CN106749805B - A kind of atom transfer radical polymerization method acted on using low temperature eutectic - Google Patents
A kind of atom transfer radical polymerization method acted on using low temperature eutectic Download PDFInfo
- Publication number
- CN106749805B CN106749805B CN201611069769.4A CN201611069769A CN106749805B CN 106749805 B CN106749805 B CN 106749805B CN 201611069769 A CN201611069769 A CN 201611069769A CN 106749805 B CN106749805 B CN 106749805B
- Authority
- CN
- China
- Prior art keywords
- low temperature
- radical polymerization
- reaction
- temperature eutectic
- eutectic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of atom transfer radical polymerization methods acted on using low temperature eutectic, it is characterized in that, this method is in the environment of low temperature eutectic, mix monomer, initiator and catalyst three, so that so that monomer is carried out atom transition free radical polymerization reaction generates corresponding polymer；Low temperature eutectic is liquid.The present invention is by improving media environment used by atom transition free radical polymerization reaction, using low temperature eutectic as the solvent of polymerization system or ligand, the component of Atom Transfer Radical Polymerization System can be advanced optimized, overcome that ligand used in atom transfer radical polymerization method in the prior art is expensive, the shortcomings that being more toxic.
Description
Technical field
The invention belongs to high molecular reactive polymerization fields, more particularly, to a kind of original acted on using low temperature eutectic
Sub- transfer radical polymerization method, the atom transfer reaction that this method is acted on using low temperature eutectic prepare controllable polymer, are
The atom transfer radical polymerization method of kind green.
Background technique
Atom transfer radical polymerization method can solve the problem of controlling difference in conventional free radical polymerization because of it, then
Realization is widely used to the topological structure of macromolecular and the design effectively of terminal functionality.But common atom transfer is certainly
The ligand as used in base polymerization be mostly volatile organic polar solvent, be more toxic containing N, P-compound or ion
Liquid is not only harmful but also expensive to environment.More will there is biocompatibility, cheap ligand to be applied to atom
It is the inevitable choice for optimizing polymerization, expanding its application range in transferring free-radical polymerization system.
Low temperature eutectic also has other than with the property similar with ionic liquid such as chemical inertness, non-volatile, nonflammable
There is raw material to be easy to get, it is degradable, preparation is simple and preparation process in do not generate waste, it is the advantages that Environmental compatibility is good, net in gas
The fields such as change, electrochemical deposition, organic and biocatalysis have broad application prospects.If low temperature eutectic can be applied to
Atom transfer radical polymerization field, it would be possible to obtain the ligand component in general Atom Transfer Radical Polymerization System greatly
Optimization reduces reaction cost, promotes the development of green living polymerisation process.But up to the present, do not have low temperature eutectic also
Report for atom transfer radical polymerization field or other living polymerization fields.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, low-temperature eutectic is utilized the purpose of the present invention is to provide a kind of
The atom transfer radical polymerization method of body effect, wherein by used by its critical atoms transition free radical polymerization reaction
Media environment improves, can be to atom transferred free radical using low temperature eutectic as the solvent of polymerization system or ligand
The component of polymerization system is advanced optimized, and ligand valence used in atom transfer radical polymerization method in the prior art is overcome
Lattice are expensive, the shortcomings that being more toxic, which does not need to add in any conventional atom transition free radical polymerization reaction
Organic compound or polar solvent have the advantages that environmentally protective as ligand；In addition, the present invention can be total by adjusting low temperature
Type and dosage regulation reaction rate, product yield and the polymerization controlling of melt, produce so that required polymerization be prepared
Object.
To achieve the above object, it is proposed, according to the invention, it is free to provide a kind of atom transfer using low temperature eutectic effect
Base polymerization, which is characterized in that this method is to make monomer, initiator and catalyst three in the environment of low temperature eutectic
Person mixes, so that so that the monomer is carried out atom transition free radical polymerization reaction generates corresponding polymer；
The low temperature eutectic is liquid.
As present invention further optimization, the fusing point of the low temperature eutectic is lower than the atom transfer radical polymerization
The reaction temperature of reaction.
