CN106832065B - The recovery method of catalyst in the atom transfer radical polymerization that molysite is catalyzed at room temperature - Google Patents
The recovery method of catalyst in the atom transfer radical polymerization that molysite is catalyzed at room temperature Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 28
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 238000004064 recycling Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 49
- 235000019441 ethanol Nutrition 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 30
- 239000003505 polymerization initiator Substances 0.000 claims description 18
- 150000001298 alcohols Chemical class 0.000 claims description 12
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 6
- ODVRHJKVXOGKEJ-UHFFFAOYSA-N iron 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical group [Fe].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 ODVRHJKVXOGKEJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 acrylate monomethyl ether ester Chemical class 0.000 claims description 4
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical group CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims 1
- 229920001515 polyalkylene glycol Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 33
- 239000003999 initiator Substances 0.000 abstract description 12
- 230000001939 inductive effect Effects 0.000 abstract description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 229960004756 ethanol Drugs 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000003708 ampul Substances 0.000 description 8
- 238000000502 dialysis Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000012773 waffles Nutrition 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BBRDYEXYVDCLGB-UHFFFAOYSA-N [Fe].C1(=CC=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Fe].C1(=CC=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 BBRDYEXYVDCLGB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
-
- 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
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (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
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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
- C08F4/42—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
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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
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses the recovery methods of catalyst in a kind of atom transfer radical polymerization of catalysis of molysite at room temperature.Specifically, method includes the following steps: 1) carrying out ATRP polymerization in paraxylene/alcohol mixed solvent；2) after polymerizeing, a certain amount of water inducing solution is added to be layered, obtains the solution and polymer containing catalyst through processing；3) new monomer, initiator ligand and ultraviolet light photoinitiator are added into the catalyst solution of recycling, carries out next round polymerization.ATRP reaction of the invention realizes uses molysite as catalyst at room temperature, is polymerize under ultraviolet light irradiation, obtains the good polymer of controlling, and can recycling and reusing catalyst, and keep the residual quantity of catalyst in polymer extremely low.
Description
Technical field
The invention belongs to the activity polymerizating technology fields of molysite catalysis, and in particular to the atom transfer of molysite catalysis at room temperature
The recovery method of catalyst in free radical polymerization.
Background technique
Atom transfer radical polymerization (ATRP) is a kind of using wide living polymerisation process, and catalyst is in ATRP
In play key effect, but a large amount of metal residual has seriously affected polymer material in electronic material and biomaterial
Etc. application, be developed so far, there are mainly three types of methods to solve the residue problem of catalyst.First is that development is without metal catalytic
ATRP, but structure is complicated for catalyzed organic catalyst, it is more difficult to synthesize, and exist about their toxicity very much
Arguement；Second is that developing AGET-ATRP or ICAR-ATRP, react in situ raw with the transition metal of high-valence state using various reducing agents
At the catalyst of lower valency, so as to lower the dosage of catalyst；Third is that develop the recycling separation system of catalyst, relative to
For first two method, method three can not only reduce the catalyst residual quantity in polymer, and can recycle catalyst and follow
Ring uses, and is more in line with economic benefit.And in the ATRP of numerous metal-regulatories, the ATRP of molysite catalysis is all the time standby
By the concern of people, because molysite has very big advantage, main body for the metal salt that other are used to ATRP
Its hypotoxicity now, reserves abundant and preferable biocompatibility.Photochemistry is due to its exclusive mild polymerization item
Part and high reaction efficiency, have obtained development at full speed in recent years, but existing catalyst recovery system is by various limitations, than
It cannot be used for photochemical polymerization system as temperature is high；Special defect is exactly that can not recycle pure catalyst, and big multi-method returns
What is received is all the complex compound that catalyst and ligand are formed, and can not really realize the recycling of catalyst.So developing molysite at room temperature
The recovery method of catalyst is imperative in the atom transfer radical polymerization of catalysis.
Summary of the invention
In view of the above-mentioned problems, the invention discloses a kind of sides for recycling atom transfer radical polymerization catalyst at room temperature
Method；The recycling of pure catalyst is really realized for the first time, can not only keep the metal salt in final polymer to remain in extremely low dense
Degree, and can effectively increase catalyst recycles efficiency.
