, the dosage of alkali and reaction time adjusting
Close reaction process；
(3) after polymerization reaction reaches scheduled reaction time interval, a certain amount of reaction mixture is taken out from reactor,
It is cooling to stop reaction, to obtain the polymer of differentiated yields；
(4) after removing unreacted vinyl monomer, catalyst and alkali, it is dried to obtain pure polymerizate.
The vinyl monomer be methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate,
One of styrene, vinyl chloride, acrylic acid, acrylamide, acrylonitrile and vinylacetate；
The halogenated hydrocarbons is 2- Bromophenylacetic acid ethyl ester, 2- isobutyl ethyl bromide, 2- isobutyl bromide methyl esters, 2 bromopropionic acid second
One of ester, 2 bromoethyl benzene, ethyl chloroacetate, 2- chloroethyl nitrile and 2- bromopropionitrile；
The alkali is at least one of inorganic base and organic base, wherein the inorganic base is sodium carbonate, sodium bicarbonate, carbon
Sour potassium, saleratus, sodium hydroxide, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium thiosulfate, hydrogen-oxygen
Change one of iron and basic alumina, the organic base is potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, butyl lithium, butyl
One of magnesium, butylmagnesium chloride, ethanol amine, ethylenediamine, 11 carbon -7- alkene of triethylamine, imidazoles and 1,8- diazabicylo；Its
Described in catalyst one of using ferric bromide, copper bromide, iron chloride and ferric chloride hexahydrate.
Preferably, reaction temperature described in step (2) may depend on the type of vinyl monomer, and scope control generally may be used
In the range of control polymerization, 50~120 DEG C；Protective gas described in step (2) is one of inert gas or nitrogen；Step
(2) reaction time depending on purpose, studies kinetics, and the time is 3~15 hours, prepares specific polymerization produce
Object, time are 3 hours or more.
The following are specific embodiments:
Embodiment 1:
After purification by methyl methacrylate monomer, 2- isobutyl ethyl bromide halogenated hydrocarbons and sodium phosphate, polymerization reaction is carried out
Group assignment system, methyl methacrylate, 2- isobutyl ethyl bromide, ferric bromide (high-valence state transition-metal catalyst) and sodium phosphate rub
You are than being 200:1:1:2.Process for preparation are as follows: weigh 0.0836 gram of ferric bromide in glove box and 0.0928 gram of sodium phosphate is put into eggplant
In shape bottle, 6 milliliters of methyl methacrylate monomers are taken to be added in eggplant-shape bottle, magnetic agitation after twenty minutes, it is micro- to add 37.7
2- isobutyl ethyl bromide is risen, continues stirring 2 minutes, obtains pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C；Polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
Remove unreacted monomer, catalyst and alkali, calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolution, by 200~
The neutral alumina pillar of 300 mesh removes catalyst, is dried to obtain polymethyl methacrylate product.
Embodiment 2:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester halogenated hydrocarbons, sodium hydroxide, it carries out polymerizeing anti-
Assignment system, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferric bromide (high-valence state transition-metal catalyst), hydrogen-oxygen should be organized
Change sodium molar ratio is 200:1:1:2.Process for preparation are as follows: 0.0836 gram of ferric bromide and 0.032 gram of hydroxide are weighed in glove box
Sodium is put into eggplant-shape bottle, and 6 milliliters of methyl methacrylate monomers is taken to be added in eggplant-shape bottle, magnetic agitation after twenty minutes, then plus
Enter 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters, continues stirring 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is respectively 60 DEG C and 90
℃；After polymerization reaction reaches scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into flask cooling
Stop reaction, removes unreacted monomer, catalyst and alkali and calculate conversion ratio, dissolved product with 2~5 milliliters of tetrahydrofurans,
Catalyst is removed by the neutral alumina pillar of 200~300 mesh, is dried to obtain polymethyl methacrylate product.
Fig. 1 shows concentration variation and the time (ln [M] of monomer under different temperatures0/ [M]-t) it is in a linear relationship, show this
Under the conditions of polymerization reaction be first order kinetics reaction process, temperature more high reaction rate is faster.
