CN113999354A - Amphiphilic block polymer nanoparticles with different morphologies and preparation method and application thereof - Google Patents
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Abstract
The invention provides amphiphilic block polymer nanoparticles with different morphologies, a preparation method and application thereof, and relates to the technical field of polymers. Under the catalytic action of a Lewis acid-base pair, an acrylate monomer stable chain segment monomer and a nucleation chain segment monomer are subjected to polymerization reaction to obtain amphiphilic block polymer nanoparticles with different morphologies; the nucleating segment monomer comprises trifluoroethyl methacrylate or benzyl methacrylate. The Lewis acid-base pair used as the catalyst can efficiently synthesize highly asymmetric amphiphilic block polymer nanoparticles with different morphologies by a one-pot one-step method, and the polymer nanoparticles have the advantages of definite structure, less monomer insertion errors, good polymerization controllability and narrow molecular weight distribution. The amphiphilic block polymer nanoparticles with spherical morphology, worm morphology and vesicle morphology can be obtained by controlling the dosage ratio of the two monomers.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to amphiphilic block polymer nanoparticles with different morphologies and a preparation method and application thereof.
Background
The self-assembly of amphiphilic block copolymer in solution is a powerful method for synthesizing polymer nano-materials, the traditional solution self-assembly needs to firstly synthesize and purify block polymer, then disperse the block polymer in selective solvent, and utilize the solubility difference of the selective solvent to each block in the amphiphilic block polymer and the relative proportion difference of each block so as to obtain assemblies such as spheres, vesicles and the like, but the method requires extremely low assembly concentration (< 1%) and a complex process of 'polymer synthesis + post-polymerization assembly', and the defects greatly limit the practical application of the method in industry.
The advent of the polymerization induced self-assembly (PISA) process effectively avoided the above problems. The PISA has the greatest advantages of capability of polymerization and assembly at very high concentration, strong repeatability, simple operation and wide industrial application. The advent of various living/controlled polymerization technologies provides conditions for the rapid development of PISA, such as radical polymerization (reversible addition-fragmentation chain transfer polymerization (RAFT), Atom Transfer Radical Polymerization (ATRP), and nitroxide-mediated polymerization (NMP)), ring-opening metathesis polymerization (ROMP), and living anion polymerization, among others. Among these polymerization methods, the radical polymerization usually requires a "two-pot two-step" synthesis, i.e., a macroinitiator is synthesized in the first pot, and self-assembly while chain-growth synthesis of the amphiphilic block polymer occurs after the macroinitiator in the second pot after separation and purification, which is usually time-consuming and usually requires heating, and energy-consuming; ROMP and living anion polymerization are usually synthesized by a "one pot two step" method, i.e. a catalyst and a solvent-philic segment monomer are added in one pot, after the first monomer is polymerized, the second monomer is added directly without quenching, and various different morphologies are self-assembled while the amphiphilic block copolymer is synthesized; the ROMP and living anionic polymerization processes are relatively simple relative to free radical polymerization, but also require continuous feeding.
Yuan Ying et al (see Huo M, D Li, Song G, et al. semi-Fluorinated polyesters: A Class of Versatile Monomers for Polymerization-Induced seif-Assembly [ J ]. Macromolecular Rapid Communications,2018:1700840.) disclose that polymer assemblies with adjustable size and morphology are prepared by free radical Polymerization, which give worm-like micelles and sheets (monomer conversion of 50.2%) after 3 hours and 5 hours of Polymerization, and vesicle-shaped polymers after 7 hours of Polymerization, the reaction scheme is as in formula (1). However, the method can be prepared only by two steps in two pots, and the process is complex. .
