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1.
Polymers (Basel) ; 14(12)2022 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-35746007

RESUMO

Polylactides (PLAs) are thermoplastic materials known for their wide range of applications. Moreover, the equimolar mixtures of poly(L-Lactide) (PLLA) and poly(D-Lactide) (PDLA) can form stereocomplexes (SCs), which leads to the formation of new non-covalent complex macromolecular architectures. In this work, we report the synthesis and characterization of non-covalent triblock terpolymers of polystyrene-b-stereocomplex PLA-b-poly(2-vinylpyridine) (PS-b-SC-b-P2VP). Well-defined ω-hydroxy-PS and P2VP were synthesized by "living" anionic polymerization high-vacuum techniques with sec-BuLi as initiator, followed by termination with ethylene oxide. The resulting PS-OH and P2VP-OH were used as macroinitiators for the ring-opening polymerization (ROP) of DLA and LLA with Sn(Oct)2 as a catalyst to afford PS-b-PDLA and P2VP-b-PLLA, respectively. SC formation was achieved by mixing PS-b-PDLA and P2VP-b-PLLA chloroform solutions containing equimolar PLAs segments, followed by precipitation into n-hexane. The molecular characteristics of the resulting block copolymers (BCPs) were determined by 1H NMR, size exclusion chromatography, and Fourier-transform infrared spectroscopy. The formation of PS-b-SC-b-P2VP and the effect of molecular weight variation of PLA blocks on the resulting polymers, were investigated by differential scanning calorimetry, X-ray powder diffraction, and circular dichroism spectroscopies.

2.
Biomacromolecules ; 23(6): 2441-2458, 2022 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-35588158

RESUMO

This paper reports novel hybrid arborescent polypeptides based on poly(γ-benzyl l-glutamate)-co-poly(γ-tert-butyl l-glutamate)-g-polysarcosine [P(BG-co-Glu(OtBu))-g-PSar]. The synthesis is launched by ring-opening polymerization (ROP) of N-carboxyanhydride of γ-benzyl l-glutamate (BG-NCA) and γ-tert-butyl l-glutamate (Glu(OtBu)-NCA) to synthesize a random copolymer P(BG-co-Glu(OtBu)) serving as a precursor for the arborescent system, followed by deprotection of the tert-butyl (tBu) groups to afford free COOH moieties serving as coupling sites. Two copolymerization reactions were carried out to afford the side chains. One type of side chain was a random copolymer P(BG-co-Glu(OtBu)), while the other type was a triblock copolymer PGlu(OtBu)-b-PBG-b-PGlu(OtBu). The peptide coupling reactions were conducted between the COOH moieties on the precursor and the terminus amine on the chain end of the P(BG-co-Glu(OtBu)) random copolymer or the PGlu(OtBu)-b-PBG-b-PGlu(OtBu) triblock copolymer to obtain G0 polymers. Afterward, hydrolyzing the tBu moieties of the G0 substrates yielded randomly functionalized G0 and end-functionalized G0. Randomly functionalized G0 was used as a substrate for the next generation G1 (randomly functionalized and end-functionalized G1 after deprotection) or coated with polysarcosine (PSar) to gain G0-g-PSar. The G0 substrate prepared with the triblock copolymer PGlu(OtBu)-b-PBG-b-PGlu(OtBu) was only grafted with PSar after deprotection, resulting in G0-eg-PSar. Depending on the functionality mode of the G1 substrate, the PSar coating yielded two different graft polymers, G1-g-PSar and G1-eg-PSar, for randomly functionalized and end-functionalized G1, respectively. The PSar hydrophilic shell was decorated with the sequence of (arginine, glycine, and aspartic acid) tripeptides (RGD) as a targeting ligand to improve the potentiality of the arborescent unimolecular micelles as drug carriers. Preparative size exclusion chromatography (SEC) was used to fractionate these complex macromolecular architectures. Nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR), Raman spectroscopy, and SEC were used for molecular characterization of all intermediate and final products and dynamic light scattering (DLS), transmission electron microscopy (TEM), and atomic force microscopy (AFM) for micellar characterization. A comparison between randomly grafted (g) and end-grafted (eg) unimolecular micelles demonstrates that the former has an undefined core-shell structure, unlike its end-grafted analog. In addition, this study has proved that decoration of the shell with RGD contributed to avoiding micelle aggregation but limited chemotherapy agent encapsulation. However, more than their naked analog, the sustained release was noticeable in decorated micelles. Doxorubicin was utilized as a chemotherapy model, and loading was achieved successfully by physical entrapment.