Embodiment 3:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester halogenated hydrocarbons and sodium carbonate, it carries out polymerizeing anti-
Assignment system, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferric bromide (high-valence state transition-metal catalyst) and carbonic acid should be organized
Sodium molar ratio is 200:1:1:4.Process for preparation are as follows: weigh 0.0836 gram of ferric bromide in glove box and 0.120 gram of sodium carbonate is put
Enter in eggplant-shape bottle, takes 6 milliliters of methyl methacrylate monomers to be added in eggplant-shape bottle, magnetic agitation after twenty minutes, adds
49.5 microlitres of 2- Bromophenylacetic acid ethyl esters continue stirring 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C, polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
It goes unreacted monomer, catalyst and alkali to calculate conversion ratio, product is dissolved with 2~5 milliliters of tetrahydrofurans, passes through 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain polymethyl methacrylate product.
Fig. 2 be polymerization system molecular weight and molecualr weight distribution under higher alkali content with the change curve of conversion ratio, table
Bright polymerization system under this condition has preferable controlling.
Embodiment 4:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester halogenated hydrocarbons and potassium hydroxide, it is polymerize
Reactive component is prepared, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferric bromide (high-valence state transition-metal catalyst) and hydrogen
Potassium oxide molar ratio is 200:1:1:2 process for preparation are as follows: 0.0836 gram of ferric bromide and 0.032 gram of hydroxide are weighed in glove box
Potassium is put into eggplant-shape bottle, and 6 milliliters of methyl methacrylate monomers is taken to be added in eggplant-shape bottle, magnetic agitation after twenty minutes, then plus
Enter 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters, continues stirring 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C；Polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
It goes unreacted monomer, catalyst and alkali to calculate conversion ratio, product is dissolved with 2~5 milliliters of tetrahydrofurans, passes through 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain polymethyl methacrylate product.
Embodiment 5:
After purification by Butyl Acrylate Monomer, benzyl chloride halogenated hydrocarbons and sodium carbonate, polymerization reaction group assignment system, propylene are carried out
Acid butyl ester, benzyl chloride, iron chloride (high-valence state transition-metal catalyst) and sodium carbonate molar ratio are 200:1:1:2.Process for preparation
Are as follows: 0.0459 gram of iron chloride is weighed in glove box and 0.06 gram of sodium carbonate is put into eggplant-shape bottle, takes 6 milliliters of butyl acrylate lists
Body is added in eggplant-shape bottle, and magnetic agitation after twenty minutes, adds 7.2 microlitres of benzyl chlorides, continues stirring 2 minutes, is obtained pre- anti-
Answer mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C；Polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
It goes unreacted monomer, catalyst and alkali to calculate conversion ratio, product is dissolved with 2~5 milliliters of tetrahydrofurans, passes through 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain butyl polyacrylate product.
Embodiment 6:
After purification by methyl methacrylate monomer, polymethyl methacrylate macromolecular halogenated hydrocarbons, sodium carbonate, gathered
It closes reactive component to prepare, methyl methacrylate, polymethyl methacrylate macromolecular halogenated hydrocarbons, ferric bromide (high-valence state transition
Metallic catalyst) and sodium carbonate molar ratio be 500:1:1:2.Process for preparation are as follows: weighed in glove box 0.0836 gram of ferric bromide,
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 methacrylic acids
Methylmethacrylate monomer is added in eggplant-shape bottle, and magnetic agitation after twenty minutes, obtains pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C；Polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
It goes unreacted monomer, catalyst and alkali to calculate conversion ratio, is sampled behind scheduled reaction time interval, with 2~5 milliliters of tetrahydro furans
It mutters and removes catalyst by product dissolution, by the neutral alumina pillar of 200~300 mesh, be dried to obtain poly-methyl methacrylate
Ester products.
Embodiment 7:
After purification by acetonitrile, 2- Bromophenylacetic acid ethyl ester halogenated hydrocarbons and potassium hydroxide, the distribution of cyclic voltammetry group is carried out
System, 2- Bromophenylacetic acid ethyl ester and potassium hydroxide molar ratio are 1:2.Process for preparation are as follows: 1.6116 gram four is weighed in glove box
Butylammonium bromide and 0.00675 gram of potassium hydroxide are put into eggplant-shape bottle, take 50 milliliters of acetonitriles and 10.5 microlitres of 2- Bromophenylacetic acids
Ethyl ester is added in four-hole bottle, and magnetic agitation obtains cyclic voltammetry mixed liquor in static 2 minutes after twenty minutes.