Disclosure of Invention
In view of the above, the present invention provides amphiphilic block polymer nanoparticles with different morphologies, and a preparation method and an application thereof. The preparation method provided by the invention can efficiently synthesize the amphiphilic block polymer nanoparticles with different morphologies by one pot and one step, and has simple process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of amphiphilic block polymer nanoparticles with different morphologies, which comprises the following steps:
mixing a stable chain segment monomer, a nucleation chain segment monomer, Lewis acid, Lewis base and an aromatic solvent, and carrying out polymerization reaction on the obtained mixed reaction liquid to obtain amphiphilic block polymer nanoparticles with different morphologies;
the stable chain segment monomer is an acrylate monomer;
the nucleating segment monomer comprises trifluoroethyl methacrylate, 2,3, 3-tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, heptafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, phenyl methacrylate, pentafluorophenyl methacrylate or benzyl methacrylate.
Preferably, the acrylic monomer includes dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, or 2-ethylhexyl acrylate.
Preferably, the molar ratio of the stabilizing segment monomer to the nucleating segment monomer is 1: 1 to 5.5.
Preferably, the Lewis base is an azacycloalkene, the azacycloalkeneThe hydrocarbon is
Preferably, the Lewis acid is BHTAliBu2。
Preferably, the molar ratio of lewis base, lewis acid and stabilizing segment monomer is 1: 2-10: 50 to 100.
Preferably, the temperature of the polymerization reaction is 0-100 ℃, and the time is 18-163 min.
Preferably, the solid content of the mixed reaction liquid is 5-20%.
The invention provides amphiphilic block polymer nanoparticles with different morphologies, wherein the amphiphilic block polymer nanoparticles are obtained by the preparation method in the technical scheme, and the different morphologies comprise one or more of spheres, worms and vesicles.
The invention provides application of the amphiphilic block polymer nanoparticles with different morphologies as an anti-friction agent, an emulsifying agent, a reinforcing agent, a drug delivery carrier or a nano reactor.
The invention provides a preparation method of amphiphilic block polymer nanoparticles with different morphologies, which comprises the following steps: mixing a stable chain segment monomer, a nucleation chain segment monomer, Lewis acid, Lewis base and an aromatic solvent, and carrying out polymerization reaction on the obtained mixed reaction liquid to obtain amphiphilic block polymer nanoparticles with different morphologies; the polymerization reaction time is 18-163 min; the stable chain segment monomer is an acrylate monomer; the nucleating segment monomer comprises trifluoroethyl methacrylate. The preparation method provided by the invention can synthesize highly asymmetric amphiphilic block polymer nanoparticles with different morphologies by using the Lewis acid-base pairs as catalysts through a one-pot one-step method, and the process is simple; lewis acid and base have high catalytic activity to acrylic ester monomers, trifluoroethyl methacrylate and benzyl methacrylate, the polymerization reaction time can be obviously shortened, the polymerization reaction time is short, and the prepared amphiphilic block polymer nanoparticles with different morphologies have definite structures, few monomer insertion errors, good polymerization controllability and narrow molecular weight distribution. Moreover, the preparation method provided by the invention is simple to operate and suitable for industrial production.
Furthermore, by controlling the dosage ratio of the two stable chain segment monomers and the nucleating chain segment monomer, the amphiphilic block polymer nano particles with different morphologies, such as a sphere morphology, a worm morphology and a vesicle morphology, can be controllably prepared.
Furthermore, the preparation method provided by the invention can be used for carrying out polymerization reaction at room temperature, and has the advantages of mild reaction conditions, no need of heating and low energy consumption.
The invention provides amphiphilic block polymer nanoparticles with different morphologies, wherein the amphiphilic block polymer nanoparticles are obtained by the preparation method in the technical scheme, and the different morphologies comprise one or more of spheres, worms and vesicles. The amphiphilic block polymer nanoparticles with different morphologies provided by the invention have the advantages of definite structure, less monomer insertion errors, good polymerization controllability and narrow molecular weight distribution.
