CN114230739B - Linear-nonlinear block polymer and preparation method thereof - Google Patents
Linear-nonlinear block polymer and preparation method thereof Download PDFInfo
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- CN114230739B CN114230739B CN202111528420.3A CN202111528420A CN114230739B CN 114230739 B CN114230739 B CN 114230739B CN 202111528420 A CN202111528420 A CN 202111528420A CN 114230739 B CN114230739 B CN 114230739B
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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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention discloses a linear-nonlinear block polymer and a preparation method thereof, belonging to the field of polymer synthesis. The invention discloses a linear-nonlinear block polymer which is formed by a nonlinear structure formed by polymerizing a linear polymer chain segment and a polyvinyl monomer, and is a polymer with a brand new topological structure. The invention also discloses a preparation method of the linear-nonlinear block polymer, which is based on the controllable polymerization of the polyvinyl monomer and is prepared by using a macromolecular RAFT reagent to regulate and control or using a macromolecular ATRP to initiate the polymerization of the polyvinyl monomer in one step under the anaerobic condition. The method has the advantages of relatively mild reaction conditions, controllable polymerization product composition, controllable molecular weight and molecular weight distribution, and easy adjustment of polymer topology structure, and is suitable for large-scale production and application, and has important application value.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to a linear-nonlinear block polymer and a preparation method thereof.
Background
Reversible addition-fragmentation chain transfer radical polymerization (RAFT) and Atom Transfer Radical Polymerization (ATRP) are widely used in the preparation of polymers due to the advantages of milder polymerization conditions, wide monomer application range, easy control of polymer composition and structure, etc. With the progressive penetration of research and application of nonlinear topologies, nonlinear topological structure high molecules are found to exhibit significantly different performance from linear topologies. Monovinyl monomers containing only one vinyl function by RAFT or ATRP polymerization tend to yield only linear polymers. The polymer with the nonlinear topological structure such as brush type, star type, hyperbranched, cyclized and the like can be prepared by modifying a RAFT reagent, an ATRP initiator or a free radical initiator on molecules with specific topological structures in advance and then carrying out RAFT or ATRP polymerization on a monovinyl monomer. In addition, research based on the regulation of small-molecule RAFT chain transfer agents or the initiation of polymerization of multi-vinyl monomers by small-molecule ATRP initiators to synthesize cyclized and branched polymers has been advanced.
The linear-nonlinear block polymer has a unique tadpole-like topological structure and completely different properties from those of linear, brush-type, star-type, hyperbranched, cyclized and other polymers, such as hydrodynamic volume, glass transition temperature, interfacial properties and the like, so that the linear-nonlinear block polymer has great application potential in the fields of biomedicine, paint, engineering materials and the like. However, all the above methods cannot synthesize polymers with linear-nonlinear topologies in one step. At present, the synthesis of linear-nonlinear block polymers is mainly carried out by segmented polymerization and splicing by non-covalent bond. Because of the great difficulty and low efficiency of the nonlinear structure synthesis, the linear-nonlinear block polymer synthesis needs to consider the polymerization sequence of the nonlinear structure and the linear chain segment, the block combination mode and other factors, so that the linear-nonlinear block polymer synthesis is very challenging.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the present invention is directed to a linear-nonlinear block polymer and a preparation method thereof, so as to solve the problem of insufficient preparation methods of the current linear-nonlinear block polymer.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a linear-nonlinear block polymer, which consists of a nonlinear structure formed by polymerizing a linear polymer chain segment and a polyvinyl monomer, and has the following structural formula:
wherein m=5 to 20, p=5 to 100, q=5 to 100;
R 1 is Br or
R 2 Is that
Wherein n=10 to 200.
The invention also discloses a preparation method of the linear-nonlinear block polymer, wherein a macromolecular RAFT reagent is used as chain transfer, and a polyvinyl monomer is initiated by an initiator to perform reversible addition-fragmentation chain transfer free radical polymerization reaction; another preparation method is to initiate a multi-vinyl monomer by a macromolecular ATRP initiator, and perform atom transfer radical polymerization reaction by using a ligand and a catalyst to obtain a linear-nonlinear block polymer.