As present invention further optimization, the catalyst is the catalyst containing metallic element, described to utilize low temperature
Eutectic effect atom transfer radical polymerization method the following steps are included:
Under conditions of anhydrous and isolation oxygen, the monomer and the catalyst containing metallic element are mixed to form
First mixture；Then first mixture is heated to the reaction temperature of preset atom transition free radical polymerization reaction
Degree；Then, the low temperature eutectic is added in first mixture, and initiator is added into first mixture,
The monomer starts to carry out the corresponding polymer of atom transition free radical polymerization reaction generation；
The molar ratio of both the monomer and the catalyst containing metallic element is 50:1~500:1；
The molar ratio of both the monomer and the initiator is 50:1~500:1；The monomer and the low-temperature eutectic
The volume ratio of body is 3:1~200:1；
As present invention further optimization, the low temperature eutectic be acetamide-caprolactam, acetamide-urea, oneself
Lactams-urea, choline chloride-lactic acid, choline chloride-malonic acid, choline chloride-oxalic acid, choline chloride-ethylene glycol, chlorination
Choline-glycerol, tetrabutylammonium bromide-ethylene glycol, tetrabutylammonium bromide-glycerol, cetyl trimethylammonium bromide-ethylene glycol,
Tetrabutylammonium bromide-ethanol amine, potassium rhodanide-acetamide, potassium rhodanide-caprolactam, ammonium thiocyanate-acetamide, thiocyanic acid
Any one in ammonium-caprolactam, ammonium thiocyanate-urea；
The monomer be methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene,
At least one of vinyl chloride, acrylic acid, acrylamide, acrylonitrile and vinylacetate；The initiator is 2- bromophenyl second
Any one of acetoacetic ester, 2- isobutyl ethyl bromide, 2- isobutyl bromide methyl esters, 2 bromopropionic acid ethyl ester and 2 bromoethyl benzene；
The catalyst containing metallic element is at least one in ferrous bromide, cuprous bromide, ferric bromide and iron chloride
Kind.
As present invention further optimization, first mixture is stirred under conditions of protective gas
What 20min~30min was obtained.
As present invention further optimization, the reaction temperature of the preset atom transition free radical polymerization reaction
It is 30 DEG C~120 DEG C.
As present invention further optimization, the reaction time of the atom transition free radical polymerization reaction is not less than 0.5
Hour；Preferably, the reaction time of the atom transition free radical polymerization reaction is 0~21 hour；
Preferably, the atom transition free radical polymerization reaction is terminated by cooling reaction system, generation it is described
Corresponding polymer is obtained by removing catalyst described in the reaction system and the unreacted monomer purification.
As present invention further optimization, the protective gas is nitrogen or inert gas.
It is described that the low temperature eutectic is added in first mixture as present invention further optimization, be
The low temperature eutectic is first heated to the reaction temperature of the preset atom transition free radical polymerization reaction, then again
The low temperature eutectic after heating is added in first mixture.
Contemplated above technical scheme through the invention, compared with prior art, due to being acted on using low temperature eutectic
Under atom transfer radical polymerization method, be under atom transfer radical polymerization good controlling basis, by system
It is middle to be introduced into organising in simple and easy to get, Environmental compatibility low temperature eutectic substitution conventional atom transition free radical polymerization reaction
Close object or polar solvent (such as conventional ligands), exclude present in existing ligand it is expensive, be more toxic with volatility etc.
Disadvantage, and reaction rate and product yield are further regulated and controled by the type of adjusting low temperature eutectic and dosage.Low temperature is total
The introducing of melt forms labile coordination compound with metallic catalyst and plays catalytic action to polymerization system；Moreover, low temperature eutectic is also
The solvent that can serve as reaction system is effectively reduced the viscosity and reaction heat of system, improves reaction rate and conversion ratio.The present invention
It no longer needs to add additional organic compound or polar solvent, reduces the cost of material of atom transition free radical polymerization reaction, letter
The last handling process of product is changed, so that system more greenization.Low temperature eutectic needed for the invention is cheap and easy to get
Composition is prepared, and Atom economy is high.
It, can be total by adjusting low temperature using the atom transfer radical polymerization method of low temperature eutectic effect in the present invention
Type and dosage the regulation reaction rate and product yield of melt, obtain required polymerizate.Low temperature in the present invention is total
Melt can be acetamide-caprolactam, acetamide-urea, caprolactam-urea, choline chloride-lactic acid, choline chloride-
Malonic acid, choline chloride-oxalic acid, choline chloride-ethylene glycol, choline chloride-glycerol, tetrabutylammonium bromide-ethylene glycol, the tetrabutyl
Ammonium bromide-glycerol, cetyl trimethylammonium bromide-ethylene glycol, tetrabutylammonium bromide-ethanol amine, potassium rhodanide-acetamide,
It is potassium rhodanide-caprolactam, ammonium thiocyanate-acetamide, ammonium thiocyanate-caprolactam, any one in ammonium thiocyanate-urea
Kind.Monomer can be methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, chloroethene
One of alkene, acrylic acid, acrylamide, acrylonitrile and vinylacetate；The initiator is 2- Bromophenylacetic acid ethyl ester, 2-
Any one of isobutyl ethyl bromide, 2- isobutyl bromide methyl esters, 2 bromopropionic acid ethyl ester and 2 bromoethyl benzene.