Drawings
FIG. 1 is a GPC chart of amphiphilic block polymer nanoparticles with different morphologies prepared in examples 1-4;
FIG. 2 is a GPC chart of amphiphilic block polymer nanoparticles with different morphologies prepared in comparative example 3;
FIG. 3 is a GPC chart of the polymer prepared in comparative example 5;
FIG. 4 is a GPC chart of the polymer prepared in comparative example 6;
FIG. 5 is a hydrogen spectrum of a PDMAEA homopolymer prepared in comparative example 4;
FIG. 6 is a DOSY diagram of amphiphilic block polymer nanoparticles with different morphologies prepared in example 1;
FIG. 7 shows the polymers prepared in example 1 and comparative examples 1 to 213C NMR spectrum;
FIG. 8 is a DSC of amphiphilic block polymer nanoparticles with different morphologies prepared in example 1;
FIG. 9 is a TEM image of amphiphilic block polymer nanoparticles with different morphologies prepared in examples 1-4;
FIG. 10 is a DLS diagram of amphiphilic block polymer nanoparticles with different morphologies prepared in examples 1-2 and 4;
FIG. 11 is a TEM image of amphiphilic block polymer nanoparticles with different morphologies prepared in examples 5-7.
Detailed Description
The invention provides a preparation method of amphiphilic block polymer nanoparticles with different morphologies, which comprises the following steps:
mixing a stable chain segment monomer, a nucleation chain segment monomer, Lewis acid, Lewis base and an aromatic solvent, and carrying out polymerization reaction on the obtained mixed reaction liquid to obtain the amphiphilic block polymer nanoparticles with different morphologies.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the stable segment monomer is an acrylate monomer, preferably including dimethylaminoethyl acrylate (DMAEA), diethylaminoethyl acrylate (DEAEA), Methyl Acrylate (MA), Ethyl Acrylate (EA), Butyl Acrylate (BA), 2-methoxyethyl acrylate (MEA), or 2-ethylhexyl acrylate (2-EHA). In the present invention, the nucleating segment monomer includes trifluoroethyl methacrylate (TFEMA), 2,3, 3-tetrafluoropropyl methacrylate (TFPMA), octafluoropentyl methacrylate (OFPMA), heptafluorobutyl methacrylate (HFBMA), dodecafluoroheptyl methacrylate (DFHMA), Phenyl Methacrylate (PMA), pentafluorophenyl methacrylate (PFMA), or benzyl methacrylate (BnMA). In the present invention, the molar ratio of the stabilizing segment monomer to the nucleating segment monomer is preferably 1: 1 to 5.5, more preferably 75: 265-400 or 100: 100 to 500.
In the present invention, the Lewis base is preferably an azacyclo-olefin, and the azacyclo-olefin is preferably an azacyclo-olefin
In the present invention, the Lewis acid is preferably BHTAliBu2。
In the present invention, the aromatic solvent preferably includes one or more of toluene, o-xylene, and mesitylene. In the invention, the solid content of the mixed reaction liquid is preferably 5-20%, more preferably 5-15%, and most preferably 10-15%, wherein the solid content is the proportion of the total mass of the stable chain segment monomer, the nucleation chain segment monomer, the Lewis acid and the Lewis base in the total mass of the stable chain segment monomer, the nucleation chain segment monomer, the Lewis acid, the Lewis base and the aromatic solvent.
In the present invention, the molar ratio of the lewis base and lewis acid to the stabilizing segment monomer is preferably 1: 2-10: 50-100, more preferably 1: 2-5: 60-80. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed; the temperature of the mixing is preferably room temperature; the mixing sequence is preferably that the stable chain segment monomer and the nucleation chain segment monomer are added into the aromatic solvent, the Lewis acid is added for premixing, and then the Lewis base is added; the time for premixing is preferably 2-10 min, and more preferably 2-5 min.
In the present invention, the polymerization reaction temperature is preferably 0 to 100 ℃, more preferably 10 to 90 ℃, and further preferably 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃; the time of the polymerization reaction is preferably 18-163 min, more preferably 20-120 min, and further preferably 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min or 110 min; in the examples of the present invention, the time of the polymerization reaction is preferably determined by testing the hydrogen spectrum of the polymerization reaction system: (1HNMR) that the polymerization reaction was complete when the polymerization reaction system contained no stabilizing segment monomer and no nucleating segment monomer (i.e., 100% conversion of both monomers); the polymerization is preferably carried out in a glove box. In the invention, the stable chain segment monomer and the nucleation chain segment monomer are subjected to Michael addition polymerization reaction under the catalysis of Lewis acid-base pair in the polymerization reaction process and are self-assembled at the same time to obtain the productAmphiphilic block polymer nanoparticles with different morphologies.
The invention provides amphiphilic block polymer nanoparticles with different morphologies, wherein the amphiphilic block polymer nanoparticles are obtained by the preparation method in the technical scheme, and the different morphologies comprise one or more of spheres, worms and vesicles. In the invention, the polymerization degree ratio of the stable segment monomer to the nucleation segment monomer in the amphiphilic block polymer nanoparticles with different morphologies is preferably 1: 1 to 5.5, more preferably 75: 265-400 or 100: 100-500, specifically, when the polymerization degree of the stable chain segment in the amphiphilic block polymer nanoparticles with different morphologies is 75, the polymerization degree of the nucleation chain segment polymer segment is 265-400; when the polymerization degree of the stable chain polymer segment is 100, the polymerization degree of the nucleation chain segment polymer segment is 100-500, more preferably 200-500, and most preferably 265-400.
In the invention, the particle size of the amphiphilic block polymer nanoparticles with different morphologies is preferably 50-290 nm, more preferably 50-200 nm, and further preferably 50-150 nm.
The invention provides application of the amphiphilic block polymer nanoparticles with different morphologies as an anti-friction agent, an emulsifying agent, a reinforcing agent, a drug delivery carrier or a nano reactor. In the invention, the anti-friction agent is preferably an anti-friction agent of automobile engine oil; the emulsifier is preferably Pickering emulsifier; the reinforcing agent is preferably an epoxy resin or coating reinforcing agent.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
Adding DMAEA and TFEMA into toluene at room temperature, adding Lewis acid for premixing for 2min, and adding Lewis alkali, carrying out polymerization reaction on the obtained mixed reaction liquid for 18min to obtain an amphiphilic block polymer nano particle solution, determining the morphology of the amphiphilic block polymer nano particles in the solution, adding n-hexane into the amphiphilic block polymer nano particle solution for quenching, filtering, washing the obtained solid product for 3 times by using the n-hexane, and then draining to obtain the amphiphilic block polymer nano particles (marked as PDMAEA)75-b-PTFEMA265Where 75 and 265 represent the degree of polymerization), followed by subsequent characterization and testing.
Wherein the Lewis base is
The Lewis acid is BHTAliBu2(ii) a The solid content of the mixed reaction liquid is 15%; lewis base: lewis acid: DMAEA: the molar ratio of TFEMA is 1:2:75: 265.
Examples 2 to 7
Amphiphilic block polymer nanoparticles were prepared according to the method of example 1, with the preparation conditions shown in table 1:
TABLE 1 preparation conditions of examples 1 to 7
Comparative example 1
Prepared according to the method of example 1, except that no DMAEA was added to give trifluoroethyl methacrylate homopolymer (PTFEMA).
Comparative example 2
Prepared according to the method of example 1, except that no TFEMA was added to give a dimethylaminoethyl acrylate homopolymer (PDMAEA) unlike example 1.
Comparative example 3
Amphiphiles with different morphologies were prepared according to the method of example 1Block polymer nanoparticles, differing from example 1 in that the Lewis acid is (BHT)2AlMe, yielding an amphiphilic block copolymer.
Comparative example 4
Amphiphilic block polymer nanoparticles having different morphologies were prepared according to the method of example 1, except that the Lewis acid was (BHT)2AliBu, to give PDMAEA homopolymer.
Comparative example 5
Amphiphilic block polymer nanoparticles with different morphologies were prepared according to the method of example 1, which is different from example 1 in that the Lewis acid was BHTAliBu2The Lewis base is PEt3。
Comparative example 6
Amphiphilic block polymer nanoparticles with different morphologies were prepared according to the method of example 1, which is different from example 1 in that the Lewis acid was BHTAliBu2The Lewis base is
Test example
(1) Gel Permeation Chromatography (GPC)
The polymer nanoparticles prepared in examples 1 to 4 and comparative example 3 were dissolved in DMF solvent to obtain polymer solutions with a concentration of 2mg/mL, and then GPC of the polymer solutions was tested, and the results of the molecular weight and molecular weight distribution test of the amphiphilic block polymer nanoparticles with different degrees of polymerization are shown in FIGS. 1 to 4.
Fig. 1 is a Gel Permeation Chromatography (GPC) of the amphiphilic block polymer nanoparticles with different morphologies prepared in examples 1 to 4, and it can be known from fig. 1 that the molecular weights of the amphiphilic block polymer nanoparticles with different morphologies gradually increase with the increase of the TFEMA monomer ratio, so that the amphiphilic block polymer nanoparticles with different morphologies prepared by the present invention are copolymers.
FIG. 2 is a Gel Permeation Chromatogram (GPC) of the amphiphilic block copolymer nanoparticles prepared in comparative example 3, as can be seen from FIG. 2, when (BHT) was used)2AlMe instead of BHTAliBu2As Lewis acids, the GPC curve shows a bimodal distribution and a broad distribution.
FIG. 3 is a GPC chart of the polymer prepared in comparative example 5, and it can be seen from FIG. 3 that PEt3+ BHTAliBu2The initiation efficiency of the catalyst is low, the molecular weight of the obtained polymer is high, and the molecular weight distribution is wide, which is unfavorable for the regulation and control of the morphology of the amphiphilic block polymer nano-particles.
FIG. 4 is a GPC chart of the polymer prepared in comparative example 6, and from FIG. 4, the polymer prepared in comparative example 6 has a bimodal distribution, one peak of TFEMA homopolymer in addition to the peak of the copolymer, while PTFEMA is insoluble in a toluene solution, and thus BHTAl was usediBu2+
The polymerization system obtained as the catalyst is unstable and precipitates are generated, and the catalyst is not suitable for adjusting the morphology of the amphiphilic block polymer nano particles.
FIG. 5 shows the hydrogen spectrum of the PDMAEA homopolymer prepared in comparative example 4. As shown in FIG. 5, the polymer prepared in comparative example 41HNMR showed only the peak of PDMAEA, indicating that when used (BHT)2AliBu as a Lewis acid, only DMAEA monomer was polymerized, but TFEMA monomer was not polymerized. Therefore, when using (BHT)2AlMe and (BHT)2AliBu, two Lewis acids, has poor control of the polymerization reaction.
(2) Two-dimensional Diffusion Order Spectrum (DOSY)
10mg of the amphiphilic block polymer nanoparticles prepared in example 1 were dissolved in 550. mu.L of deuterated chloroform, and 500M 2D NMR was measured at room temperature. The test results are shown in fig. 6, and it can be seen from fig. 6 that all points on the spectrum are on a straight line, which indicates that the amphiphilic block polymer nanoparticles prepared by the present invention have the same diffusion coefficient and are a copolymer chain rather than a mixture of two homopolymers.
(3)13C NMR
FIG. 7 shows an embodimentOf the polymers prepared in example 1 and comparative examples 1 to 213C NMR spectrum, as can be seen from FIG. 7, the position and shape of the peak of the carbonyl region of the amphiphilic block polymer nanoparticles are consistent with those of the homopolymers prepared in comparative examples 1-2, which indicates that the amphiphilic block polymer nanoparticles prepared by the invention are block copolymers rather than random copolymers.
(4)DSC
Fig. 8 is a DSC diagram of amphiphilic block polymer nanoparticles prepared in example 1. As can be seen from FIG. 8, the amphiphilic block polymer nanoparticles prepared by the present invention have two glass transition temperatures TgDSC testing of random copolymers, corresponding to PDMAEA and PTFEMA respectively, has only one TgIt is illustrated that example 1 of the present invention produces block copolymers rather than random copolymers.
(5) Topography characterization
TEM test: diluting the reaction solution after the polymerization reaction by 100 times with toluene to obtain a diluent, dripping 10 mu L of the diluent on a carbon-supported film copper net for testing TEM, volatilizing overnight at room temperature, then testing TEM, and observing different assembly appearances through the TEM.
Dynamic Light Scattering (DLS) test: diluting the reaction solution after the polymerization reaction by 100 times with toluene to obtain a diluent, and then placing 1mL of the diluent in a glass sample cell for testing an instrument for testing the particle size distribution.
FIG. 9 is a TEM image of amphiphilic block polymer nanoparticles prepared in examples 1-4, and FIG. 10 is a DLS image of amphiphilic block polymer nanoparticles prepared in examples 1-2 and 4. As can be seen from fig. 9 to 10, when the DP of the fixed PDMAEA is 75, and when the DP of the PTFEMA is 265, 310 and 400, respectively, amphiphilic block polymer nanoparticles with spherical, worm and vesicle morphologies can be obtained, and the particle size measured by Dynamic Light Scattering (DLS) is consistent with that of the TEM, which indicates that the preparation method provided by the present invention can well control the morphology of the amphiphilic block polymer nanoparticles.
FIG. 11 is a TEM image of the amphiphilic block polymer nanoparticles prepared in examples 5-7, and it can be seen from FIG. 10 that the amphiphilic block polymer nanoparticles with spherical to vermicular morphology can be obtained by increasing the polymerization degree of PDMAEA.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of amphiphilic block polymer nanoparticles with different morphologies is characterized by comprising the following steps:
mixing a stable chain segment monomer, a nucleation chain segment monomer, Lewis acid, Lewis base and an aromatic solvent, and carrying out polymerization reaction on the obtained mixed reaction liquid to obtain amphiphilic block polymer nanoparticles with different morphologies;
the stable chain segment monomer is an acrylate monomer;
the nucleating segment monomer comprises trifluoroethyl methacrylate, 2,3, 3-tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, heptafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, phenyl methacrylate, pentafluorophenyl methacrylate or benzyl methacrylate.
2. The method of claim 1, wherein the acrylic monomer comprises dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, or 2-ethylhexyl acrylate.
3. The method of claim 1, wherein the mole ratio of the stabilizing segment monomer to the nucleating segment monomer is 1: 1 to 5.5.
4. The production process according to claim 1, wherein the Lewis base is an azacycloalkene, and the azacycloalkene is
5. The method according to claim 1, wherein the Lewis acid is BHTAliBu2。
6. The production method according to any one of claims 1 to 5, wherein the molar ratio of the Lewis base, the Lewis acid and the stable segment monomer is 1: 2-10: 50 to 100.
7. The method according to any one of claims 1 to 5, wherein the polymerization reaction is carried out at a temperature of 0 to 100 ℃ for 18 to 163 min.
8. The method according to any one of claims 1 to 5, wherein the solid content of the mixed reaction solution is 5 to 20%.
9. Amphiphilic block polymer nanoparticles with different morphologies obtained by the preparation method of any one of claims 1 to 8, wherein the different morphologies comprise one or more of a spherical shape, a worm shape and a vesicle shape.
10. Use of amphiphilic block polymer nanoparticles of claim 9 having different morphologies as an anti-friction agent, an emulsifier, an enhancer, a drug delivery vehicle or a nanoreactor.
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| US20060194935A1 (en) * | 2005-02-28 | 2006-08-31 | Canon Kabushiki Kaisha | Process for producing polyalkenyl ether |
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