Preferably, the polyvinyl monomer is divinylbenzene, di (meth) acrylate, tri (meth) acrylate, bisphenol a polyoxyethylene ether diacrylate, 1, 4-butanediol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate or trimethylolpropane triacrylate.
Preferably, the reversible addition-fragmentation chain transfer free radical polymerization comprises the steps of:
1) Fully dissolving a polyvinyl monomer, a macromolecular RAFT reagent and an initiator in a solvent to obtain a reaction mixed system;
2) Deoxidizing the reaction mixed system, and performing polymerization reaction after deoxidization is finished;
3) And purifying the product to obtain the linear-nonlinear block polymer.
Further preferably, in step 1), the macromolecular RAFT agent has a molecular weight of 500-50000Da and is obtained by coupling polyethylene glycol monomethyl ether with 4-cyanovaleric dithiobenzoic acid, dithioesters, dithiocarbamates, trithiocarbonates or xanthates.
Further preferably, in step 1), the molar ratio of the polyvinyl monomer, the macromolecular RAFT agent and the initiator is (50 to 1000): 1: (0.1 to 1);
the initiator is azodiisobutyronitrile, 4' -azo (4-cyanovaleric acid) or benzoyl peroxide; the solvent is 2-butanone.
Preferably, the atom transfer radical polymerization comprises the steps of:
1) Fully dissolving a polyvinyl monomer, a macromolecular ATRP initiator, a ligand and a catalyst in a solvent to obtain a reaction mixed system;
2) Deoxidizing the reaction mixed system; carrying out polymerization reaction after deoxidization is finished;
3) And purifying the product to obtain the linear-nonlinear block polymer.
Further preferably, in step 1), the molecular weight of the macromolecular ATRP initiator is 500-50000Da, and the macromolecular ATRP initiator is obtained by coupling polyethylene glycol monomethyl ether with halogenated alkane.
Further preferably, in step 1), the molar ratio of the polyvinyl monomer, the macromolecular ATRP initiator, the ligand and the catalyst is (50 to 1000): 1: (0.5-5): (0.05 to 0.5);
the ligand is N, N, N' -pentamethyl divinyl triamine and the catalyst is CuBr 2 The solvent is dimethyl sulfoxide.
Further preferably, the polymerization temperature of the reversible addition-fragmentation chain transfer radical polymerization and the atom transfer radical polymerization is 20 ℃ to 80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a linear-nonlinear block polymer, which consists of a linear polymer chain segment and a nonlinear structure polymerized by multiple vinyl groups, is a polymer with a brand new topological structure, the topological structure of the polymer is easy to adjust, and the obtained polymer contains a large number of unreacted double bonds, can be modified and modified by a plurality of methods such as Michael addition, click chemistry and the like, can further improve the functions of the polymer, and expands the application field of the polymer.
The invention also discloses a preparation method of the linear-nonlinear block polymer, wherein one preparation method is to take a macromolecular RAFT reagent as chain transfer, initiate the polyvinyl monomer by an initiator, and perform reversible addition-fragmentation chain transfer free radical polymerization under the anaerobic condition, and the other preparation method is to initiate the polyvinyl monomer by a macromolecular ATRP initiator, and perform atom transfer free radical polymerization under the anaerobic condition by using a ligand and a catalyst, so as to obtain the linear-nonlinear block polymer. The preparation method opens up a new way for synthesizing the linear-nonlinear topological structure polymer, enriches the types of the topological structure polymer, and has important implication significance for chemical synthesis of the topological structure polymer; the method has the advantages of wide and easily obtained reaction raw materials, mild reaction conditions, easy regulation and control of polymer composition, structure, molecular weight and molecular weight distribution, simple post-treatment of products, easy operation of polymerization, and suitability for large-scale production and application.