Although some type of low temperature eutectic is liquid at room temperature, since viscosity is larger, if directly existed
It is mixed at room temperature with reaction system, not only charging is inconvenient, while the coordination between low temperature eutectic and catalyst can also made
Weaker with and with intermiscibility between monomer, therefore, the present invention further preferably heats low temperature eutectic with catalyst system simultaneously
It is remixed to reaction temperature and (since the ratio between the volume of monomer and volume of low temperature eutectic are 3:1~200:1, works as low-temperature eutectic
When the volume of body is much smaller than the volume of monomer, due to addition low temperature eutectic influence of the temperature to temperature of reaction system compared with
It is small, at this point, low temperature eutectic can also be added directly into reaction system, that is, in the first mixture), to avoid these problems.
In addition, the present invention is also preferably controlled by the type to low temperature eutectic, can further preferably gather atom transferred free radical
Close the reaction effect of reaction.
The present invention is by by both monomer in atom transition free radical polymerization reaction and the catalyst containing metallic element
The molar ratio that molar ratio is preferably controlled in both 50:1~500:1 (more preferably 50:1~200:1), monomer and initiator is preferred
Control is 50:1~500:1；The volume ratio of monomer and low temperature eutectic is preferably controlled to 3:1~200:1, passes through each reaction item
The overall co-ordination of part, it can be ensured that effective generation of atom transition free radical polymerization reaction guarantees reaction rate appropriate, product
Conversion ratio and polymerization controlling.In addition, the present invention by being preferably by the reaction temperature of atom transition free radical polymerization reaction
30 DEG C~120 DEG C, the reaction time is preferably 0.5 hour or more, it can be ensured that generates specific subject polymer product.
In the present invention, low temperature eutectic may be used as the reaction medium or solvent of organic reaction, substitute traditional organic match
Body and metallic catalyst form labile coordination compound；And low temperature eutectic may be used as the solvent of reaction system, be effectively reduced
The viscosity and reaction heat of system improve reaction rate and conversion ratio.
The present invention combines low temperature eutectic and atom transfer radical polymerization, good in atom transfer radical polymerization
On the basis of good controlling, atom transferred free radical reactive component is advanced optimized by the introducing of low temperature eutectic, is reduced
Cost of material improves the Environmental compatibility of ligand, has for the development of green Atom Transfer Radical Polymerization System great
Directive significance.
Detailed description of the invention
Fig. 1 a is polymerization system [methyl methacrylate] in embodiment 10: [2- Bromophenylacetic acid ethyl ester]0: [protobromide
Iron]0: [low temperature eutectic]0The kinetics of polymerization curve that=100:1:1:1 is reacted at 60 DEG C；
Fig. 1 b is molecular weight and molecualr weight distribution corresponding with kinetics of polymerization curve in embodiment 1 with the change of conversion ratio
Change curve.
Fig. 1 a, Fig. 1 b targeted low temperature eutectic is acetamide-ammonium thiocyanate low temperature eutectic, acetamide-thiocyanic acid
Potassium low temperature eutectic, urea-ammonium thiocyanate low temperature eutectic and urea-potassium rhodanide low temperature eutectic are using this four groups
Low temperature eutectic is tested respectively, and other than the type of low temperature eutectic is different, other keep with embodiment 1 experiment condition
Unanimously.
Fig. 2 is the polymerization system applied in embodiment 5, [methyl methacrylate]0: [polymethyl methacrylate divides greatly
Sub- initiator]0: [ferrous bromide]0: [tetrabutylammonium bromide-glycerol]0The different molecular weight that=400:1:1:1 is reacted at 60 DEG C is poly-
Object elution curve is closed, is followed successively by 0h, 1h, 3h, 4h, 4.3h, 4.5h from left to right.
