CN107573447B - Method for preparing clean controllable polymer in situ by atom transfer radical polymerization - Google Patents
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Abstract
The invention relates to the technical field of metal-catalyzed controllable polymerization, and discloses a method for preparing a clean controllable polymer in situ by atom transfer radical polymerization, which comprises the following steps: s1: adding a polymerization monomer, an initiator, a metal catalyst, a ligand and a mercapto-functionalized solid reducing agent into a reaction vessel containing a first organic solvent, sealing, and heating and polymerizing under magnetic stirring; s2: unsealing the reaction container, and filtering to remove the solid reducing agent adsorbed with the metal catalyst to obtain a clean controllable polymer solution; s3: pouring the controllable polymer solution into a second organic solvent for precipitation; s4: the resulting precipitate was filtered and dried under vacuum to yield a clean, controlled polymer. Compared with the prior art, the method utilizes the function that the sulfydryl functionalized solid reducing agent has high-efficiency reduction and precursor adsorption, realizes the synchronous separation of the metal catalyst and the reducing agent by-products, and prepares the clean controllable polymer in situ.
Description
Technical Field
The invention relates to the technical field of metal-catalyzed controllable polymerization, in particular to a method for preparing a clean controllable polymer in situ by atom transfer radical polymerization.
Background
Simple and efficient fine control of molecular weight, molecular weight distribution and topological structure of polymers is a goal pursued by high molecular scientists. Atom Transfer Radical Polymerization (ATRP) is taken as a powerful active/controllable radical polymerization method, has attracted great attention in academia and industry since the last 90 th century, and particularly provides a simple, convenient and efficient method for precise regulation and control of a polymer structure by atom transfer radical polymerization (AGET ATRP) of an electron transfer generation catalyst developed in the later period. However, as a multicomponent polymerization system, a large amount of metal catalyst and reducing agent is inevitably added during the polymerization process to control the polymerization equilibrium process, and a large amount of by-products of the metal catalyst and reducing agent inevitably remains in the polymer thus obtained, which not only accelerates the aging of the polymer during use, but also causes environmental and safety problems.
In recent years, the following solutions have been mainly adopted for the problem of metal catalyst residue: one is to design a highly active catalytic system to reduce the amount of metal catalyst, which often requires the addition of excess ligand and reducing agent to establish a suitable activation-deactivation balance; secondly, the method needs to use a large amount of organic dye as a catalyst for developing a novel organic catalyst to realize ATRP without metal catalysis, and has the problem of harmful organic substance residue; thirdly, a technology for developing high-efficiency metal catalyst recovery and recycling is mainly divided into the following types: (a) polymer post-treatment, (b) supported catalytic system, (c) liquid/liquid two-phase catalytic system. The above recovery method is designed only for metal catalysts, ignoring the problem of in situ separation of large amounts of reductant by-product.
In summary, the three main methods, although each of them has advantages, have some disadvantages and shortcomings, which are shown in that the focus is too much on eliminating the problem of metal catalyst remaining in the polymer, and neglecting the problem of other components remaining in the prepared controllable polymer, the clean controllable polymer can not be really obtained, thereby affecting the application occasion and the service life of the controllable polymer.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a method for preparing a clean controllable polymer in situ by atom transfer radical polymerization, which utilizes the function of a sulfydryl functionalized solid reducing agent with efficient reduction and precursor adsorption to synchronously separate a metal catalyst and a reducing agent byproduct and prepare the clean controllable polymer.
The technical scheme is as follows: the invention provides a method for preparing a clean controllable polymer in situ by atom transfer radical polymerization, which comprises the following steps: s1: adding a polymerization monomer, an initiator, a metal catalyst, a ligand and a mercapto-functionalized solid reducing agent into a reaction vessel containing a first organic solvent, sealing, and heating and polymerizing under magnetic stirring; s2: unsealing the reaction container, and filtering to remove the solid reducing agent adsorbed with the metal catalyst to obtain a clean controllable polymer solution; s3: pouring the controllable polymer solution into a second organic solvent for precipitation; s4: the resulting precipitate was filtered and dried under vacuum to yield a clean, controlled polymer.
Further, the molar ratio of the polymerization monomer to the initiator to the metal catalyst to the ligand is 400: 1 ~ 4: 0.25: 0.5 ~ 1, the molar ratio of the metal catalyst to the mercapto group in the mercapto group functionalized solid reducing agent is 0.25: 1 ~ 2.6.6, the molar ratio of the polymerization monomer to the initiator to the metal catalyst to the ligand is preferably 400: 2: 0.25: 0.5, and the molar ratio of the metal catalyst to the hydroxyl group in the mercapto group functionalized solid reducing agent is preferably 0.25: 2.6.
