CN114230739A - Linear-nonlinear block polymer and preparation method thereof - Google Patents
Linear-nonlinear block polymer and preparation method thereof Download PDFInfo
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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 composed of a linear polymer chain segment and a nonlinear structure polymerized by multiple vinyl monomers and is a polymer with a brand new topological structure. The invention also discloses a preparation method thereof, which is characterized in that on the basis of controllable polymerization of the polyvinyl monomer, the linear-nonlinear block polymer is prepared in one step by using macromolecule RAFT reagent to regulate and control or macromolecule ATRP to initiate polymerization of the polyvinyl monomer under the anaerobic condition. The method has the advantages of relatively mild reaction conditions, controllable composition, molecular weight and molecular weight distribution of the polymerization product, and easily-adjusted polymer topological structure, 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 for the preparation of polymers due to the advantages of mild polymerization conditions, wide monomer application range, easy control of polymer composition and structure, and the like. With the gradual and intensive research and application of the nonlinear topological structure, the nonlinear topological structure polymer is found to show obviously different performance from the linear topological structure. Polymerization of monovinyl monomers containing only one vinyl function by RAFT or ATRP often gives only linear macromolecules. The non-linear topological structure macromolecules such as brush type, star type, hyperbranched and cyclized macromolecules can be prepared by modifying a RAFT reagent, an ATRP initiator or a free radical initiator to a molecule with a specific topological structure in advance and then polymerizing the RAFT or ATRP of a single vinyl monomer. In addition, research on synthesis of cyclized and branched polymers by polymerization of polyvinyl monomers initiated based on small molecule RAFT chain transfer agent regulation or small molecule ATRP initiator has been advanced to some extent.
The linear-nonlinear block polymer shows performances completely different from linear, brush-shaped, star-shaped, hyperbranched, cyclized and other polymers due to the unique topological structure similar to tadpole, such as hydrodynamic volume, glass transition temperature, interface performance and the like, so that the linear-nonlinear block polymer has huge application potential in the fields of biomedicine, coatings, engineering materials and the like. However, all the above methods cannot synthesize linear-nonlinear topological structure polymer in one step. At present, the linear-nonlinear block polymer is mainly synthesized by adopting segmented polymerization and spliced by the non-covalent bond effect. Because the nonlinear structure is difficult to synthesize and low in efficiency, and meanwhile, 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, 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 provides a linear-nonlinear block polymer and a preparation method thereof, which solves the problems of the conventional linear-nonlinear block polymer preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a linear-nonlinear block polymer, which is composed of a linear polymer chain segment and a nonlinear structure polymerized by polyvinyl monomers, and has the following structural formula:
wherein m is 5 to 20, p is 5 to 100, and q is 5 to 100;
R1is Br or
R2Is composed of
Wherein n is 10 to 200.
The invention also discloses a preparation method of the linear-nonlinear block polymer, wherein the preparation method comprises the steps of initiating a polyvinyl monomer by an initiator by taking a macromolecular RAFT reagent as chain transfer to perform reversible addition-fragmentation chain transfer free radical polymerization; another preparation method is to initiate a polyvinyl monomer by a macromolecule ATRP initiator, and carry out 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 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 carrying out polymerization reaction after the deoxidization is finished;
3) purifying the product to obtain the linear-nonlinear block polymer.
Further preferably, in step 1), the molecular weight of the macromolecular RAFT reagent is 500-50000Da and is obtained by coupling polyethylene glycol monomethyl ether with dithiobenzoic acid, dithioester, dithiocarbamate, trithiocarbonate or xanthate of 4-cyanovaleric acid.
Further preferably, in the step 1), the molar ratio of the polyvinyl monomer, the macro RAFT agent and the initiator is (50-1000): 1: (0.1 to 1);
the initiator is azobisisobutyronitrile, 4' -azo (4-cyanovaleric acid) or benzoyl peroxide; the solvent is 2-butanone.
Preferably, the atom transfer radical polymerization comprises the following steps:
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 deoxygenation is finished;
3) 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 is obtained by coupling polyethylene glycol monomethyl ether with halogenated alkane.