Drawings
FIG. 1 is a GPC chart of macromolecular RAFT reagent mPEG-CPABD of the invention before and after synthesis;
FIG. 2 is a GPC chart of the macromolecular ATRP initiator mPEG-Br before and after synthesis;
FIG. 3 is a schematic diagram of the synthesis of a linear-nonlinear block polymer in example 1 of the present invention;
FIG. 4 is a schematic diagram of the synthesis of a linear-nonlinear block polymer in example 2 of the present invention;
FIG. 5 is a block polymer of the invention of example 1 1 HNMR spectrogram;
FIG. 6 is a block polymer of example 2 of the present invention 1 HNMR spectrogram;
FIG. 7 is a GPC chart showing the molecular weight change of linear-nonlinear block polymers during the reaction of example 1 of the present invention;
FIG. 8 is a GPC chart showing the molecular weight change of linear-nonlinear block polymers during the reaction of example 2 of the present invention;
FIG. 9 is a fitted kinetic curve of the polymerization process of the linear-nonlinear block polymer of example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a linear-nonlinear block polymer which is formed by a nonlinear structure formed by polymerizing a linear polymer chain segment and a polyvinyl monomer, and is a polymer with a brand new topological structure.
The invention discloses a preparation method of a linear-nonlinear block polymer, which comprises the steps of taking a macromolecular RAFT reagent as chain transfer, initiating a polyvinyl monomer through an initiator to perform reversible addition-fragmentation chain transfer free radical polymerization reaction, initiating the polyvinyl monomer through a macromolecular ATRP initiator, and performing atom transfer free radical polymerization reaction through a ligand and a catalyst to obtain the linear-nonlinear block polymer.
The construction steps of the macromolecular RAFT reagent in the invention are as follows:
macromolecular RAFT reagents were synthesized using commercial polyethylene glycol monomethyl ether (mPEG) coupled with 4-cyanovaleric acid dithiobenzoic acid (CPADB), dithioesters, dithiocarbamates, trithiocarbonates or xanthates. Firstly, mPEG, 4-cyano valeric dithiobenzoic acid (CPADB) and 4- (dimethylamino) pyridine (DMAP) are dissolved in Dichloromethane (DCM), nitrogen is introduced for protection, secondly, the system is placed in an ice bath environment, a cyclohexyl carbodiimide (DCC) solution dissolved in the DCM is slowly added dropwise, and after the dropwise addition is finished, the reaction is carried out at room temperature under stirring for 40 hours. And then filtering the obtained product, precipitating and purifying by diethyl ether, dialyzing, and freeze-drying to obtain the macromolecule RAFT reagent mPEG-CPADB.
The construction steps of the macromolecular ATRP initiator in the invention are as follows:
commercial mPEG and haloalkanes were used to synthesize macromolecular ATRP initiators. First, mPEG, triethylamine (TEA) were dissolved in DCM. 2-Bromoisobutyryl bromide (BIB) dissolved in DCM was slowly added dropwise under ice-bath conditions and the reaction was continued with stirring at room temperature for 24h. After the reaction was completed, the water-soluble triethylamine hydrochloride was removed by washing with deionized water, and then the organic phase was dried, concentrated, and precipitated twice in glacial ethyl ether. And finally, collecting the product, and drying in a vacuum oven to obtain the macromolecular ATRP initiator mPEG-Br.
The reversible addition-fragmentation chain transfer radical polymerization reaction in the present invention comprises the steps of:
1) Fully dissolving a polyvinyl monomer, a macromolecular RAFT reagent and an initiator Azodiisobutyronitrile (AIBN) in 2-butanone to obtain a reaction mixed system; the mol ratio of the polyvinyl monomer, the macromolecular RAFT reagent and the initiator is (50-1000): 1: (0.1 to 1);
2) The reaction mixed system adopts inert gas replacement to fully deoxidize, and polymerization reaction is carried out at 40-80 ℃ after deoxidization is finished;
3) Monitoring the molecular weight of the polymer using Gel Permeation Chromatography (GPC), stopping the reaction when the molecular weight reaches 1000-50000 Da;
4) Purifying the product by adopting a precipitation method to obtain a linear-nonlinear block polymer with the molecular weight of 1000-50000 Da;
5) Through nuclear magnetic resonance hydrogen spectrum 1 HNMR) and Gel Permeation Chromatography (GPC) to determine the composition, knots, of a polymerStructure, molecular weight and molecular weight distribution.