Further, in S2, after the reaction vessel is decrypted and sealed, an appropriate amount of the first organic solvent is added to the reaction solution and left to stand, and then the solid reducing agent is filtered and removed.
Preferably, in the S1, the heating temperature during the heating polymerization is 60 ~ 110 ℃, the heating mode is oil bath heating, and the polymerization time is 1.5 ~ 4.5.5 h.
Preferably, the first organic solvent is an organic solvent capable of dissolving the controllable polymer. Toluene, anisole, tetrahydrofuran or acetonitrile are preferred.
Preferably, the second organic solvent is an organic solvent that can precipitate the controllable polymer. Methanol, n-hexane or petroleum ether is preferred.
Preferably, the thiol-functionalized solid reducing agent is any one of the following: thiol-functionalized cellulose paper, thiol-functionalized cloth, thiol-functionalized wood or thiol-functionalized glassine paper, preferably thiol-functionalized cellulose paper.
Further, if the thiol-functionalized solid reducing agent is a thiol-functionalized cellulose paper, the preparation method thereof is as follows: immersing cellulose paper in a sodium hydroxide aqueous solution with the mass fraction of 10%, shaking for a preset time (preferably 16 h), taking out the cellulose paper, washing with ethanol, and soaking in ethanol for later use; transferring the cellulose paper into anhydrous toluene, adding a certain amount of thioglycolic acid and catalytic amount of p-toluenesulfonic acid into the toluene, and refluxing for a preset time (preferably 16 h) under the protection of argon; and (3) cooling the solution, taking out the paper sheet, ultrasonically washing and drying in vacuum to obtain the sulfydryl functionalized cellulose paper, and storing in an argon atmosphere for later use.
Preferably, the polymerized monomer is a vinyl monomer, and the vinyl monomer is any one of the following: methyl Methacrylate (MMA), styrene (St), Methyl Acrylate (MA), polyethylene glycol monomethyl ether methacrylate (mPEGMA), N-dimethylaminoethyl methacrylate (DMAEMA), N-isopropylacrylamide (NIPAM) or N, N-Dimethylacrylamide (DMAA), more preferably MMA, mPEGMA, most preferably MMA.
Preferably, the initiator is any one of the following: ethyl α -bromophenylacetate (EBPA), α -bromophenylethane (PEBr), ethyl 2-bromoisobutyrate (EBiB) or 2-Bromopropionitrile (BPN), preferably EBPA.
Preferably, the metal catalyst is any one of: cupric bromide (CuBr)2) Copper chloride dihydrate (CuCl)2·2H2O) or pentahydrate and copper sulfate (CuSO)4·5H2O), preferably CuBr2。
Preferably, the ligand is any one of the following: pentamethyldiethylenetriamine (PMDETA), bipyridine (Bpy), and tris [ (2-methylamine) ethyl group]Amine (Me)6TREN) or tris (2-pyridylmethyl) amine (TPMA), preferably PMDETA.
Has the advantages that: the polymerization of the invention is carried out in a transparent reaction vessel, after each polymerization component is added into the reaction vessel, the direct melting and tube sealing without deoxidization are not needed, the invention creatively uses a sulfhydryl functionalized solid reducing agent in AGET ATRP, the solid reducing agent participates in the polymerization in a solid phase form, a large amount of sulfhydryl on the surface of the solid reducing agent is taken as a reducing agent, the sulfhydryl is oxidized into a disulfide bond while reducing high-valence metal ions in a metal catalyst into low-valence metal ions, then the high-valence metal ions and the low-valence metal ions can be complexed with the disulfide bond, the complex is adsorbed on the surface of the solid reducing agent, after the polymerization is finished, the vessel is unsealed, after a proper amount of first organic solvent is added to dilute viscous controllable polymer solution, the blackened solid reducing agent is separated, and the purpose of synchronously separating the metal catalyst and reducing agent by-products from the controllable polymer is realized, clean, controlled polymers are produced directly in situ that are substantially free of metal catalyst and reducing agent by-products.