Four-hole bottle mixed liquor is transferred in heating device, control 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. 3 is that cyclic voltammetric method probes into whether alkali can activate halogenated hydrocarbons, and wherein a is following for 2- Bromophenylacetic acid ethyl ester
Ring volt-ampere curve, b are the cyclic voltammetry curve of 2- Bromophenylacetic acid ethyl ester after potassium hydroxide is added, it can be seen that alkali reduces halogen
For the redox potential size of hydrocarbon, halogenated hydrocarbons has been activated.Alkali activation halogenated hydrocarbons effect of the present invention turns without the reversed atom of ligand
Free radical polymerisation process is moved, any additional ligand can not used in reaction process, reaction system still has good control
Property processed, and another aspect reaction mechanism cannot be explained with the system mechanism containing ligand, therefore, the present invention is in mechanism study
Aspect has used calculating chemical simulation method and cyclic voltammetric technology explore to reaction mechanism to solve the problems, such as this.
Embodiment 8:
After purification by n-BMA monomer, 2- Bromophenylacetic acid ethyl ester halogenated hydrocarbons and sodium carbonate, it is polymerize
Reactive component is prepared, and methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, catalyst (high-valence state) and sodium carbonate molar ratio are
200:1:1:2.Process for preparation are as follows: the high-valence state transition-metal catalyst and 0.06 gram of sodium carbonate of corresponding amount are weighed in glove box
Be put into eggplant-shape bottle, 8 milliliters of n-BMA monomers taken to be added in eggplant-shape bottle, magnetic agitation after twenty minutes, then plus
Enter 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters, continues stirring 2 minutes, obtain pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C；Polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
It goes unreacted monomer, catalyst and alkali to calculate conversion ratio, product is dissolved with 2~5 milliliters of tetrahydrofurans, passes through 200~300
Purpose neutral alumina pillar removes catalyst, is dried to obtain Vinalac 5920 product.
Embodiment 9:
After purification by methyl methacrylate monomer, 2- isobutyl ethyl bromide halogenated hydrocarbons and sodium phosphate, polymerization reaction is carried out
Group assignment system, methyl methacrylate, 2- isobutyl ethyl bromide, ferric bromide (high-valence state transition-metal catalyst) and sodium phosphate rub
You are than being 400:1:1:0.2.Process for preparation are as follows: weigh 0.0836 gram of ferric bromide in glove box and 0.0093 gram of sodium phosphate is put into
In eggplant-shape bottle, 12 milliliters of methyl methacrylate monomers are taken to be added in eggplant-shape bottle, magnetic agitation after twenty minutes, adds 37.7
Microlitre 2- isobutyl ethyl bromide continues stirring 2 minutes, obtains pre-reaction mixed liquor.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C；Polymerization reaction
After reaching scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping reaction of flask, is removed
Remove unreacted monomer, catalyst and alkali, calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolution, by 200~
The neutral alumina pillar of 300 mesh removes catalyst, is dried to obtain polymethyl methacrylate product.
Rate of polymerization and controllability are adjusted by changing the type of catalyst, uses ferric bromide, iron chloride, bromination respectively
Copper, Iron(III) chloride hexahydrate repeat the preparation of aforementioned pre-reaction mixed liquor and the polymerization reaction mistake without ligand as catalyst
Journey；Rate of polymerization and controllability are adjusted by changing type and the dosage of alkali, uses inorganic base: sodium carbonate, bicarbonate respectively
Sodium, potassium carbonate, saleratus, sodium hydroxide, potassium hydroxide, sodium thiosulfate, iron hydroxide and basic alumina, and
Organic base potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, butyl lithium, dibutyl magnesium, butylmagnesium chloride, ethanol amine, ethylenediamine, triethylamine,
Imidazoles and 11 carbon -7- alkene of 1,8- diazabicylo repeat the preparation of aforementioned pre-reaction mixed liquor and the polymerization reaction mistake without ligand
The polymer of corresponding vinyl monomer can be obtained in journey, tool.
In addition to monomeric species specific in above-described embodiment, the monomeric species that the present invention is applicable in 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；Polymerization reaction is also possible to more either the homopolymerization that a kind of monomer participates in
The copolyreaction that kind monomer participates in；Corresponding halogenated hydrocarbons, catalyst, can be adjusted flexibly according to specific monomeric species.