The atom transfer radical polymerization reaction in the invention comprises the following steps:
1) The polyvinyl monomer, macromolecular ATRP initiator, ligand N, N, N' -pentamethyl divinyl triamine and catalyst CuBr 2 Fully dissolving in dimethyl sulfoxide (DMSO) to obtain a reaction mixed system; the molar ratio of the polyvinyl monomer, the macromolecular ATRP initiator, the ligand and the catalyst is (50-1000): 1: (0.5-5): (0.05 to 0.5);
2) The reaction mixed system adopts inert gas replacement to fully deoxidize, and polymerization reaction is carried out at 20-40 ℃ after deoxidization is finished;
3) Monitoring the molecular weight of the polymer using Gel Permeation Chromatography (GPC), stopping the reaction when the molecular weight reaches a specific value of 1000-50000 Da;
4) Purifying the product to obtain a linear-nonlinear block polymer with the molecular weight of 1000-50000 Da;
5) Through nuclear magnetic resonance hydrogen spectrum 1 HNMR) and Gel Permeation Chromatography (GPC) to determine the composition, structure, molecular weight, and molecular weight distribution of the polymer.
The linear-nonlinear block polymer prepared by the preparation method is composed of a nonlinear structure formed by polymerizing a linear polymer chain segment and a polyvinyl monomer, and has the following chemical structural formula:
wherein m=5 to 20, p=5 to 100, q=5 to 100; r is R 1 The structure can be the following two types:
1)*Br；2)
wherein R is 2 The structure can be the following two types:
1)
2)
wherein n=10 to 200.
Specific examples are as follows:
example 1
Based on RAFT polymerization mechanism: divinylbenzene (DVB, 1.3019g,10 mmol) was first thoroughly dissolved in a reaction flask with 50mL of 2-butanone, and then the macromolecular RAFT reagent mPEG-CPADB (mw=5000 da,250mg,0.05 mmol) and initiator (AIBN, 2.73mg,0.0167 mmol) were added and mixed with stirring. The obtained reaction system adopts an argon replacement deoxidization method to remove dissolved oxygen in the reaction system and air in a bottle at room temperature, and the replacement deoxidization time is 30min. After the oxygen removal is completed, the reaction is carried out at 80℃and the molecular weight is monitored by GPC. After 9.5 hours of reaction, the reaction was stopped and the free radical was quenched. The product was purified by precipitation and a linear-nonlinear block polymer with a molecular weight of 20000Da was obtained, the synthetic scheme is shown in fig. 3, and the performance test results are as follows:
referring to fig. 1, in the GPC spectra before and after the synthesis of mPEG-CPABD of the macromolecular RAFT reagent prepared by the invention, the peak time after the reaction is obviously shifted to the left, the molecular weight is increased, and the molecular weight increment is consistent with the molecular weight of CPABD, which proves that the coupling of mPEG and CPABD is realized.
Referring to FIG. 7, which shows the GPC chart of the molecular weight change of the linear-nonlinear block polymer during the reaction in example 1 of the present invention, it is understood that the molecular weight distribution of the polymer does not increase significantly as the reaction proceeds, i.e., intermolecular crosslinking does not occur, and the reaction can achieve good control over the polymerization.
Referring to FIG. 9, a graph showing the reaction time versus ln ([ M ] is shown for the kinetics of the polymerization of the linear-nonlinear block polymer of example 1 of the present invention] 0 /[M] t ) Linear correlation, where [ M ]] 0 To react the initial monomer concentration, [ M ]] t For the monomer concentration at time t corresponding to the reaction time, the reaction satisfies the first order kinetic model.