Compared with the prior art, the invention has the following advantages:
1) aiming at the problem that a large amount of organic matters such as metal catalysts, reducing agent byproducts and the like are remained in a controllable polymer prepared by AGET ATRP, the invention creatively uses a sulfydryl functionalized solid as a reducing agent, and realizes the synchronous separation of the metal catalysts, the reducing agent byproducts and the prepared controllable polymer, so that a clean controllable polymer is obtained in situ, the polymerization rate is high, the monomer conversion rate is high, and at present, reports in the aspect are basically absent, and a simple, convenient and efficient method is provided for preparing the clean controllable polymer;
2) the system inherits the characteristics of wide monomer application range and precise structure regulation of an ATRP method, and can prepare clean controllable polymers with different structural units and various topological structures according to requirements;
3) the invention can use green natural polymer cellulose as a reducing agent precursor, can simply prepare a clean controllable polymer, basically realizes a green ATRP process, and lays a solid theoretical foundation for promoting the industrialization of ATRP.
Drawings
FIG. 1 is a comparative plot of the surface of a thiol-functionalized solid reducing agent before and after polymerization;
FIG. 2 is a schematic view of the polymerization reaction principle.
FIG. 3 is a schematic representation of the kinetic behavior of a polymerization reaction;
FIG. 4 is a schematic representation of molecular weight versus molecular weight distribution as a function of conversion during polymerization;
FIG. 5 is a nuclear magnetic hydrogen spectrum of a controllable polymer PMMA;
figure 6 is a GPC outflow graph before and after chain extension of the controllable polymer PMMA.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Chemical reagents:
monomer (b): methyl methacrylate (CAS #:80-62-6, 99%, chemical reagents of national drug group, Inc.);
initiator: ethyl alpha-bromophenylacetate (CAS #:2882-19-1, 98%, Alfa Angsa chemical Co., Ltd.);
ligand: pentamethyldiethylenetriamine (CAS #:3030-47-5, 98%, Prodweiser technologies, Inc.);
catalyst: copper bromide (CAS #:7789-45-9, 98%, chemical reagents of national drug group, Inc.);
other reagents: cellulose paper (whatman); toluene (CAS #:108-88-3, analytically pure, Shanghai chemical Co., Ltd., China medicine (group)); tetrahydrofuran (CAS #:109-99-9, analytically pure, Shanghai chemical Co., Ltd., Chinese medicine (group)); n-hexane (CAS #:110-54-3, analytically pure, Shanghai chemical reagents, Inc. of Chinese medicine (group)); methanol (CAS #:67-56-1, analytically pure, Shanghai chemical Co., Ltd., China medicine (group)).
Testing instruments and conditions:
gel permeation chromatograph: japan Tosoh corporation (TOSOH) HLC-8320 type GPC; and (3) testing conditions are as follows: tskgel Super MultiporeHZ-N (4.6 x 150) two columns were used in combination with a differential detector, tetrahydrofuran (0.35 mL/min) as mobile phase, column temperature 40 ℃,
nuclear magnetic resonance: bruker 300MHz NMR instrument, DMSO as solvent.
Embodiment 1:
(1) synthesis of thiol-functionalized cellulose paper:
immersing 1.5 g of cellulose paper in 300 mL of newly prepared sodium hydroxide aqueous solution with the mass fraction of 10%, shaking overnight, taking out the cellulose paper, washing the cellulose paper with ethanol for three times, and soaking the cellulose paper in the ethanol for standby. And transferring the cellulose paper to 200 mL of anhydrous toluene, adding 1.94 mL of thioglycolic acid, 27.9 mmol of thioglycolic acid and 200 mg of p-toluenesulfonic acid into a toluene solution, refluxing overnight under the protection of argon, cooling the solution, taking out the cellulose paper, performing ultrasonic washing on the cellulose paper by using a proper amount of methanol, ethanol, acetone and dichloromethane in sequence, performing vacuum drying to obtain the thiol-functionalized cellulose paper, and storing the thiol-functionalized cellulose paper for later use under the atmosphere of argon.
(2) Synthesis of the controlled Polymer PMMA:
MMA (2.0 mL, 18.9 mmol) as a polymerization monomer, EBPA (8.3. mu.L, 4.72X 10 mmol) as an initiator-2mmol), metal catalyst CuBr2（5.3 mg, 2.36×10-2mmol), ligand PMDETA (9.8. mu.L, 4.72X 10)-2mmol) and mercapto-functionalized cellulose paper (50 mg, 0.125 mmol, as shown in FIG. 1 a) were added to a 5 mL ampoule, 1 mL of toluene was added to the ampoule and the ampoule was directly melt-sealed and transferred to 90oC, polymerizing for 3.5 h in an oil bath kettle under magnetic stirring, cooling, breaking the tube, adding a proper amount of toluene, standing to dissolve the polymer, taking out the blackened cellulose paper (shown in figure 1 b), pouring the toluene solution of the polymer into a large amount of methanol to precipitate a large amount of white solid, performing suction filtration, performing vacuum drying at room temperature to obtain a clean controllable polymer PMMA, and measuring the monomer conversion rate to be 78.2% by using a weighing method. The above color change of the cellulose paper shows that the metal catalyst is effectively adsorbed on the cellulose paper, and the metal catalyst and the reducing agent by-product can be effectively separated from the controlled polymer PMMA by separating the cellulose paper, as shown in fig. 2.