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 atom transfer radical polymerization method under low temperature eutectic effect in the present invention, is the work in low temperature eutectic
Under, atom transition free radical polymerization reaction is carried out after monomer, catalyst and initiator are mixed, does not need to add any tradition
Organic compound or polar solvent in atom transition free radical polymerization reaction passes through adjusting low temperature eutectic as ligand
Type and dosage regulation reaction rate and product yield, obtain required polymerizate.It specifically, may include following step
It is rapid:
(1) low temperature eutectic component is mixed according to corresponding ratio, slowly heating forms the transparent eutectic without precipitating,
Cooling, when use, is heated to polymeric reaction temperature；
(2) polymerization reaction component, in polymerization reaction component, mole of monomer and initiator are prepared under the conditions of anhydrous and oxygen-free
Than for 50:1~500:1, volume ratio 3:1~200:1 of monomer and low temperature eutectic；
(3) reactive component of step (2) is mixed be placed in the reactor full of protective gas stir 20 at room temperature~
30min keeps the components such as catalyst fully dispersed in monomer and dissolves, then places it in heating device and heat for example
5min；
(4) the resulting low temperature eutectic component of step (1) is added in step (3) resulting polymeric component, passes through change
Reaction temperature, initiator type, the type of low temperature eutectic and dosage and reaction time telo merization process；
(5) 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；
(6) after removing unreacted monomer and catalyst, it is dried to obtain pure polymerizate.
The following are specific embodiments:
Embodiment 1:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are 100:
(low temperature eutectic is respectively four groups, that is, acetamide-ammonium thiocyanate low temperature is total for 1:1, methyl methacrylate and low temperature eutectic
Melt, acetamide-potassium rhodanide low temperature eutectic, urea-ammonium thiocyanate low temperature eutectic, urea-potassium rhodanide low-temperature eutectic
Body) volume ratio be 100:1.Process for preparation are as follows: weigh 0.122 gram of ferrous bromide in glove box and be put into eggplant-shape bottle, take 6 millis
It rises methyl methacrylate monomer to be added in eggplant-shape bottle, 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 of heating stirrings five
Minute, it adds 60 microlitres of low temperature eutectics and 90 microlitres of 2- Bromophenylacetic acid ethyl esters starts to react, polymerization reaction reaches predetermined
Reaction time interval after, a certain amount of mixture is taken out from reactor and pours into that flask is cooling to stop reaction, removes unreacted
Monomer and catalyst calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolution, pass through the neutral oxygen of 200~300 mesh
Change aluminium pillar and remove catalyst, is dried to obtain polymethyl methacrylate product.
Concentration variation and the time (ln [M] of Fig. 1 a displaying monomer0/ ln [M]-t) it is in a linear relationship, show under this condition
Polymerization reaction is first order kinetics reaction process.Fig. 1 b is that the corresponding molecular weight and molecualr weight distribution of kinetics of polymerization curve exists
With the change curve of conversion ratio in the presence of low temperature eutectic.
Embodiment 2:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are 200:
The volume ratio of 1:1, methyl methacrylate and low temperature eutectic is that (low temperature eutectic is divided into three kinds to 3:1, i.e. caprolactam-second
Amide low temperature eutectic, acetamide-urea low temperature eutectic, caprolactam-urea low temperature eutectic).Process for preparation are as follows: in hand
0.061 gram of ferrous bromide is weighed in casing to be put into eggplant-shape bottle, and 6 milliliters of methyl methacrylate monomers is taken to be added to eggplant-shape bottle
In, 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 of heating stirrings five
Minute, it adds 2 milliliters of low temperature eutectics and 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters starts to react, polymerization reaction reaches predetermined
Reaction time interval after, a certain amount of mixture is taken out from reactor and pours into that flask is cooling to stop reaction, removes unreacted
Monomer and catalyst calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolution, pass through the neutral oxygen of 200~300 mesh
Change aluminium pillar and remove catalyst, is dried to obtain polymethyl methacrylate product.
Embodiment 3:
After purification by n-BMA monomer, 2- Bromophenylacetic acid ethyl ester initiator, polymerization reaction component is carried out
It prepares, n-BMA, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are
50:1:1, methyl methacrylate and acetamide-potassium rhodanide low temperature eutectic volume ratio are 50:1.Process for preparation are as follows:
0.122 gram of ferrous bromide is weighed in glove box to be put into eggplant-shape bottle, and 4 milliliters of n-BMA monomers is taken to be added to eggplant shape
In bottle, 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 of heating stirrings five
Minute, it adds 30 microlitres of acetamides-potassium rhodanide low temperature eutectic and 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters starts to react,
After polymerization reaction reaches scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping of flask
Reaction, removes unreacted monomer and catalyst calculates conversion ratio, dissolves product with 2~5 milliliters of tetrahydrofurans, passes through 200
The neutral alumina pillar of~300 mesh removes catalyst, is dried to obtain Vinalac 5920 product.