Further preferably, in the step 1), the molar ratio of the polyvinyl monomer, the macromolecular ATRP initiator, the ligand and the catalyst is (50-1000): 1: (0.5-5): (0.05-0.5);
the ligand is N, N, N' -pentamethyl divinyl triamine, and the catalyst is CuBr2And the solvent is dimethyl sulfoxide.
Further preferably, the polymerization temperature of the reversible addition-fragmentation chain transfer radical polymerization reaction and the atom transfer radical polymerization reaction is 20-80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a linear-nonlinear block polymer, which is composed of a linear polymer chain segment and a polyvinyl polymerized nonlinear structure, is a polymer with a brand new topological structure, is easy to adjust the topological structure of the polymer, contains a large number of unreacted double bonds, can be 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 that macromolecule RAFT reagent is used as chain transfer, a polyvinyl monomer is initiated by an initiator, reversible addition-fragmentation chain transfer free radical polymerization is carried out under the anaerobic condition, and the other preparation method is that macromolecule ATRP initiator is used to initiate the polyvinyl monomer, and atom transfer free radical polymerization is carried out under the anaerobic condition by using a ligand and a catalyst, so as to obtain the linear-nonlinear block polymer. The preparation method disclosed by the invention opens up a new way for synthesizing the linear-nonlinear topological structure polymer, enriches the types of the topological structure polymer and has important revelation significance for the chemical synthesis of the topological structure polymer; and the reaction raw materials are widely and easily available, the reaction condition is mild, the composition, the structure, the molecular weight and the molecular weight distribution of the polymer are easy to regulate and control, the product post-treatment is simple, the polymerization is easy to operate, and the method is suitable for large-scale production and application.
Drawings
FIG. 1 shows GPC spectra before and after synthesis of macromolecular RAFT reagent mPEG-CPABD of the present invention;
FIG. 2 is GPC spectra before and after synthesis of macromolecular ATRP initiator mPEG-Br in accordance with the present invention;
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 drawing showing the preparation of a linear-nonlinear block polymer in example 1 of the present invention1HNMR spectrogram;
FIG. 6 is a diagram showing the preparation of a linear-nonlinear block polymer in example 2 of the present invention1HNMR spectrogram;
FIG. 7 is a GPC chart of the change in molecular weight of a linear-nonlinear block polymer during the reaction of example 1 of the present invention;
FIG. 8 is a GPC chart of the change in molecular weight of a linear-nonlinear block polymer during the reaction of example 2 of the present invention;
FIG. 9 is a curve fitted to the kinetics of the linear-nonlinear block polymer polymerization process of example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or 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 composed of a linear polymer chain segment and a nonlinear structure polymerized by multiple vinyl monomers 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 initiating a polyvinyl monomer by an initiator by using a macromolecular RAFT (reversible addition fragmentation chain transfer) reagent as chain transfer, and carrying out reversible addition-fragmentation chain transfer free radical polymerization reaction.
The construction steps of the macromolecular RAFT reagent 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-cyanovaleric acid dithiobenzoic acid (CPADB) and 4- (dimethylamino) pyridine (DMAP) are dissolved in Dichloromethane (DCM), nitrogen is introduced for protection, then the system is placed in an ice bath environment, a cyclohexyl carbodiimide (DCC) solution dissolved in DCM is slowly dripped, and after dripping is finished, the temperature is changed to room temperature for further stirring and reaction for 40 hours. Then, filtering the obtained product, precipitating and purifying by using diethyl ether, dialyzing, and freeze-drying to obtain the macromolecular RAFT reagent mPEG-CPADB.