The specific reaction temperature used by the atom transition free radical polymerization reaction in above-described embodiment and other than the time, instead
Answer temperature that can be adjusted flexibly with the reaction time；Reaction temperature depends on the type of monomer, and scope control is general controllable poly-
In the range of conjunction, such as 50~120 DEG C；Reaction time depending on purpose, studies kinetics, then the reaction time is 3~15 small
When prepare specific polymer product, then the reaction time be 3 hours or more.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect, which is characterized in that the polymerization
Without using organic ligand and radical initiator, polymerization system includes vinyl monomer, halogenated hydrocarbons, alkali and high-valence state transition gold
Metal catalyst makes the vinyl monomer carry out reverse atom transfer radical polymerization anti-by activation of the alkali to halogenated hydrocarbons
The polymer with Narrow Molecular Weight Distribution should be generated；The polymerization specifically includes the following steps:
(1) under conditions of anhydrous and isolation oxygen, by the vinyl monomer, alkali, high-valence state transition-metal catalyst and halogen
It is uniformly mixed for hydrocarbon and forms pre-reaction mixed liquor；
Wherein, the molar ratio of the vinyl monomer and high-valence state transition-metal catalyst is 200:1~500:1；The ethylene
The molar ratio of base monomer and the halogenated hydrocarbons is 200:1~500:1；The alkali rubs with the high-valence state transition-metal catalyst
You are than being 0.2:1~4:1；
(2) the pre-reaction mixed liquor of step (1) is placed under scheduled reaction temperature and is reacted, the vinyl monomer i.e. start into
The reaction of row reverse atom transfer radical polymerization generates the polymer with Narrow Molecular Weight Distribution；The Narrow Molecular Weight Distribution polymerization
The molecular weight distributing index of object is 1.07~1.25；
Wherein, the halogenated hydrocarbons is 2- Bromophenylacetic acid ethyl ester, 2- isobutyl ethyl bromide, 2- isobutyl bromide methyl esters, 2 bromopropionic acid
Any one in ethyl ester, 2 bromoethyl benzene, ethyl chloroacetate, 2- chloroethyl nitrile and 2- bromopropionitrile；
In the case where not adding any extra ligand, the carbon-halogen bond of halogenated hydrocarbons described in the alkali direct activation reduces the halogen
For the redox potential of hydrocarbon, accelerate the generation of living radical, so that electronics transfer is easier to occur, thus by the high price
State transition-metal catalyst restores and reverse atom transfer radical polymerization reaction is occurred.
2. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
The radical initiator is azo-initiator or peroxide type initiators.
3. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
The vinyl monomer is methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, chlorine
At least one of ethylene, acrylic acid, acrylamide, acrylonitrile and vinylacetate；
The alkali is at least one of inorganic base or organic base, wherein the inorganic base is sodium carbonate, sodium bicarbonate, carbonic acid
Potassium, saleratus, sodium hydroxide, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate, sodium thiosulfate, iron hydroxide and alkaline three oxygen
Change at least one of two aluminium；The organic base is potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, butyl lithium, dibutyl magnesium, butyl chloride
Change at least one of magnesium, ethanol amine, ethylenediamine, 11 carbon -7- alkene of triethylamine, imidazoles and 1,8- diazabicylo；
The high-valence state transition-metal catalyst is high-valence state metal halide.
4. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
The high-valence state transition-metal catalyst is at least one of ferric bromide, copper bromide, iron chloride and ferric chloride hexahydrate.
5. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
Step (1) the pre-reaction mixed liquor is to be stirred 20~30 minutes to obtain under the atmosphere of protective gas.
6. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
Step (2) the predetermined reaction temperature is 50 DEG C~120 DEG C.
7. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
Step (2) the reverse atom transfer radical polymerization reaction time is no less than 3 hours.
8. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
Step (2) the reverse atom transfer radical polymerization reaction time is 3~15 hours.
9. the reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect as described in claim 1, which is characterized in that
The reverse atom transfer radical polymerization reaction of the alkali activation halogenated hydrocarbons effect is terminated by cooling reaction system, is generated
The polymer with Narrow Molecular Weight Distribution be by removing catalyst, alkali and unreacted ethylene in the reaction system
Base monomer purification obtains.
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| WO2000056795A1 (en) * | 1999-03-23 | 2000-09-28 | Carnegie Mellon University | Catalytic processes for the controlled polymerization of free radically (co)polymerizable monomers and functional polymeric systems prepared thereby |
| CN106699938A (en) * | 2016-11-29 | 2017-05-24 | 华中科技大学 | Ligand-free atom transfer radical polymerization method under action of alkali |
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| WO2000056795A1 (en) * | 1999-03-23 | 2000-09-28 | Carnegie Mellon University | Catalytic processes for the controlled polymerization of free radically (co)polymerizable monomers and functional polymeric systems prepared thereby |
| CN106699938A (en) * | 2016-11-29 | 2017-05-24 | 华中科技大学 | Ligand-free atom transfer radical polymerization method under action of alkali |
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