Assuntos
Ácido Glutâmico , Micelas , Oligopeptídeos , Peptídeos/química , Polímeros/química
3.
Polymers (Basel) ; 14(6)2022 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-35335467

RESUMO

Studying the effect of functional groups on the porosity structure and adsorption efficiency of polymer materials is becoming increasingly interesting. In this work, a novel porous polyaminal-linked polymer, based on naphthalene and melamine (PAN-NA) building blocks, was successfully synthesized by a one-pot polycondensation method, and used as an adsorbent for both CO2 and heavy metals. Fourier transform infrared spectroscopy, solid-state 13 C NMR, powder X-ray diffraction, and thermogravimetry were used to characterize the prepared polymer. The porous material structure was established by field-emission scanning electron microscope and N2 adsorption-desorption methods at 77 K. The polymer exhibited excellent uptake of CO2, 133 mg/g at 273 K and 1 bar. In addition, the adsorption behavior of PAN-NA for different metal cations, including Pb(II), Cr(III), Cu(II), Cd(II), Ni(II), and Ba(II), was investigated; a significant adsorption selectivity toward the Pb(II) cation was detected. The influence of pH, adsorbent dose, initial concentrations, and contact time was also assessed. Our results prove that the introduction of naphthalene in the polymer network improves the porosity and, thus, CO2 adsorption, as well as the adsorption of heavy metals.

4.
Biomacromolecules ; 22(12): 5243-5255, 2021 12 13.
Artigo em Inglês | MEDLINE | ID: mdl-34852198

RESUMO

Fluorescent drug delivery systems have received increasing attention in cancer therapy because they combine drug delivery and bioimaging into a single platform. For example, polymers with aggregation-induced emission (AIE) fluorophores, such as tetraphenylethylene (TPE), have emerged as an elegant choice for drug delivery/bioimaging applications. In this work, we report one-pot sequential organocatalytic ring-opening polymerization of ε-caprolactone (CL) and ethylene oxide (EO) using TPE-(OH)2 as a difunctional initiator, in the presence of a t-BuP2/TEB Lewis pair (catalyst), in THF at room temperature. Two well-defined triblock copolymers with inverse block sequences, TPE-(PCL-b-PEO)2 and TPE-(PEO-b-PCL)2, were synthesized by altering the sequential addition of CL and EO. The physicochemical properties, including hydrodynamic diameter, morphology, and AIE properties of the synthesized amphiphilic triblock copolymers were investigated in aqueous media. The block copolymer micelles were loaded with anticancer drugs doxorubicin and curcumin to serve as drug delivery vehicles. In vitro studies revealed the accelerated drug release at lower pH (5.5), which mimics the tumor microenvironment, different from the physiological pH (7.4). In vitro cytotoxicity studies demonstrated that the neat block copolymer micelles are biocompatible, while drug-loaded micelles exhibited a significant cytotoxic effect in cancer cells. Cellular uptake, examined by confocal laser scanning microscopy, showed that the block copolymer micelles were rapidly internalized by the cells with simultaneous emission of TPE fluorophore. These results suggest that these triblock copolymers can be utilized for intracellular bioimaging.


Assuntos
Sistemas de Liberação de Medicamentos , Micelas , Doxorrubicina/química , Doxorrubicina/farmacologia , Portadores de Fármacos/química , Liberação Controlada de Fármacos , Polietilenoglicóis/química , Polímeros/química
5.
Nat Commun ; 12(1): 7124, 2021 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-34880211

RESUMO

The synthesis of well-defined block copolymers from a mixture of monomers without additional actions ("one-pot/one-step") is an ideal and industrially valuable method. In addition, the presence of controlled alternating sequences in one or both blocks increases the structural diversity of polymeric materials, but, at the same time, the synthetic difficulty. Here we show that the "one-pot/one-step" ring-opening terpolymerization of a mixture of three monomers (N-sulfonyl aziridines; cyclic anhydrides and epoxides), with tert-butylimino-tris(dimethylamino)phosphorene (t-BuP1) as a catalyst, results in perfect diblock dialternating terpolymers having a sharp junction between the two blocks, with highly-controllable molecular weights and narrow molecular weight distributions (Ð < 1.08). The organocatalyst switches between two distinct polymerization cycles without any external stimulus, showing high monomer selectivity and kinetic control. The proposed mechanism is based on NMR, in-situ FTIR, SEC, MALDI-ToF, reactivity ratios, and kinetics studies.

6.
Polymers (Basel) ; 13(18)2021 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-34578032

RESUMO

The morphology and crystallization behavior of two triblock terpolymers of polymethylene, equivalent to polyethylene (PE), poly (ethylene oxide) (PEO), and poly (ε-caprolactone) (PCL) are studied: PE227.1-b-PEO4615.1-b-PCL3210.4 (T1) and PE379.5-b-PEO348.8-b-PCL297.6 (T2) (superscripts give number average molecular weights in kg/mol and subscripts composition in wt %). The three blocks are potentially crystallizable, and the triple crystalline nature of the samples is investigated. Polyhomologation (C1 polymerization), ring-opening polymerization, and catalyst-switch strategies were combined to synthesize the triblock terpolymers. In addition, the corresponding PE-b-PEO diblock copolymers and PE homopolymers were also analyzed. The crystallization sequence of the blocks was determined via three independent but complementary techniques: differential scanning calorimetry (DSC), in situ SAXS/WAXS (small angle X-ray scattering/wide angle X-ray scattering), and polarized light optical microscopy (PLOM). The two terpolymers (T1 and T2) are weakly phase segregated in the melt according to SAXS. DSC and WAXS results demonstrate that in both triblock terpolymers the crystallization process starts with the PE block, continues with the PCL block, and ends with the PEO block. Hence triple crystalline materials are obtained. The crystallization of the PCL and the PEO block is coincident (i.e., it overlaps); however, WAXS and PLOM experiments can identify both transitions. In addition, PLOM shows a spherulitic morphology for the PE homopolymer and the T1 precursor diblock copolymer, while the other systems appear as non-spherulitic or microspherulitic at the last stage of the crystallization process. The complicated crystallization of tricrystalline triblock terpolymers can only be fully grasped when DSC, WAXS, and PLOM experiments are combined. This knowledge is fundamental to tailor the properties of these complex but fascinating materials.

7.
Polymers (Basel) ; 13(15)2021 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-34372044

RESUMO

The crystallization and morphology of two linear diblock copolymers based on polymethylene (PM) and poly(vinylidene fluoride) (PVDF) with compositions PM23-b-PVDF77 and PM38-b-PVDF62 (where the subscripts indicate the relative compositions in wt%) were compared with blends of neat components with identical compositions. The samples were studied by SAXS (Small Angle X-ray Scattering), WAXS (Wide Angle X-ray Scattering), PLOM (Polarized Light Optical Microscopy), TEM (Transmission Electron Microscopy), DSC (Differential Scanning Calorimetry), BDS (broadband dielectric spectroscopy), and FTIR (Fourier Transform Infrared Spectroscopy). The results showed that the blends are immiscible, while the diblock copolymers are miscible in the melt state (or very weakly segregated). The PVDF component crystallization was studied in detail. It was found that the polymorphic structure of PVDF was a strong function of its environment. The number of polymorphs and their amount depended on whether it was on its own as a homopolymer, as a block component in the diblock copolymers or as an immiscible phase in the blends. The cooling rate in non-isothermal crystallization or the crystallization temperature in isothermal tests also induced different polymorphic compositions in the PVDF crystals. As a result, we were able to produce samples with exclusive ferroelectric phases at specific preparation conditions, while others with mixtures of paraelectric and ferroelectric phases.

8.
Chem Sci ; 12(32): 10732-10741, 2021 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-34447562

RESUMO

The "coordination-insertion" ring-opening polymerization (ROP) mechanism has so far been the monopoly of metal catalysts. In this work, we present a metal-free "coordination-insertion" ROP of trimethylene carbonate (TMC) and ε-caprolactone (ε-CL), as well as their sequential block copolymerization, with N-trimethylsilyl-bis (trifluoromethanesulfonyl)imide (TMSNTf2) as the non-metallic initiator/catalyst. TMSNTf2 was proposed to work through an unprecedented metal-free "coordination-insertion" mechanism, which involves the coordination of monomer to the Si atom of TMSNTf2, the nucleophilic attack of the -NTf2 group on the coordinated monomer, and the cleavage of the acyl-oxygen bond of the monomer. The proposed metal-free "coordination-insertion" ROP was studied by NMR, SEC, and MALDI-TOF analyses. In addition, the TMSNTf2-mediated ROP of TMC and ε-CL led to linear and cyclic polymers following two-stage first-order polymerization processes, as evidenced by structural analyses and kinetics study, which further demonstrated the metal-free "coordination-insertion" mechanism.

9.
Angew Chem Int Ed Engl ; 60(41): 22469-22477, 2021 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-34387919

RESUMO

A series of alkyl-subsituted dienyltriphenylarsonium ylides were synthesized and used as monomers in borane-initiated polymerization to obtain practically pure C5-polymers (main-chain grows by five carbon atoms at a time). The impact of triethylborane (Et3 B), tributylborane (Bu3 B), tri-sec-butylborane (s-Bu3 B), and triphenylborane (Ph3 B) initiators on C5 polymerization was studied. Based on NMR and SEC results, we have shown that all synthesized polymers have C5 units with a unique unsaturated backbone where two conjugated double bonds are separated by one methylene. The synthesized C5-polymers possess predictable molecular weights and narrow molecular weight distributions (Mn,NMR =2.8 -11.9 kg mol-1 , Ð=1.04-1.24). It has been found that increasing the steric hindrance of both the monomer and the initiator can facilitate the formation of more C5 repeating units, thus driving the polymerization to almost pure C5-polymer (up to 95.8 %). The polymerization mechanism was studied by 11 B NMR and confirmed by DFT calculations. The synthesized C5-polymers are amorphous with tunable glass-transition temperatures by adjusting the substituents of monomers, ranging from +30.1 °C to -38.4 °C. Furthermore, they possess blue photoluminescence that changes to yellow illuminating the polymers for 5 days with UV radiation of 365 nm (IIE, isomerization induced emission).

10.
Polymers (Basel) ; 13(5)2021 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-33803241

RESUMO

A series of well-defined (polyisoprene)2(polystyrene), I2S, single graft copolymers with similar total molecular weights but different compositions, fPS, were blended with a low molecular weight polyisoprene homopolymer matrix at a constant concentration 2 wt%, and the micellar characteristics were studied by small-angle x-ray scattering. To investigate the effect of macromolecular architecture on the formation and characteristics of micelles, the results on the single graft copolymers were compared with those of the corresponding linear polystyrene-b-polyisoprene diblock copolymers, SI. The comparison reveals that the polystyrene core chains are more stretched in the case of graft copolymer micelles. Stretching turned out to be purely a result of the architecture due to the second polyisoprene block in the corona. The micellization of a (polystyrene)2(polyisoprene), S2I, graft copolymer was also studied, and the comparison with the results of the corresponding I2S and SI copolymers emphasizes the need for a critical core volume rather than a critical length of the core-forming block, in order to have stable micelles. Finally, the absence of micellization in the case of the I2S copolymer with the highest polystyrene volume fraction is discussed. For this sample, macrophase separation occurs, with polyisoprene cylinders formed in the copolymer-rich domains of the phase-separated blends.

11.
Carbohydr Polym ; 261: 117903, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-33766381

RESUMO

A facile and effective "grafting from" method by ROP of N-sulfonyl aziridines toward cellulose-g-polysulfonamides has been developed for efficient oil/water separation. The cellulose paper was initially succinylated to transform the hydroxyl to carboxyl acid groups, which act as the initiating sites for the ring-opening copolymerization of fluorescent 2-methyl-1-dansylaziridine and 2-methyl-1-tosylaziridine (TsMAz) towards the grafted cellulose. Both steps are catalyzed by the same compound, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). The grafted polysulfonamide ratio was up to 136 wt%, and the surface contact angle up to 147°. A one-pot tandem strategy was applied to produce the grafted cellulose paper with a grafting ratio ranging from 96 to 150 % and a contact angle over 127°. The modified cellulose paper material showed promising properties for efficient oil/water separations.

12.
Angew Chem Int Ed Engl ; 60(15): 8431-8434, 2021 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-33432725

RESUMO

The first C5 polymerization is reported, where the main-chain is growing by five carbon atoms of the monomer at a time. Three dienyltriphenylarsonium ylide monomers were synthesized and polymerized with triethylborane as an initiator, leading to random terpolymers (C1, C3, C5) with mainly C5 repeating units (up to 84.1 %). It has been found that the methyl group (electron-donating substituent) on the conjugated double bond of the ylides facilitates the formation of C5 segments. A mechanism was proposed based on NMR characterization and DFT calculations. The high C5 content ensures that things are on the right track for pure C5 homopolymerization.

13.
Angew Chem Int Ed Engl ; 60(2): 889-895, 2021 01 11.
Artigo em Inglês | MEDLINE | ID: mdl-32935922

RESUMO

Functionalized polypeptides have attracted tremendous interest in recent years and found many stimulating applications owing to their tunable physicochemical characteristics including hydrophilicity and stimuli-responsive behavior. The development of new strategies to produce these polymers without metallic contaminants is crucial for their applications in high-value and sensitive domains, such as biomedical, microelectronic, food-packaging, and personal beauty care fields. Herein, a highly efficient strategy to access well-defined site-specific functionalized polypeptides is developed by combining Michael reaction with hydrogen-bonding organocatalytic ROP of NCA. A library of chain-end and chain-middle functionalized polypeptides (14 examples) with predesigned molecular weights and low polydispersities are readily prepared with this approach. Specifically, the whole synthetic process is metal-free, fulfilling high activity and selectivity at room temperature.

14.
Angew Chem Int Ed Engl ; 60(3): 1593-1598, 2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-32989882

RESUMO

The direct copolymerization of p-tosyl isocyanate (TSI) with epoxides, initiated by onium salts in the presence of trialkylborane, to produce polyurethanes is reported. The rate of copolymerization and the (regio)selectivity were investigated in relation to the trialkylborane and the initiator used. Under optimized conditions such copolymerizations have been successfully performed for a wide range of epoxides, including ethylene oxide, propylene oxide, 1-octene oxide, cyclohexene oxide, and allyl glycidyl ether. These copolymerizations afford a new category of polyurethanes, clear of side products such as cyclic oxazolidinone, isocyanurate, and poly(isocyanate) linkages. The experimental conditions used in this work are compatible with those for the organocatalytic (co)polymerization of other oxygenated monomers and CO2 , holding the potential for their terpolymerization with p-tosyl isocyanate and the development of new materials with unprecedented properties.

15.
Angew Chem Int Ed Engl ; 60(1): 331-337, 2021 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-33031601

RESUMO

A novel synthetic strategy gives reversible cross-linked polymeric materials with tunable fluorescence properties. Dimaleimide-substituted tetraphenylethene (TPE-2MI), which is non-emissive owing to the photo-induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross-link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE-2MI in DMF showed reversible fluorescence with "on/off" behavior depending on the Diels-Alder (DA)/retro-DA process, which is easily adjusted by temperature. At high temperatures, the retro-DA reaction is dominant, and the fluorescence is quenched by the photo-induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE-2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent "turn on/off" behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.

16.
Angew Chem Int Ed Engl ; 60(13): 6949-6954, 2021 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-33351198

RESUMO

We report a new synthetic methodology for poly(ester amide)s by anionic ring-opening copolymerization of N-sulfonyl aziridines and cyclic anhydrides. Phosphazenes organocatalysts have been found to promote a highly-active, controlled, and selective alternating copolymerization in the absence of any competitive side reaction (zwitterionic mechanism and exchange transacylations). Mechanistic studies have shown first-order dependence of the copolymerization rate in N-sulfonyl aziridines and phosphazenes, and zero-order in cyclic anhydrides. This one-pot methodology leads not only to homopolymers but also to poly(ester amide)-based block copolymers. Two catalytic cycles involving ring-opening alternating copolymerization of N-sulfonyl aziridines with cyclic anhydrides and ring-opening polymerization of N-sulfonyl aziridines have been proposed to explain the one pot synthesis of poly(ester amide)-based homo- and block copolymers.

17.
Macromolecules ; 54(15): 7244-7257, 2021 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-35663800

RESUMO

We investigate for the first time the morphology and crystallization of two novel tetrablock quarterpolymers of polyethylene (PE), poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) with four potentially crystallizable blocks: PE18 7.1 -b-PEO37 15.1 -b-PCL26 10.4 -b-PLLA19 7.6 (Q1) and PE29 9.5 -b-PEO26 8.8 -b-PCL23 7.6 -b-PLLA22 7.3 (Q2) (superscripts give number average molecular weights in kg/mol, and subscripts give the composition in wt %). Their synthesis was performed by a combination of polyhomologation (C1 polymerization) and ring-opening polymerization techniques using a ″catalyst-switch″ strategy, either ″organocatalyst/metal catalyst switch″ (Q1 sample, 96% isotactic tetrads) or ″organocatalyst/organocatalyst switch″ (Q2 sample, 84% isotactic tetrads). Their corresponding precursors-triblock terpolymers PE-b-PEO-b-PCL, diblock copolymers PE-b-PEO, and PE homopolymers-were also studied. Cooling and heating rates from the melt at 20 °C/min were employed for most experiments: differential scanning calorimetry (DSC), polarized light optical microscopy (PLOM), in situ small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS), and atomic force microscopy (AFM). The direct comparison of the results obtained with these different techniques allows the precise identification of the crystallization sequence of the blocks upon cooling from the melt. SAXS indicated that Q1 is melt miscible, while Q2 is weakly segregated in the melt but breaks out during crystallization. According to WAXS and DSC results, the blocks follow a sequence as they crystallize: PLLA first, then PE, then PCL, and finally PEO in the case of the Q1 quarterpolymer; in Q2, the PLLA block is not able to crystallize due to its low isotacticity. Although the temperatures at which the PEO and PCL blocks and the PE and PLLA blocks crystallize overlap, the analysis of the intensity changes measured by WAXS and PLOM experiments allows identifying each of the crystallization processes. The quarterpolymer Q1 remarkably self-assembles during crystallization into tetracrystalline banded spherulites, where four types of different lamellae coexist. Nanostructural features arising upon sequential crystallization are found to have a relevant impact on the mechanical properties. Nanoindentation measurements show that storage modulus and hardness of the Q1 quarterpolymer significantly deviate from those of the stiff PE and PLLA blocks, approaching typical values of compliant PEO and PCL. Results are mainly attributed to the low crystallinity of the PE and PLLA blocks. Moreover, the Q2 copolymer exhibits inferior mechanical properties than Q1, and this can be related to the PE block within Q1 that has thinner crystal lamellae according to its much lower melting point.

18.
ACS Macro Lett ; 10(10): 1287-1294, 2021 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-35549048

RESUMO

Two novel allylic arsonium ylide monomers with a phenyl (steric and electronic effect) group at different positions were synthesized and used in boron-catalyzed polymerization to produce a series of well-defined polymers, poly(2-phenyl-propenylene-co-2-phenyl-propenylidene) (P2-PhAY) and poly(3-phenyl-propenylene-co-3-phenyl-propenylidene) (P3-PhAY), with unusual structures but a controllable molecular weight and relatively low polydispersity. The backbone of these polymers consists of a mixture of C1 (chain grows by one carbon atom at a time) and C3 (chain grows by three carbon atoms at a time) monomeric units, as determined by 1H, 13C, and 1H-13C HSQC 2D NMR. Based on the experimental results and density functional theoretical (DFT) calculations, we were able to propose a mechanism that takes into account not only the steric hindrance, but also the electron effect of the phenyl group. In addition, a nontraditional intrinsic luminescence was observed from the nonconjugated P2-PhAY and P3-PhAY; such unexpected emission is attributed to the formation of C3-unit clusters, as evidenced by ultraviolet-visible and fluorescence spectroscopy.


Assuntos
Boro , Polímeros , Boro/química , Carbono , Catálise , Polimerização , Polímeros/química
19.
Macromolecules ; 53(15): 6682-6689, 2020 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-32904834

RESUMO

Supramolecular block copolymers (PS-DAT-sb-PI-Thy) were synthesized via noncovalent hydrogen bonding between well-defined thymine end-functionalized polyisoprene (PI-Thy) and diaminotriazine (DAT) end-functionalized polystyrene (PS-DAT). Three covalently linked block copolymers were also synthesized for comparison with the noncovalent supramolecular block copolymers. The complementary DAT/Thy interaction resulted in the microphase separation of the supramolecular block copolymer system. Detailed characterization of all functionalized homopolymers and block copolymers was carried out via proton nuclear magnetic resonance (1H NMR) spectroscopy, gel permeation chromatography, matrix-assisted laser desorption/ionization-time of flight mass spectrometry, and differential scanning calorimetry. The self-assembly process of supramolecular block copolymers was evidenced by transmission electron microscopy. Small-angle X-ray scattering was also performed to study the microphase separation of supramolecular and covalently linked block copolymers. Comparison of microphase separation images of supramolecular block copolymers and the corresponding covalently linked analogues reveals differences in d-spacing and microdomain shape.

20.
Macromolecules ; 53(13): 5297-5307, 2020 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-32905284

RESUMO

Various oxirane monomers including alkyl ether or allyl-substituted ones such as 1-butene oxide, 1-hexene oxide, 1-octene oxide, butyl glycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether were anionically copolymerized with CO2 into polycarbonates using onium salts as initiator in the presence of triethylborane. All copolymerizations exhibited a "living" character, and the monomer consumption was monitored by in situ Fourier-transform infrared spectroscopy. The various polycarbonate samples obtained were characterized by 1H NMR, GPC, and differential scanning calorimetry. In a second step, all-polycarbonate triblock copolymers demonstrating elastomeric behavior were obtained in one pot by sequential copolymerization of CO2 with two different epoxides, using a difunctional initiator. 1-Octene oxide was first copolymerized with CO2 to form the central soft poly(octene carbonate) block which was flanked by two external rigid poly(cyclohexene carbonate) blocks obtained through subsequent copolymerization of cyclohexene oxide with CO2. Upon varying the ratio of 1-octene oxide to cyclohexene oxide and their respective ratios to the initiator, three all-polycarbonate triblock samples were prepared with molar masses of about 350 kg/mol and 22, 26, and 29 mol % hard block content, respectively. The resulting triblock copolymers were analyzed using 1H NMR, GPC, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy. All three samples demonstrated typical elastomeric behavior characterized by a high elongation at break and ultimate tensile strength in the same range as those of other natural and synthetic rubbers, in particular those used in applications such as tissue engineering.

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