The controlled polymer PMMA obtained by different polymerization times is dried in vacuum, the conversion rate is calculated by a weighing method, the molecular weight and the molecular weight distribution are tested on the HLC-8320 type GPC of Tosoh corporation (TOSOH) in Japan by taking PMMA as a standard sample, and as shown in figure 3, the first-order linear kinetic data of the polymerization reaction show that: the concentration of the growing free radical in the system is basically kept constant, and the influence of side reactions such as chain termination and the like on polymerization can be ignored; as shown in FIG. 4, the molecular weight increases linearly with conversion and the molecular weight distribution is narrower, further indicating that the system is a living polymerization system with a higher GPC molecular weight than the theoretical molecular weight, probably due to the lower initiator initiation efficiency and the presence of some unavoidable chain transfer and chain termination.
FIG. 5 shows a controlled polymer nuclear magnetic hydrogen spectrum (in DMSO-d)6As solvent, TMS as internal standard), it can be seen that all protons on the controllable polymer backbone can find the corresponding signal peak on the nuclear magnetic hydrogen spectrum, and there is the phenyl signal peak of the EBPA initiator fragment at the chemical shift of 7.25ppm, indicating that EBPA initiates the polymerization of the polymerized monomer well.
As shown in fig. 6, the GPC flow curves before and after chain extension of the polymer PMMA (where 1 represents polymethyl methacrylate (PMMA) before chain extension, GPC molecular weight = 4200 g/mol, molecular weight distribution = 1.12, and 2 represents polymethyl methacrylate (PMMA) obtained after chain extension using 1 as a macroinitiator, GPC molecular weight = 25500 g/mol, and molecular weight distribution = 1.13), it was found that the molecular weight of PMMA was significantly increased, and the polymer PMMA prepared by the present embodiment was a living polymer.
Embodiment 2:
(1) synthesis of thiol-functionalized cellulose paper: the same as embodiment 1.
(2) Synthesis of controllable Polymer PSt:
polymerizing monomer styrene (2.0 mL, 17.5 mmol), initiator EBiB （12.6 μL ，8.75×10-2mmol), metal catalyst CuCl2（3.0 mg, 2.19×10-2mmol), ligand TPMA (4.85 mg, 4.38X 10)-2mmol) and mercapto-functionalized cellulose paper (50 mg, 0.125 mmol) were added to a 5 mL ampoule, 1 mL of toluene was added to the ampoule and the ampoule was directly melt-sealed and transferred to 110oC, polymerizing for 4 hours in an oil bath kettle under magnetic stirring, cooling, breaking the tube, adding a proper amount of toluene, standing to dissolve the polymer, taking out the blackened cellulose paper, pouring the toluene solution of the polymer into a large amount of methanol to precipitate a large amount of white solids, and performing suction filtrationAnd dried under vacuum at room temperature to obtain a clean controllable polymer PSt, and the monomer conversion rate is measured by a weighing method to be 40.5%.
Embodiment 3:
(1) synthesis of thiol-functionalized cellulose paper: the same as embodiment 1.
(2) Synthesis of controllable polymer PEGMA:
polymerizing monomer mPEG MA500(2.0 mL, 4.4 mmol), initiator BPN (2.2. mu.L, 4.4X 10)-2mmol), metal catalyst CuCl2（1.5 mg, 1.1×10-2mmol), ligand Bpy (6.9 mg, 4.4X 10)-2mmol) and mercapto-functionalized cloth (50 mg, 0.125 mmol) were added to a 5 mL ampoule, 1 mL of toluene was added to the ampoule and the ampoule was directly melt-sealed and transferred to 60oAnd C, polymerizing for 2 hours in an oil bath kettle under magnetic stirring, cooling, breaking the tube, adding a proper amount of toluene, standing to dissolve the polymer, taking out the blackened cellulose paper, pouring the toluene solution of the polymer into a large amount of methanol to precipitate a large amount of white solids, performing suction filtration, performing vacuum drying at room temperature to obtain a clean controllable polymer PEGMA, and measuring the monomer conversion rate to be 56.8 percent by using a weighing method.