To achieve the above object of the invention, the present invention adopts the following technical scheme: a kind of atom of the catalysis of molysite at room temperature turns
Move the recovery method of catalyst in free radical polymerization, including the following steps: be catalyzed water-soluble monomer, polymerization initiator, molysite
Agent, ligand, ultraviolet light photoinitiator are mixed with mixed solvent；Then ultraviolet light irradiation reaction is carried out at room temperature；After reaction
Water is added；It is finally separating upper and lower level solution, realizes the recycling of catalyst；The mixed solvent is benzene kind solvent and alcohols solvent
Mixed solvent.
In above-mentioned technical proposal, the benzene kind solvent is paraxylene；Alcohols solvent is ethyl alcohol.Compared to other two-phase mixtures
The solvent of system, the dicyandiamide solution that the present invention limits reach low-down residual quantity in removal process, are lower than 10ppm, achieve
Unexpected technical effect.
In above-mentioned technical proposal, the water-soluble monomer, polymerization initiator, ligand, ultraviolet light photoinitiator be not special
Limitation, be suitable for atom transfer radical polymerization, such as the monomer include Methylacrylic acid polyethylene glycol single armor ether ester,
Methacrylic N, N-dimethylamino ethyl ester, n-isopropyl acrylamide, N, N- dimethacrylamide.
Preferably, the iron salt catalyst is tetraphenylporphyrin iron；The water-soluble monomer is the poly- second two of methacrylic acid
Alcohol monomethyl ether ester；The initiator is alpha-brominated ethyl phenylacetate；The catalyst is tetraphenylporphyrin iron；The ultraviolet light light
Initiator is (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide.Not only monomer can achieve very high conversion ratio, and only 4
Hour, high conversion rate is up to 64.8%, and especially theoretical molecular weight is very close with actual molecular weight under this condition, and especially molysite is residual
It stays very low.
In above-mentioned technical proposal, the amount of the additional amount of water and the paraxylene of in the mixed solvent and ethyl alcohol is equivalent, three
Volume ratio is 1:1:1.
The present invention forms homogeneous system using paraxylene and ethyl alcohol, uses the molysite for being dissolved in paraxylene, such as four benzene
Base PORPHYRIN IRON is catalyzed, and carries out homogeneous polymerization under the conditions of ultraviolet light irradiation, after polymerization, by be added a certain amount of water come
Inducing catalysis agent phase is separated with polymer phase, realizes the separation and recovery of catalyst；Be it is a kind of at room temperature, simple and easy, separation effect
The high method of rate.
In above-mentioned technical proposal, the water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, ultraviolet light are light-initiated
The molar ratio of agent is 100: 0.5~2: 0.4~0.6: 3: 1~0.1；Preferably, the water-soluble monomer, polymerization initiator, iron
Salt catalyst, ligand, ultraviolet light photoinitiator molar ratio be 100: 1.25: 0.5: 3: 0.5.
The water-soluble monomer, benzene kind solvent, alcohols solvent volume ratio be 1: 1: 1.Monomer of the invention is in system
The up to ratio of one third is not only conducive to raw material and utilizes, increase reaction effect much higher than the ratio of monomer in the prior art
Reaction cost is greatly reduced in rate；Especially under this high concentration, still there is high conversion ratio, and there is low-down iron
Salt residual.
The present invention is polymerize in homogeneous system under conditions of room temperature, ultraviolet light irradiation, and the later period is added a certain amount of
The layering of water induction system, is dissolved in catalyst in the paraxylene phase on upper layer, to achieve the effect that recycle catalyst and guarantor
The metal residual held in polymer is extremely low.
In above-mentioned technical proposal, the time of the irradiation reaction is 4~6 hours, and power is 50~60w.The present invention is only sharp
64.8% conversion ratio can be reached in the case where polymerizeing for the first time with polymerization in 4 hours, turned in particular, recycling all improve monomer every time
Rate has reached 90.6% monomer conversion, this is that the prior art is unexpected when using catalyst the 6th time unexpectedly.
Polymer is prepared using circulation molysite catalyzing atom transfer free radical polymerization at room temperature the invention also discloses a kind of
Method, comprising the following steps:
(1) water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, ultraviolet light photoinitiator and mixed solvent are mixed
It closes；Then ultraviolet light irradiation reaction is carried out at room temperature；Water is added after reaction；It is finally separating upper and lower level solution, is recycled
Catalyst solution and polymer solution；To polymer solution dialysis treatment, polymer is obtained；The mixed solvent is benzene kind solvent
With the mixed solvent of alcohols solvent；
(2) water-soluble monomer, polymerization initiator, recycling catalyst solution, ligand, ultraviolet light photoinitiator are mixed；So
Carry out ultraviolet light irradiation reaction at room temperature afterwards；Water is added after reaction；It is finally separating upper and lower level solution, obtains catalyst solution
With polymer solution；To polymer solution dialysis treatment, polymer is obtained；
(3) step (2) are repeated, obtains polymer.
In above-mentioned technical proposal, in step (1), the water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, purple
The molar ratio of outer smooth photoinitiator is 100: 0.5~2: 0.4~0.6: 3: 1~0.1；The water-soluble monomer, benzene kind solvent, alcohol
The volume ratio of class solvent is 1: 1: 1；The water, benzene kind solvent, alcohols solvent volume ratio be 1: 1: 1；It is water-soluble in step (2)
Property monomer, polymerization initiator, ligand, the dosage of ultraviolet light photoinitiator and step (1) it is consistent.
According to the method for the present invention, the catalyst of recycling can carry out very recycled for multiple times, and catalytic efficiency is got over
It is better to come, at the 6th time in use, having reached 90.6% monomer conversion unexpectedly；Particularly, what the present invention recycled is pure catalysis
Agent solves existing recovery system without other substances such as any ligands so as to the system that can be catalyzed for any one
The problem of being interfered and greatly being limited using raw material by other substances.
The invention also discloses the method that a kind of atom transfer radical polymerization of catalysis of molysite at room temperature prepares polymer,
Include the following steps, by water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, ultraviolet light photoinitiator and mixed solvent
Mixing；Then ultraviolet light irradiation reaction is carried out at room temperature；Water is added after reaction；It is finally separating upper and lower level solution, to polymerization
Object solution dialysis treatment, obtains polymer；The mixed solvent is the mixed solvent of benzene kind solvent and alcohols solvent.
In above-mentioned technical proposal, the water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, ultraviolet light are light-initiated
The molar ratio of agent is 100: 0.5~2: 0.4~0.6: 3: 1~0.1；The water-soluble monomer, benzene kind solvent, alcohols solvent body
Product is than being 1: 1: 1；The water, benzene kind solvent, alcohols solvent volume ratio be 1: 1: 1.
After each component and solvent are mixed into homogeneously by the present invention, container is sealed and starts homogeneous polymerization reaction；It has reacted
Cheng Hou opens container, and by the way that a certain amount of water is added, induced polymer phase is mutually layered with catalyst, by simply toppling over point
From purification, separating catalyst and purer polymer can be obtained；Especially, by the polymerization system of split-phase, catalyst base
Originally it is dissolved in the paraxylene phase of upper layer, the residual concentration of catalyst is lower in underlying polymer phase.
A certain amount of water is added into reaction vessel after irradiation reaction by the present invention, until solution is layered, pipettes
Layer paraxylene phase, can be obtained the paraxylene solution containing catalyst, can utilize again；Specifically, by water-soluble monomer,
Initiator, ligand and ultraviolet light photoinitiator be added in transparent reaction container, adds isolated containing catalyst
Paraxylene solution can carry out the polymerization of a new round；According to above-mentioned separation method, catalyst can be recycled and polymerize
Object.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
1) present invention realizes catalyst in the ATRP of molysite catalysis at room temperature using ultraviolet light as the driving force of ATRP
Recycling and recycling, and the metal salt in final polymer is kept to remain in extremely low concentration, this has no in the prior art
Report, therefore the recycling of catalyst provides one kind newly in the atom transfer radical polymerization that be catalyzed for molysite at room temperature of the present invention
Method；
2) present invention can carry out under higher monomer concentration, to greatly shorten polymerization time；Solves existing skill
Art causes polymerization time longer since the interaction between solvent, recovery system generally carry out under lower monomer concentration
Defect；
3) molysite complexing power disclosed by the invention is very weak, but according to the method for the present invention, under dicyandiamide solution, benefit
With ultraviolet catalytic, monomer conversion height is not only obtained, but also obtained polymer metal residual is very low, especially 0.5
Usage amount under, 4 hours high conversion rates are up to 64.8%, and metal residual is down to 3.76ppm；Achieve unexpected technical effect；
4) method of the invention is very simple, while there is lower catalyst loss and the recycling of higher catalyst to imitate
Rate, by repeatedly recycling, polymerization is still able to maintain controllably, achieves unexpected technical effect.
Detailed description of the invention
Fig. 1 is the dynamic behavior schematic diagram of polymerization reaction；
Fig. 2 is the schematic diagram that polymerization process middle-molecular-weihydroxyethyl and molecular weight distribution change with conversion ratio；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of polymer P MPEGMA.
Specific embodiment
With reference to the accompanying drawing and specific embodiment makes further description to the present invention.Following embodiments is only used for
Illustrate technical solution of the present invention, and is not intended to limit protection scope of the present invention.
Chemical reagent:
Monomer: the Methylacrylic acid polyethylene glycol single armor ether ester (mPEGMA that molecular weight is 500500, CAS#:26915-72-
0,99%, Sigma-Aldrich)；Initiator: alpha-brominated ethyl phenylacetate (EBPA, CAS#:2882-19-1,98%, Ah
Fa Aisha Chemical Co., Ltd.)；Ligand: tetrabutylammonium bromide (TBA-Br, CAS#1643-19-2,99%, Shanghai lark waffle
Technology Co., Ltd.)；Catalyst: (Fe (III)-TPP, CAS#:16456-81-8,95%, pacifies resistance to Jilin Chemical to tetraphenylporphyrin iron
Company)；Other reagents: (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide (TPO, CAS#:75980-60-8,98%, peace
Nai Ji chemical company)；Ethyl alcohol (CAS#:64-17-5, technical grade, China Medicine (Group) Shanghai Chemical Reagent Co.)；To diformazan
Benzene (CAS#:106-42-3,99%, Shanghai lark waffle Technology Co., Ltd.)；Tetrahydrofuran (CAS#:109-99-9, analysis
It is pure, China Medicine (Group) Shanghai Chemical Reagent Co.)；Water (Hangzhou Wahaha Group Co., Ltd) is used in polymerization.
Test equipment and condition:
Gel permeation chromatograph: Japanese Tosoh company (TOSOH) HLC-8320 type GPC；Test condition: Tskgel Super
MultiporeHZ-N(4.6*150) two columns are combined, Composition distribution, and mobile phase is tetrahydrofuran (0.35 mL/min), column temperature
40℃；Nuclear magnetic resonance: Bruker 300MHz nuclear magnetic resonance spectrometer, with D2O is solvent measurement.
Embodiment 1: the recovery method of catalyst in the atom transfer radical polymerization that molysite is catalyzed at room temperature
By water-soluble monomer mPEGMA500(1.0 mL, 2.1 mmol), initiator EBPA(4.6 μ L, 2.6 × 10-2
Mmol), catalyst tetraphenylporphyrin iron Fe (III)-TPP(7.5 mg, 1.1 × 10-2Mmol), ligand normal-butyl ammonium bromide
TBA-Br(20.5 mg, 6.3 × 10-2Mmol), ultraviolet light photoinitiator TPO is added in 5 mL ampoule bottles, then is added thereto
Enter paraxylene (1.0 mL) and dehydrated alcohol (1.0 mL), melts tube sealing, and ampoule bottle is transferred to the purple that temperature is room temperature
Under outer lamp, it is polymerize under the conditions of magnetic agitation.It reaches scheduled polymerization time (4 h) and breaks pipe afterwards, and pure water (1.0 is added
ML), so that induction is mutually layered dissolved with the paraxylene phase of catalyst with the ethyl alcohol dissolved with polymer, upper layer paraxylene layer is pipetted
For being recycled, remaining alcohol layer is subjected to dialysis treatment, required polymer P MPEGMA can be obtained500, and it is in situ
Pass through1H-NMR method measures conversion ratio.
The investigation of the different light-initiated dosage of ultraviolet light.
The amount of ultraviolet light photoinitiator can largely determine the reaction speed and controlling of polymerization, for this to difference
Polymerization effect under amount is studied, and the results are shown in Table 1.
ATRP situation under the light-initiated dosage of the different ultraviolet lights of table 1
| X | Conversion ratio (%) | M n,th | M n,GPC | M w/M n |
| 1 | 90.4 | 36200 | 30800 | 1.22 |
| 0.8 | 88.4 | 35300 | 33400 | 1.18 |
| 0.5 | 64.8 | 25900 | 24400 | 1.22 |
| 0.2 | 50.7 | 20300 | 26300 | 1.13 |
| 0.1 | 31.4 | 12500 | 17400 | 1.14 |
Polymerizing condition: [mPEGMA500]0:[EBPA]0:[Fe(III)-TPP]0:[TBA-Br]0:[TPO]0=100:1.25:
0.5:3:X；V mPEGMA500 = 1.0 mL、V Paraxylene = 1.0 mL、V Ethyl alcohol= 1.0 mL；4 h of time；Light source is ultraviolet lamp lamp
(54 W).
As can be seen from Table 1, in the case where the amount of different ultraviolet initiators, it polymerize available preferable knot
Fruit, molecular weight distribution is relatively narrow, and as X=0.5, and GPC molecular weight and theoretical molecular weight are relatively；It is possible thereby to illustrate X
It is the optimal situation of polymerization when=0.5.
The investigation of different polymerization initiator amounts
The amount of polymerization initiator can determine aggregate target molecular weight to a certain extent, for this to the polymerization effect under not same amount
It is studied, the results are shown in Table 2
ATRP situation under the different polymerization initiator amounts of table 2
| X | Conversion ratio (%) | M n,th | M n,GPC | M w/M n |
| 2 | 56.1 | 14000 | 14000 | 1.18 |
| 1.5 | 71.3 | 23800 | 19800 | 1.17 |
| 1.25 | 64.8 | 25900 | 24400 | 1.22 |
| 1 | 64.5 | 32300 | 24600 | 1.16 |
| 0.5 | 75.6 | 75600 | 35400 | 1.24 |
Polymerizing condition: [mPEGMA500]0:[EBPA]0:[Fe(III)-TPP]0:[TBA-Br]0:[TPO]0=100:X:0.5:
3:0.5；V mPEGMA500 = 1.0 mL、V Paraxylene = 1.0 mL、V Ethyl alcohol= 1.0 mL；4 h of time；Light source is ultraviolet lamp lamp (54
W).
As can be seen from Table 2, in the case where different polymerization initiator amounts, polymerization it is available preferable as a result,
Molecular weight distribution is relatively narrow, and as X=1.25, GPC molecular weight with theoretical molecular weight relatively and polymerization speed is very fast；
It is possible thereby to be the optimal situation of polymerization when illustrating X=1.25.
The polymer P mPEGMA freeze-drying that different irradiation times are obtained, is used1H-NMR method calculates its conversion ratio, with
PMMA is standard sample, tests its molecular weight and molecular weight distribution on Japanese Tosoh company (TOSOH) HLC-8320 type GPC.Such as
Shown in Fig. 1 and Fig. 2, the level-one linear dynamics data of polymerization reaction may indicate that the Propagating Radical concentration in system is basic
It keeps constant, the side reactions such as chain termination is substantially not present；Molecular weight is linearly increasing with conversion ratio, and molecular weight distribution compared with
Narrow, GPC molecular weight is close with theoretical molecular weight.4 hours conversion ratios reach 64.8%, and 6 hours are even more to reach 80.9%.
By polymer nuclear-magnetism hydrogen spectrogram as shown in Figure 3 (with D2O is solvent, using TMS as internal standard) it is found that main polymer chain
On proton can find corresponding signal peak on nucleus magnetic hydrogen spectrum figure, and be to have at 7.2-7.5 ppm in chemical shift
The phenyl signal peak of EBPA initiator fragments illustrates that EBPA has caused the polymerization of monomer well.
Embodiment 2: the recycling experiment of catalyst
The method have the characteristics that the residual metal level in polymer can be kept extremely low after polymerization, and it can recycle and make
With catalyst, after polymerization, the paraxylene phase (being dissolved with catalyst) on upper layer is taken out, it is isometric dry to be placed in another
In net ampoule bottle, the ethyl alcohol of the monomer of predetermined amount, initiator, ligand, ultraviolet light photoinitiator and predetermined volume need to only be added
(amount for the remaining ingredient that this recovery experiment is added is equal with before recycling), can carry out the polymerization of next round.Difference recycling time
Single-point experiment under several is as shown in table 2.
Single site polymerisation Experimental comparison's table under the different recovered frequencies of table 2
| Access times | Conversion ratio (%) | Theoretical molecular weight (g/mol) | GPC molecular weight (g/mol) | PDI | Residual metal level (ppm) in polymer |
| For the first time | 64.8 | 25900 | 24400 | 1.22 | 11.8 |
| Second | 75.8 | 30300 | 18900 | 1.21 | 9.17 |
| For the third time | 78.3 | 31300 | 20400 | 1.20 | 6.51 |
| 4th time | 79.2 | 31700 | 19500 | 1.20 | 4.13 |
| 5th time | 87.6 | 35000 | 21900 | 1.18 | 5.30 |
| 6th time | 90.6 | 36200 | 22900 | 1.21 | 3.76 |
Polymerizing condition: the 1st use: [mPEGMA500]0:[EBPA]0:[Fe(III)-TPP]0:[TBA-Br]0:[TPO]0=
100:1.25:0.5:3:0.5；V mPEGMA500 = 1.0 mL, V Paraxylene = 1.0 mL, V Ethyl alcohol=1.0 mL, temperature=room temperature,
Time=4 h；Following cycle uses: the paraxylene solution of circulationV Paraxylene=1.0 mL,V mPEGMA500=1.0 mL,V Ethyl alcohol=1.0
ML, light source are ultraviolet lamp lamp (54 W), and temperature=room temperature, the time=4 h, addition pure water is 1.0 mL.
As can be seen from Table 2, by 6 circulation experiments, molecular weight distribution is all narrow.It is worth noting that, through
It crosses and is used for multiple times, the residual metal level in obtained polymer is all relatively low.
Embodiment 3: the recovery method of catalyst in the atom transfer radical polymerization that molysite is catalyzed at room temperature
According to the ratio of embodiment two, by water-soluble monomer n,N-dimethylaminoethyl methacrylate, initiator
EBPA, catalyst tetraphenylporphyrin iron Fe (III)-TPP, ligand normal-butyl ammonium bromide TBA-Br, ultraviolet light photoinitiator TPO add
Enter into 5 mL ampoule bottles, then paraxylene (1.0 mL) and dehydrated alcohol (1.0 mL) are added thereto, melts tube sealing, and will
Ampoule bottle is transferred under the ultraviolet lamp that temperature is room temperature (50 W), is polymerize under the conditions of magnetic agitation.It reaches scheduled poly-
Close time (4 h) and break pipe afterwards, and pure water (1.0 mL) is added, thus induction dissolved with catalyst paraxylene phase with dissolved with polymerizeing
The ethyl alcohol of object is mutually layered, and pipettes upper layer paraxylene layer for being recycled, remaining alcohol layer is carried out dialysis treatment
Required polymer is obtained, and is passed through in situ1H-NMR method measures conversion ratio；Conversion ratio is 62% for the first time, and metal residual is
12ppm, six times circulation after conversion ratio be 89%, metal residual 4.6ppm.