Embodiment 4:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferric bromide (high-valence state transition-metal catalyst) and ascorbic acid rub
, than being 500:1:1:2, the volume ratio of methyl methacrylate and low temperature eutectic is that (low temperature eutectic is divided into four fourths to 500:1 for you
Base ammonium bromide-glycerol low temperature eutectic, tetrabutylammonium bromide-ethylene glycol low temperature eutectic, choline chloride-glycerol low-temperature eutectic
Body, choline chloride-ethylene glycol low temperature eutectic, choline chloride-malonic acid low temperature eutectic).Process for preparation are as follows: in glove box
It weighs 0.033 gram of ferric bromide and 0.02 gram of ascorbic acid is put into eggplant-shape bottle, 6 milliliters of methyl methacrylate monomers is taken to be added to
In eggplant-shape bottle, 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 of heating stirrings five
Minute, it adds 2 milliliters of low temperature eutectics and 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters starts to react, polymerization reaction reaches predetermined
Reaction time interval after, a certain amount of mixture is taken out from reactor and pours into that flask is cooling to stop reaction, removes unreacted
Monomer and catalyst calculate conversion ratio, with 2~5 milliliters of tetrahydrofurans by product dissolution, pass through the neutral oxygen of 200~300 mesh
Change aluminium pillar and remove catalyst, is dried to obtain polymethyl methacrylate product.
Embodiment 5:
After purification by methyl methacrylate monomer, polymethyl methacrylate macromole evocating agent, polymerization reaction is carried out
Group assignment system, methyl methacrylate, polymethyl methacrylate macromole evocating agent and ferrous bromide (lower valency transition metal
Catalyst) molar ratio be 400:1:1, methyl methacrylate and tetrabutylammonium bromide-glycerol low temperature eutectic volume ratio
For 400:1.Process for preparation are as follows: 0.038 gram of ferric bromide and 1.736 grams of polymethyl methacrylate macromoleculars are weighed in glove box
Initiator is put into eggplant-shape bottle, and 7.5 milliliters of methyl methacrylate monomers is taken to be added in eggplant-shape bottle, and magnetic agitation 20 minutes
Afterwards, pre-reaction mixed liquor is obtained.
Pre-reaction mixed liquor in eggplant-shape bottle is transferred in heating device, control reaction temperature is 60 DEG C of heating stirrings five
Minute, it adds 38 microlitres of tetrabutylammonium bromide-glycerol low temperature eutectic and starts to react, when polymerization reaction reaches scheduled reaction
Between be spaced after, a certain amount of mixture is taken out from reactor and pours into that flask is cooling to stop reaction, remove unreacted monomer and
Catalyst calculates conversion ratio, dissolves product with 2~5 milliliters of tetrahydrofurans, passes through the neutral alumina pillar of 200~300 mesh
Catalyst is removed, the polymethyl methacrylate product of chain extension is dried to obtain.
Fig. 2 is that polymethyl methacrylate causes the different molecular weight that monomer polymerization obtains as macromole evocating agent again
Polymer elution curve, be followed successively by 0h, 1h, 3h, 4h, 4.3h, 4.5h from left to right.
Embodiment 6:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are 200:
1:1, methyl methacrylate and choline chloride-lactic acid low temperature eutectic volume ratio are 200:1.Process for preparation are as follows: in gloves
0.061 gram of ferrous bromide is weighed in case to be 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, 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 of heating stirrings five
Minute, it adds 30 microlitres of choline chlorides-lactic acid low temperature eutectic and 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters starts to react, gather
After conjunction reaction reaches scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping of flask instead
Answer, remove unreacted monomer and catalyst and 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 7:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are 200:
1:1, methyl methacrylate and tetrabutylammonium bromide-ethanol amine low temperature eutectic volume ratio are 200:1.Process for preparation are as follows:
0.061 gram of ferrous bromide is weighed in glove box to be put into eggplant-shape bottle, and 6 milliliters of methyl methacrylate monomers is taken to be added to eggplant shape
In bottle, 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 of heating stirrings five
Minute, it adds 30 microlitres of tetrabutylammonium bromide-ethanol amine low temperature eutectic and 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters starts
Reaction, after polymerization reaction reaches scheduled reaction time interval, a certain amount of mixture is taken out from reactor, and to pour into flask cold
But stop reaction, remove unreacted monomer and catalyst calculates conversion ratio, product is dissolved with 2~5 milliliters of tetrahydrofurans, is logical
The neutral alumina pillar for crossing 200~300 mesh removes catalyst, is dried to obtain polymethyl methacrylate product.