The above embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for preparing a clean controllable polymer in situ by atom transfer radical polymerization, which is characterized by comprising the following steps:
s1: adding a polymerization monomer, an initiator, a metal catalyst, a ligand and a mercapto-functionalized solid reducing agent into a reaction vessel containing a first organic solvent, sealing, and heating and polymerizing under magnetic stirring;
s2: unsealing the reaction container, and filtering to remove the solid reducing agent adsorbed with the metal catalyst to obtain a clean controllable polymer solution;
s3: pouring the controllable polymer solution into a second organic solvent for precipitation;
s4: filtering and vacuum drying the obtained precipitate to obtain a clean controllable polymer;
wherein, the mercapto-functionalized solid reducing agent is any one of the following: a mercapto-functionalized cellulose paper, a mercapto-functionalized cloth, a mercapto-functionalized wood or a mercapto-functionalized cellophane;
the first organic solvent is toluene, anisole, tetrahydrofuran or acetonitrile;
the second organic solvent is methanol, petroleum ether or n-hexane.
2. The method for preparing the clean controllable polymer in situ by the atom transfer radical polymerization according to claim 1, wherein the molar ratio of the polymerization monomer, the initiator, the metal catalyst and the ligand is 400: 1 ~ 4: 0.25: 0.5 ~ 1, and the molar ratio of the metal catalyst to the mercapto group in the mercapto group functionalized solid reducing agent is 0.25: 1 ~ 2.6 by calculating from the element analysis result.
3. The method for preparing a controlled polymer in situ by atom transfer radical polymerization according to claim 1, wherein in S2, after the reaction vessel is sealed and decrypted, the first organic solvent is added into the reaction solution in a proper amount and left standing, and then the solid reducing agent is filtered and removed.
4. The method for preparing the controlled polymer in situ by atom transfer radical polymerization as claimed in claim 1, wherein in S1, the heating temperature for heating polymerization is 60 ~ 110 ℃, the heating mode is oil bath heating, and the polymerization time is 1.5 ~ 4.5.5 h.
5. The method for preparing clean controllable polymer in situ by atom transfer radical polymerization according to any one of claims 1 to 4, wherein if the thiol-functionalized solid reducing agent is thiol-functionalized cellulose paper, the method is as follows:
immersing cellulose paper in a sodium hydroxide aqueous solution with the mass fraction of 10%, shaking for a preset time, taking out the cellulose paper, washing with ethanol, and soaking in ethanol for later use;
transferring the cellulose paper to anhydrous toluene, adding a certain amount of thioglycollic acid and catalytic amount of p-toluenesulfonic acid into the toluene, and refluxing for a preset time under the protection of argon;
and (3) cooling the solution, taking out the paper sheet, ultrasonically washing and drying in vacuum to obtain the sulfydryl functionalized cellulose paper, and storing in an argon atmosphere for later use.
6. The method for preparing the clean controllable polymer in situ by atom transfer radical polymerization according to any one of claims 1 to 4, wherein the polymerized monomer is a vinyl monomer.
7. The method for preparing the clean controllable polymer in situ by the atom transfer radical polymerization according to claim 6, wherein the ethylene monomer is any one of the following monomers:
methyl methacrylate, styrene, methyl acrylate, polyethylene glycol monomethyl ether methacrylate, N-dimethylaminoethyl methacrylate, N-isopropylacrylamide or N, N-dimethylacrylamide.
8. The method for preparing clean controllable polymer in situ by atom transfer radical polymerization according to any one of claims 1 to 4, wherein the initiator is any one of the following:
ethyl alpha-bromophenylacetate, alpha-bromophenylethane, ethyl 2-bromoisobutyrate or 2-bromopropionitrile.
9. The method for preparing clean controllable polymer in situ by atom transfer radical polymerization according to any one of claims 1 to 4, wherein the metal catalyst is any one of the following:
copper bromide, copper chloride dihydrate or copper sulfate pentahydrate.
10. The method for preparing clean controllable polymer in situ by atom transfer radical polymerization according to any one of claims 1 to 4, wherein the ligand is any one of the following:
pentamethyldiethylenetriamine, bipyridine, tris [ (2-methylamine) ethyl ] amine or tris (2-pyridylmethyl) amine.
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