Embodiment 4: the recovery method of catalyst in the atom transfer radical polymerization that molysite is catalyzed at room temperature
According to the ratio of embodiment two, by water-soluble monomer n-isopropyl acrylamide, initiator EBPA, four benzene of catalyst
Base PORPHYRIN IRON Fe (III)-TPP, ligand normal-butyl ammonium bromide TBA-Br, ultraviolet light photoinitiator TPO are added to 5 mL ampoule bottles
In, then paraxylene (1.0 mL) and dehydrated alcohol (1.0 mL) are added thereto, tube sealing is melted, and ampoule bottle is transferred to temperature
Degree is (54 W) under the ultraviolet lamp of room temperature, is polymerize under the conditions of magnetic agitation.Scheduled polymerization time (4 h) is reached to break afterwards
Pipe, and pure water (1.0 mL) is added, so that induction is mutually layered dissolved with the paraxylene phase of catalyst with the ethyl alcohol dissolved with polymer,
Upper layer paraxylene layer is pipetted for being recycled, remaining alcohol layer is subjected to dialysis treatment, required polymerization can be obtained
Object, and pass through in situ1H-NMR method measures conversion ratio；Conversion ratio is 66% for the first time, metal residual 12.3ppm, after six circulations
Conversion ratio is 92%, metal residual 4.5ppm.
Embodiment 5: the recovery method of catalyst in the atom transfer radical polymerization that molysite is catalyzed at room temperature
According to the ratio of embodiment two, by water-soluble monomer N,N-DMAA, initiator EBPA, catalyst four
Phenyl PORPHYRIN IRON Fe (III)-TPP, ligand normal-butyl ammonium bromide TBA-Br, ultraviolet light photoinitiator TPO are added to 5 mL ampoules
In bottle, then paraxylene (1.0 mL) and dehydrated alcohol (1.0 mL) are added thereto, melt tube sealing, and ampoule bottle is transferred to
Temperature is (60W) under the ultraviolet lamp of room temperature, is polymerize under the conditions of magnetic agitation.After reaching scheduled polymerization time (4 h)
Broken pipe, and pure water (1.0 mL) is added, thus paraxylene phase of the induction dissolved with catalyst and the ethyl alcohol phase dissolved with polymer point
Layer pipettes upper layer paraxylene layer for being recycled, remaining alcohol layer is carried out dialysis treatment, and required gather can be obtained
Object is closed, and is passed through in situ1H-NMR method measures conversion ratio；Conversion ratio is 61.3%, metal residual 10.3ppm for the first time, is followed for six times
Conversion ratio is 90.1% after ring, metal residual 4.8ppm.
Claims (4)
1. the recovery method of catalyst in a kind of atom transfer radical polymerization of the catalysis of molysite at room temperature, which is characterized in that packet
It includes the following steps: water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, ultraviolet light photoinitiator and mixed solvent is mixed
It closes；Then ultraviolet light irradiation reaction is carried out at room temperature；Water is added after reaction, thus paraxylene of the induction dissolved with catalyst
Mutually mutually it is layered with the ethyl alcohol dissolved with polymer；It is finally separating upper and lower level solution, realizes the recycling of catalyst, recycling is pure catalysis
Agent is free of any ligand；The mixed solvent is the mixed solvent of benzene kind solvent and alcohols solvent；The water-soluble monomer is first
Base polyalkylene glycol acrylate monomethyl ether ester, methacrylic N, N-dimethylamino ethyl ester, n-isopropyl acrylamide, N, N- bis-
One of Methacrylamide；The polymerization initiator is alpha-brominated ethyl phenylacetate；The ultraviolet light photoinitiator be (2,
4,6- trimethylbenzoyl) diphenyl phosphine oxide；The ligand is tetrabutylammonium bromide；The benzene kind solvent is to diformazan
Benzene；Alcohols solvent is ethyl alcohol；The iron salt catalyst is tetraphenylporphyrin iron；The water-soluble monomer, benzene kind solvent, alcohols are molten
The volume ratio of agent is 1: 1: 1；The water-soluble monomer, polymerization initiator, iron salt catalyst, ligand, ultraviolet light photoinitiator
Molar ratio is 100: 0.5~2: 0.4~0.6: 3: 1~0.1.
2. recovery method according to claim 1, it is characterised in that: the water-soluble monomer, polymerization initiator, molysite are urged
Agent, ligand, ultraviolet light photoinitiator molar ratio be 100: 1.25: 0.5: 3: 0.5.
3. recovery method according to claim 1, it is characterised in that: the time of the irradiation reaction is 4~6 hours, function
Rate is 50~60w.
4. recovery method according to claim 1, it is characterised in that: the volume ratio of the water, benzene kind solvent, alcohols solvent
It is 1: 1: 1.
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