Embodiment 8:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are 200:
1:1, methyl methacrylate and choline chloride-oxalic acid low temperature eutectic volume ratio are 200:1.Process for preparation are as follows: in gloves
0.061 gram of ferrous bromide is weighed in case to be 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, 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 of heating stirrings five
Minute, it adds 30 microlitres of choline chlorides-oxalic acid low temperature eutectic and 49.5 microlitres of 2- Bromophenylacetic acid ethyl esters starts to react, gather
After conjunction reaction reaches scheduled reaction time interval, a certain amount of mixture is taken out from reactor and pours into the cooling stopping of flask instead
Answer, remove unreacted monomer and catalyst and 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 9:
After purification by methyl methacrylate monomer, 2- Bromophenylacetic acid ethyl ester initiator, the distribution of polymerization reaction group is carried out
System, methyl methacrylate, 2- Bromophenylacetic acid ethyl ester, ferrous bromide (lower valency transition-metal catalyst) molar ratio are 200:
1:1, methyl methacrylate and cetyl trimethylammonium bromide-ethylene glycol low temperature eutectic volume ratio are 200:1.It prepares
Process are as follows: weigh 0.061 gram of ferrous bromide in glove box and be put into eggplant-shape bottle, 6 milliliters of methyl methacrylate monomers is taken to add
Enter into eggplant-shape bottle, 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 of heating stirrings five
Minute, add 30 microlitres of cetyl trimethylammonium bromides-ethylene glycol low temperature eutectic and 49.5 microlitres of 2- Bromophenylacetic acids
Ethyl ester starts to react, and after polymerization reaction reaches scheduled reaction time interval, a certain amount of mixture is taken out from reactor and is fallen
Enter the cooling stopping reaction of flask, removes unreacted monomer and catalyst calculates conversion ratio, will be produced with 2~5 milliliters of tetrahydrofurans
Object dissolution removes catalyst by the neutral alumina pillar of 200~300 mesh, is dried to obtain polymethyl methacrylate product.
Low temperature eutectic in the present invention is the eutectic mixture on ordinary meaning, can be matched according to corresponding compound
Each component of low temperature eutectic is mixed than ratio, slowly heating forms the transparent eutectic without precipitating, cooling, and when use adds
Heat is to polymeric reaction temperature.Low temperature eutectic can be polynary eutectic (such as binary eutectic, ternary eutectic)；Altogether
The ratio of each chemical component can be adjusted flexibly in melt, as long as ensuring poly- in preset atom transferred free radical
Under the reaction temperature for closing reaction, which is in the liquid of congruent melting.It, can be by binary composition by taking binary eutectic as an example
It mixes according to a certain percentage, stirring is heated slowly to certain temperature and supernatant liquid occurs, and cooling obtains low temperature eutectic；Two groups
/ it is eutectic (that is, low temperature eutectic) to be formed by interaction of hydrogen bond, and the fusing point of this eutectic is than the two
The fusing point of independent component will be low.(reaction temperature can be greater than low temperature eutectic system in the present invention at the reaction temperatures
Or be equal to room temperature) be all liquid (at room temperature mostly is also all liquid), fusing point it is minimum can be -66 DEG C.