The macromolecular ATRP initiator of the invention has the following construction steps:
commercial mPEG was used with haloalkanes to synthesize macromolecular ATRP initiators. First, mPEG, Triethylamine (TEA) were dissolved in DCM. 2-Bromoisobutyroylbromide (BIB) dissolved in DCM was slowly added dropwise under ice-bath conditions and the reaction was continued stirring at room temperature for 24 h. After the reaction was completed, the reaction mixture was washed with deionized water to remove water-soluble triethylamine hydrochloride, 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 free radical polymerization reaction comprises the following steps:
1) fully dissolving a polyvinyl monomer, a macromolecular RAFT reagent and an initiator Azobisisobutyronitrile (AIBN) in 2-butanone to obtain a reaction mixed system; the molar 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 is fully deoxidized by adopting inert gas replacement, and polymerization reaction is carried out at 40-80 ℃ after the deoxidization is finished;
3) monitoring the molecular weight of the polymer by using Gel Permeation Chromatography (GPC), and stopping the reaction when the molecular weight reaches 1000-50000 Da;
4) purifying the product by a precipitation method to obtain a linear-nonlinear block polymer with the molecular weight of 1000-50000 Da;
5) by nuclear magnetic resonance hydrogen spectroscopy (1HNMR) and Gel Permeation Chromatography (GPC) to determine the composition, structure, molecular weight, and molecular weight distribution of the polymer.
The atom transfer radical polymerization reaction comprises the following steps:
1) mixing polyvinyl monomer, macromolecular ATRP initiator, ligand N, N, N' -pentamethyl divinyl triamine and catalyst CuBr2Fully 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): (0.05-0.5);
2) the reaction mixed system is fully deoxidized by adopting inert gas replacement, and polymerization reaction is carried out at 20-40 ℃ after the 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) by nuclear magnetic resonance hydrogen spectroscopy (1HNMR) 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 linear polymer chain segment and a nonlinear structure polymerized by polyvinyl monomers, and the chemical structural formula of the linear-nonlinear block polymer is as follows:
wherein m is 5 to 20, p is 5 to 100, and q is 5 to 100; r1The structure can be the following two types:
1)*Br；2)
in the formula R2The structure can be the following two types:
1)
2)
wherein n is 10 to 200.
The specific embodiment is as follows:
example 1
Based on the RAFT polymerisation mechanism: divinylbenzene (DVB,1.3019g,10mmol) was first dissolved in 50mL of 2-butanone in a reaction flask, and then the macro RAFT reagent mPEG-CPADB (Mw 5000Da, 250mg, 0.05mmol) and initiator (AIBN,2.73mg,0.0167mmol) were added and mixed with stirring. And removing dissolved oxygen in the reaction system and air in the bottle by adopting an argon replacement and oxygen removal method at room temperature, wherein the replacement and oxygen removal time is 30 min. After the oxygen removal, the reaction was carried out at 80 ℃ and the molecular weight was monitored by GPC. After 9.5h of reaction, the reaction was stopped and the free radicals were quenched. The product was purified by precipitation and yielded a linear-nonlinear block polymer with molecular weight of 20000Da, the synthetic scheme of which is shown in fig. 3, and the results of the performance tests are as follows:
referring to FIG. 1, GPC spectra before and after synthesis of the macromolecular RAFT reagent mPEG-CPABD prepared by the invention show that the peak-out time after 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, thus proving that the coupling of mPEG and CPABD is realized.
Referring to FIG. 7, which is a GPC chart showing the change of molecular weight of a linear-nonlinear block polymer during the reaction of example 1 of the present invention, it can be seen that as the molecular weight linearly increases with the progress of the reaction, the molecular weight distribution of the polymer does not increase significantly, i.e., intermolecular crosslinking does not occur, and the reaction can achieve good control of polymerization.
Referring to FIG. 9, a curve is fitted to the kinetics of the linear-nonlinear block polymer polymerization process of example 1 of the present invention, from which the reaction time is shown versus ln ([ M)]0/[M]t) Linear correlation of where [ M]0For the initial monomer concentration of the reaction, [ M ]]tThe reaction satisfies the first order kinetic model for the monomer concentration at time t, which corresponds to the reaction time.
Example 2
Proceeding based on the ATRP polymerization mechanism: bisphenol A polyoxyethylene ether diacrylate (BEDA, 314.28mg,2mmol) and macromolecular ATRP initiator mPEG-Br
(Mw 2000Da,40mg,0.02mmol), ligand N, N, N', N ", N" -pentamethyldiethylenetriamine (PMDETA,2.7728mg,0.016mmol) and catalyst CuBr2(0.8934mg, 0.004mmol) was dissolved in 20mL of dimethyl sulfoxide (DMSO) in a 50mL flask and deoxygenated by bubbling argon at room temperature for 30 min. Winding 5cm of copper wire on a magneton, soaking in concentrated hydrochloric acid for 20min, taking out, repeatedly washing with acetone and water, wiping, quickly placing into a reaction flask under the nitrogen protection atmosphere, removing oxygen for a short time, reacting at 25 ℃, and performing GPC monitoring. After reaction for 3h, the reaction is stopped, and the product is purified by precipitation to obtain a linear-nonlinear block polymer with the molecular weight of 15000Da, the synthetic scheme of which is shown in figure 4, and the performance test results are as follows:
referring to FIG. 2, GPC spectrograms before and after synthesis of the macromolecular ATRP initiator mPEG-Br prepared by the invention show that the peak-out time after reaction is obviously shifted to the left, the molecular weight is increased, and the molecular weight increment is consistent with the molecular weight of a 2-Bromine Isobutyryl Bromide (BIB) substituted part, thereby proving that the synthesis of mPEG-Br is successfully realized.
Referring to FIG. 8, which is a GPC chart of the change of molecular weight of a linear-nonlinear block polymer during the reaction of example 2 of the present invention, it can be seen that as the molecular weight linearly increases with the progress of the reaction, the molecular weight distribution of the polymer does not increase significantly, i.e., intermolecular crosslinking does not occur, and the reaction can achieve good control of polymerization.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A linear-nonlinear block polymer, wherein the linear-nonlinear block polymer is comprised of a linear polymer segment and a polymerized nonlinear structure of a polyvinyl monomer having the formula:
wherein m is 5 to 20, p is 5 to 100, and q is 5 to 100;
R1is Br or
R2Is composed of
Wherein n is 10 to 200.
2. The method of claim 1, wherein the method comprises initiating the polyvinyl monomer by an initiator using a macro RAFT agent as a chain transfer to perform a reversible addition-fragmentation chain transfer radical polymerization; another preparation method is to initiate a polyvinyl monomer by a macromolecule ATRP initiator, and carry out atom transfer radical polymerization reaction by using a ligand and a catalyst to obtain a linear-nonlinear block polymer.
3. The method of claim 2, wherein 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.
4. The method of claim 2, wherein the reversible addition-fragmentation chain transfer 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 carrying out polymerization reaction after the deoxidization is finished;
3) purifying the product to obtain the linear-nonlinear block polymer.
5. The method as claimed in claim 4, wherein the molecular weight of the macromolecular RAFT reagent in step 1) is 500-50000Da and the macromolecular RAFT reagent is obtained by coupling polyethylene glycol monomethyl ether with dithiobenzoic acid, dithioester, dithiocarbamate, trithiocarbonate or xanthate of 4-cyanovaleric acid.
6. The method for preparing a linear-nonlinear block polymer according to claim 4, wherein in the step 1), the molar ratio of the polyvinyl monomer, the macro RAFT agent and the initiator is (50-1000): 1: (0.1 to 1);
the initiator is azobisisobutyronitrile, 4' -azo (4-cyanovaleric acid) or benzoyl peroxide; the solvent is 2-butanone.
7. The method of claim 2, wherein 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 deoxygenation is finished;
3) purifying the product to obtain the linear-nonlinear block polymer.
8. The method as claimed in claim 7, wherein the molecular weight of the ATRP initiator in step 1) is 500-50000Da and the ATRP initiator is obtained by coupling polyethylene glycol monomethyl ether with halogenated alkane.
9. The method for preparing a linear-nonlinear block polymer according to claim 7, wherein in the step 1), the molar ratio of the polyvinyl monomer, the macromolecular ATRP initiator, the ligand and the catalyst is (50-1000): 1: (0.5-5): (0.05-0.5);
the ligand is N, N, N' -pentamethyl divinyl triamine, and the catalyst is CuBr2And the solvent is dimethyl sulfoxide.
10. The method for preparing a linear-nonlinear block polymer according to claim 4 or 7, wherein the polymerization temperature is 20 ℃ to 80 ℃.
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