Example 2
Based on ATRP polymerization mechanism: bisphenol A polyoxyethylene ether diacrylate (BEDA, 314.28mg,2 mmol), macromolecular ATRP initiator mPEG-Br
(mw=2000 da,40mg,0.02 mmol), ligand N, N', N "-pentamethyldivinyl triamine (PMDETA, 2.7728mg,0.016 mmol) and catalyst CuBr 2 (0.8934 mg, 0.004mmol) was dissolved in a 50mL flask with 20mL dimethyl sulfoxide (DMSO), and deoxygenated by bubbling argon gas at room temperature for 30min. Taking 5cm copper wires to be wound on a magnet, soaking the magnet in concentrated hydrochloric acid for 20min, taking out the magnet, repeatedly flushing the magnet with acetone and water, wiping the magnet, rapidly putting the magnet into a reaction flask under the protection of nitrogen, carrying out temporary deoxidization, carrying out reaction at 25 ℃ and carrying out GPC monitoring. After 3h reaction, the reaction was stopped, and the product was purified by precipitation to obtain a linear-nonlinear block polymer with a molecular weight of 15000Da, the synthetic schematic diagram is shown in fig. 4, and the performance test results are as follows:
referring to FIG. 2, GPC spectra before and after synthesis of mPEG-Br as a macromolecular ATRP initiator prepared by the invention show that the peak time after reaction is obviously shifted left, the molecular weight is increased, and the molecular weight increment is consistent with the molecular weight of 2-bromoisobutyryl bromide (BIB) substituted part, thus proving that the synthesis of mPEG-Br is successfully realized.
Referring to FIG. 8, which shows the GPC chart of the molecular weight change of the linear-nonlinear block polymer during the reaction in example 2 of the present invention, it is understood that the molecular weight distribution of the polymer does not increase significantly as the reaction proceeds, i.e., intermolecular crosslinking does not occur, and the reaction can achieve good control over the polymerization.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (3)
1. A method of preparing a linear-nonlinear block polymer comprising:
1) Firstly, sufficiently dissolving divinylbenzene with 2-butanone, then adding a macromolecular RAFT reagent and an initiator, and stirring and mixing to obtain a reaction system;
wherein the dosage of divinylbenzene is 1.3019g,10mmol and the dosage of 2-butanone is 50mL;
the macromolecular RAFT reagent is mPEG-CPADB, the mw=5000 Da, the dosage is 250mg,0.05mmol; the initiator is AIBN, and the dosage is 2.73mg and 0.0167mmol;
2) Removing dissolved oxygen and air in a bottle in the reaction system by adopting an argon replacement deoxidization method at room temperature, wherein the replacement deoxidization time is 30min;
3) After the deoxidization is finished, the reaction is carried out at 80 ℃, the molecular weight is monitored by GPC, the reaction is stopped after 9.5 hours, the free radical is quenched, the product is purified by a precipitation method, and the linear-nonlinear block polymer with the molecular weight of 20000Da is obtained.
2. A method of preparing a linear-nonlinear block polymer comprising:
1) Dissolving bisphenol A polyoxyethylene ether diacrylate, a macromolecular ATRP initiator, a ligand N, N, N ', N ' ', N ' ' -pentamethyl divinyl triamine and a catalyst in a reaction flask by using dimethyl sulfoxide, and deoxidizing by bubbling argon for 30min at room temperature;
wherein the dosage of the bisphenol A polyoxyethylene ether diacrylate is 314.28mg and 2mmol;
the macromolecular ATRP initiator is mPEG-Br with Mw=2000 Da and the dosage is 40mg and 0.02mmol;
the ligand N, N, N ', N ' ', N ' ' -pentamethyldivinyl triamine is used in an amount of 2.7728mg,0.016 mmol;
the catalyst is CuBr 2 The dosage is 0.8934mg,0.004mmol;
the dosage of dimethyl sulfoxide is 20mL;
2) Winding 5cm copper wires on a magnet, soaking in concentrated hydrochloric acid for 20min, taking out, repeatedly flushing with acetone and water, wiping, rapidly placing into the reaction flask under the protection of nitrogen, carrying out transient deoxidization, then carrying out reaction at 25 ℃ and carrying out GPC monitoring;
3) Stopping the reaction after 3 hours of reaction, and purifying the product by a precipitation method to obtain the linear-nonlinear block polymer with the molecular weight of 15000 Da.
3. A linear-nonlinear block polymer prepared by the preparation method of claim 1 or claim 2.
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