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
One of nitrile and vinylacetate；Initiator is 2- Bromophenylacetic acid ethyl ester, 2- isobutyl ethyl bromide, 2- isobutyl bromide first
Any one of ester, 2 bromopropionic acid ethyl ester and 2 bromoethyl benzene；Polymerization reaction either a kind of monomer participate in homopolymerization,
It is also possible to the copolyreaction of various of monomer participation；Corresponding initiator, catalyst, can also be used existing conventional initiator,
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 low temperature eutectic, scope control
In the range of general controllable polymerization, such as 30~120 DEG C；Reaction time depending on purpose, studies kinetics, then when reacting
Between be 0~21 hour, prepare specific polymer product, then the reaction time be 0.5 hour 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 (10)
1. a kind of atom transfer radical polymerization method acted on using low temperature eutectic, which is characterized in that this method is low
In the environment of warm eutectic, mix monomer, initiator and catalyst three, so that the monomer be made to carry out atom transfer
Raolical polymerizable generates corresponding polymer；This method can be regulated and controled anti-by the type and dosage for adjusting low temperature eutectic
Rate, product yield and polymerization controlling are answered, so that required polymerizate be prepared；
The low temperature eutectic is liquid, and the low temperature eutectic is acetamide-caprolactam, acetamide-urea, in oneself
Amide-urea, choline chloride-lactic acid, choline chloride-malonic acid, choline chloride-oxalic acid, choline chloride-ethylene glycol, chlorination gallbladder
Alkali-glycerol, tetrabutylammonium bromide-ethylene glycol, tetrabutylammonium bromide-glycerol, cetyl trimethylammonium bromide-ethylene glycol, four
Butylammonium bromide-ethanol amine, potassium rhodanide-acetamide, potassium rhodanide-caprolactam, ammonium thiocyanate-acetamide, ammonium thiocyanate-
Any one in caprolactam, ammonium thiocyanate-urea；In addition, the low temperature eutectic is specifically by low temperature eutectic each component
Mixing, then heating forms what the transparent eutectic without precipitating obtained；
The catalyst be the catalyst containing metallic element, the polymerization the following steps are included:
Under conditions of anhydrous and isolation oxygen, the monomer and the catalyst containing metallic element are mixed to form first
Mixture；Then first mixture is heated to the reaction temperature of preset atom transition free radical polymerization reaction；It connects
, the low temperature eutectic is added in first mixture, and initiator, the list are added into first mixture
Body starts to carry out the corresponding polymer of atom transition free radical polymerization reaction generation；
The molar ratio of both the monomer and the catalyst containing metallic element is 50:1~500:1；
The molar ratio of both the monomer and the initiator is 50:1~500:1；The monomer and the low temperature eutectic
Volume ratio is 3:1~200:1；
The introducing of low temperature eutectic forms labile coordination compound with metallic catalyst and plays catalytic action to polymerization system；Moreover, low
Warm eutectic can also act as the solvent of reaction system, be effectively reduced the viscosity and reaction heat of system, improves reaction rate and turns
Rate.
2. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that institute
The fusing point for stating low temperature eutectic is lower than the reaction temperature of the atom transition free radical polymerization reaction.
3. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that institute
Stating monomer is methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, styrene, vinyl chloride, third
At least one of olefin(e) acid, acrylamide, acrylonitrile and vinylacetate；The initiator is 2- Bromophenylacetic acid ethyl ester, 2-
Any one of isobutyl ethyl bromide, 2- isobutyl bromide methyl esters, 2 bromopropionic acid ethyl ester and 2 bromoethyl benzene；
The catalyst containing metallic element is at least one of ferrous bromide, cuprous bromide, ferric bromide and iron chloride.
4. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that institute
Stating the first mixture is to be stirred what 20min~30min was obtained under conditions of protective gas.
5. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that institute
The reaction temperature for stating preset atom transition free radical polymerization reaction is 30 DEG C~120 DEG C.
6. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that institute
The reaction time of atom transition free radical polymerization reaction is stated not less than 0.5 hour.
7. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that institute
The reaction time for stating atom transition free radical polymerization reaction is 0~21 hour.
8. as claimed in claims 6 or 7 using the atom transfer radical polymerization method of low temperature eutectic effect, feature exists
In the atom transition free radical polymerization reaction is terminated by cooling reaction system, the corresponding polymer of generation
It is to be obtained by removing catalyst described in the reaction system and the unreacted monomer purification.
9. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as claimed in claim 4, which is characterized in that institute
Stating protective gas is nitrogen or inert gas.
10. utilizing the atom transfer radical polymerization method of low temperature eutectic effect as described in claim 1, which is characterized in that
It is described that the low temperature eutectic is added in first mixture, be first by the low temperature eutectic be heated to it is described in advance
The low temperature eutectic after heating is then added to institute again by the reaction temperature of the atom transition free radical polymerization reaction of setting
It states in the first mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611069769.4A CN106749805B (en) | 2016-11-29 | 2016-11-29 | A kind of atom transfer radical polymerization method acted on using low temperature eutectic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611069769.4A CN106749805B (en) | 2016-11-29 | 2016-11-29 | A kind of atom transfer radical polymerization method acted on using low temperature eutectic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106749805A CN106749805A (en) | 2017-05-31 |
| CN106749805B true CN106749805B (en) | 2019-07-09 |
Family
ID=58905147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611069769.4A Active CN106749805B (en) | 2016-11-29 | 2016-11-29 | A kind of atom transfer radical polymerization method acted on using low temperature eutectic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106749805B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752543B (en) * | 2018-05-03 | 2019-07-23 | 华中科技大学 | A kind of synthetic method of polyethylene glycol group block copolymer |
| CN109942220B (en) * | 2019-03-05 | 2021-07-23 | 北京工业大学 | Preparation method of salt-resistant amphoteric polycarboxylic acid high-performance water reducing agent |
| CN112708014B (en) * | 2020-12-23 | 2022-02-18 | 华南理工大学 | Recyclable self-repairing transparent conductive elastomer and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104755506A (en) * | 2012-10-16 | 2015-07-01 | 汉高知识产权控股有限责任公司 | Controlled radical polymerization of (meth)acrylic monomers |
-
2016
- 2016-11-29 CN CN201611069769.4A patent/CN106749805B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104755506A (en) * | 2012-10-16 | 2015-07-01 | 汉高知识产权控股有限责任公司 | Controlled radical polymerization of (meth)acrylic monomers |
Non-Patent Citations (2)
| Title |
|---|
| "Deep-eutectic solvents playing multiple roles in the synthesis of polymers and related materials";Carriazo, Daniel et al.;《Chemical Society Reviews》;20121231;第41卷(第14期);第4996-5014也 |
| "Novel ionic liquids as reaction medium for ATRP of acrylonitrile in the absence of any ligand";Chen Hou et al.;《Polymer》;20080728;第49卷(第16期);第3424–3427页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106749805A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106749805B (en) | A kind of atom transfer radical polymerization method acted on using low temperature eutectic | |
| Yamago et al. | Highly controlled living radical polymerization through dual activation of organobismuthines | |
| CN106699938B (en) | Under a kind of effect of alkali without ligand atom transfer radical polymerization method | |
| CN107141385A (en) | A kind of preparation method of low molecular weight brominated polystyrene | |
| JP3587530B2 (en) | Radical polymerization method | |
| CN107880229B (en) | Preparation method of end group modified polyacrylate block copolymer and polyacrylate block copolymer prepared by preparation method | |
| WO2004081020A1 (en) | Transition metal complexes, especially iron complexes, used as a catalyst component in the polymerisation of olefins | |
| CN106749778B (en) | A kind of electrochemical regulating and controlling atom transfer radical polymerization method of nontoxic ligand | |
| Thevenin et al. | Impact of Catalyzed Radical Termination (CRT) and Reductive Radical Termination (RRT) in Metal‐Mediated Radical Polymerization Processes | |
| CN107177018B (en) | A kind of effect of metal simple-substance without ligand atom transfer radical polymerization method | |
| CN107056976B (en) | A kind of reverse atom transfer radical polymerization method of alkali activation halogenated hydrocarbons effect | |
| CN103788266B (en) | A kind of method of atom transfer radical polymerization | |
| CN104163879B (en) | A kind of atom transfer radical polymerization method under magnetic field | |
| Chen et al. | Atom transfer radical polymerizations of methyl methacrylate catalyzed by EBiB/SnCl2· 2H2O (FeCl2· 4H2O)/FeCl3· 6H2O/MA5-DETA systems | |
| CN113336882B (en) | Process for preparing PMMA resin with narrow molecular weight distribution by adopting intermittent bulk polymerization method | |
| CN108752543B (en) | A kind of synthetic method of polyethylene glycol group block copolymer | |
| GB944266A (en) | Process for the production of acrylonitrile copolymers | |
| Li et al. | New Development in Rare Earth Metal Complexes Containing Anionic Bis (imino) pyrrolyl and Bis (phosphanyl) amide Ligands | |
| CN106916247A (en) | PMMA performed polymers and its preparation method and application | |
| CN108546311B (en) | A kind of atom transfer radical polymerization method of inorganic metal salt regulation | |
| CN106496386B (en) | A kind of environmental response type cationic polymer and preparation method thereof for reactive dye salt-free dyeing | |
| Yagci et al. | Acrytonitrile block copolymers: 1. Preparation of polyacrylonitrile containing azo-linkage in the main chain by anionic insertion polymerization | |
| Grishin | Organometallic compounds as reversible spin scavengers and chain growth regulators in free-radical polymerization processes | |
| JPS60192718A (en) | Production of aqueous resin dispersion | |
| CN108546310B (en) | A kind of atom transfer radical polymerization method of alkali halide regulation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |