Multicomponent Copolymers Research Articles

Color-tunable fluorescence and ultralong organic room temperature phosphorescence from multicomponent copolymers

Materials with color-tunable photoluminescence (PL) have attracted dramatically increasing interest in recent years, especially the tuning of both fluorescence (FL) and ultra-long organic room temperature phosphorescence (UOP). Herein, a series of polymer films are successfully fabricated by in situ copolymerization of carbazole derivatives, lanthanide complex, and acrylamide (AM). With a long lifetime of 2.82 s and a high quantum yield of 21.40%, these copolymers exhibit not only color-tunable FL from violet-red to blue, but also multicolor UOP scope from blue to chartreuse when the excitation wavelength is changed. Moreover, a nearly-white phosphorescence can also be observed by adjusting the excitation wavelength. Multiple information patterns with color-tunable FL and UOP emissions are captured, exhibiting promising potential in the information encryption and anti-counterfeiting fields.

Synthesis and Performance Testing of Maleic Anhydride-Ene Monomers Multicomponent Co-Polymers as Pour Point Depressant for Crude Oil.

To address the issue of pipeline blockage caused by the formation of waxy deposits inside pipelines, hindering the flow of petroleum in the Shengli oilfield, eight new-style polyacrylic acid pour point depressants (PPD) for Shengli crude oil were prepared by maleic anhydride and ene monomers with different polar and aromatic pendant chains. The synthesized Pour Point Depressants were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and polarizing optical microscopy (POM). The results were promising and demonstrated that any type of pour point depressant exhibited excellent performance on high-pour-point crude oil. The reduction in pour-point after additive addition was largely dependent on the polymer structure. Notably, polymers containing long alkyl side chains and aromatic units displayed the most impressive performance, capable of depressing the pour point by 12 °C.

Existence and stability of azeotropes in the terminal model of multicomponent copolymerization

AbstractA simple numerical algorithm for calculating the azeotropic composition of multicomponent copolymers (if such a composition exists) is presented. The method is based on regular Markov chains in the frame of the terminal model of irreversible chain propagation in chain‐growth copolymerization. It requires as few calculations as just solving two systems of linear equations. The stability of the azeotropic composition in a batch reactor is discussed. A numerical procedure that can distinguish between a stable and an unstable azeotropic composition is proposed. © 2021 Society of Industrial Chemistry.

Bridging from the Sequence to Architecture: Graft Copolymers Engineering via Successive Latent Monomer and Grafting‐from Strategies†

Main observation and conclusionThe on‐demand building copolymer structures, from sequence to architecture, is crucial in understanding the relation between polymer structure and property, meanwhile motivating the innovation of polymer hierarchy. However, the challenge is conspicuous for complicated polymer structures from inherently intricate polymerization. In this work, copolymers with tailored grafting density and distributions were achieved using successive latent monomer and grafting‐from strategies. The hydroxyl group functionalized furan/maleimide adduct (FMOH) was selected as the latent monomer for RAFT polymerization of an array of copolymers with tailored localization of hydroxyl group along the main chain. The hydroxyl group further initiated the ring opening polymerization (ROP) of L‐lactide or ε‐caprolactone, resulting in a library of multicomponent copolymers via grafting‐from strategy. The initiating efficiency reached to ~100% with variable molecular weight (21300—58600 Da) and narrow distributions (ÐM < 1.25), indicating that such graft copolymers possessed controlled density and distribution of side chains as its linear template. The investigation on thermal properties of the well‐defined graft copolymers implied that the precise tailoring over copolymer structures at the molecule level could lead to tunable chemical/physical properties. This work bridged polymer from sequence to architecture, unveiled a new method in creating graft copolymers with programmable structures and provided the insight into the structure/property relationship.

Synthesis and properties of penta-responsive ABC star quaterpolymers

The controlled synthesis of smart multicomponent copolymers can afford new insight into structure-property correlations. Given the lack of CO2 and O2 dual-gas-responsive star polymers, this study is focused on the facile synthesis and properties of multiresponsive ABC star quaterpolymers. The “core-first” strategy was adopted to generate P(ATL-co-NIPAM)-arm-PCL-arm-PDPA stars, followed by tandem amine-thiol-ene conjugation to construct the desired stars bearing O2-/oxidation-responsive and hydrogen bond-switchable Y junctions. Upon composition change, pH switching, gas bubbling and oxidation, the copolymer solution tended to show different cloud points. Furthermore, the sizes and morphologies of copolymer assemblies were strongly dependent on chemical composition and thermal, pH, CO2, O2 and oxidative stimuli, and abundant morphologies such as large compound micelles, hyperbranched micelles, disk-like micelles, spindle-like micelles, ellipsoidal micelles, and multicompartment vesicles could be formed under distinct conditions. Our study affords a promising yet straightforward approach to construct multicomponent miktoarm star polymer, and the composition-/stimuli-dependent thermoresponsive and aggregation behaviors of these polymers pave the way for multipurpose applications. By virtue of “core first” method, ABC star quaterpolymers were controllably synthesized by combination of controlled polymerization and thiolactone chemistry. The miktoarm stars were responsive to temperature, pH, CO2, O2 and oxidation, and thus the phase transition temperature, size and morphology of copolymer assemblies could be efficiently tuned via adopting a single stimulus or combined stimuli.

A Novel Approach for the Synthesis of Thermo‐Responsive Co‐Polyesters Incorporating Reversible Diels–Alder Adducts

AbstractThe proof of concept for a new copolymerization approach taking advantage of the thermally reversible aptitude of the furan/maleimide Diels–Alder (DA) adducts is reported here. A new monomer bearing two carboxylic acids as end‐groups and a Diels–Alder adduct within its structure is synthesized using benign and mild reaction conditions. Two polyesters are then fabricated from the DA‐diacid and 1,6‐hexanediol and 1,4‐benzenedimethanol, respectively, and characterized by 1H‐NMR, GPC, DSC, and TGA. Kinetic studies of these polyesters, performed by 1H‐NMR spectroscopy at variable temperatures, establish the appropriate conditions for their controlled depolymerization, through the retro Diels–Alder reaction (rDA), and their re‐construction through the DA reaction, showing moreover the reproducibility of this rDA/DA cycle. Finally, by exploiting this peculiar feature, a copolyester is successfully synthesized from the concomitant treatment of the two homopolymers, demonstrating the effectiveness of the method. The present approach provides a new method for the fabrication of multicomponent copolymers based on the DA/rDA strategy that is extendable to a variety of other polycondensation materials, such as polyesters, polyamides, polyurethanes, and epoxies, allowing the establishment of a library of novel architectures through this one‐pot approach.

Self-Consistent Field Theory within Hildebrand Approximation: Microphase Separation in Gradient Copolymers

To provide a faster calculation of the block copolymer phase diagrams a simplified version of the self-consistent field theory (SCFT) is proposed. Multi-component block copolymers with interactions between repeated units described by the -parameters satisfying the Hildebrand conditions are studied. This case is shown to correspond to a degeneration within the framework of the general SCFT approach. Remarkably, the degenerated thus multi-component block copolymers admit two-component only SCFT description. The procedure presented is applied to gradient copolymers considered as a limiting case of multi-component copolymers obeying Hildebrand conditions, the lengths of the blocks vanishing and the number of different kinds of repeated monomers tending to infinity. Finally, a melt of symmetric triblock copolymers blurred into a gradient copolymer is studied and corresponding phase diagrams are calculated.

Catalytic Aquathermolysis of Heavy Oil With Oil-soluble Multicomponent Acrylic Copolymers Combined With Cu2+

A kind of oil-soluble multicomponent acrylic copolymer combined with Cu2+ was synthesized and used for catalytic aquathermolysis of heavy oil. This work showed this copper-bearing copolymer led to 84.52% viscosity reduction for the Lukeqin heavy oil at 513.15 K, and converted 10.01% of the resin fraction and 2.85% of the asphaltene fraction into light oil content. After aquathermolysis with this catalyst, some parts of the long-chain saturated hydrocarbons were broken into short-chain ones, and the aromaticity and aromaticity condensation of the resin and asphaltene decreased.

Synthesis of multifunctional ABC stars with a reduction-labile arm by consecutive ROP, RAFT and ATRP processes

This study aims at versatile synthesis of 3-arm ABC-type (A=poly( e -caprolactone), PCL; B=poly( N -isopropylacrylamide), PNIPAM; C=poly( tert -butyl acrylate), P t BA, or poly(acrylic acid), PAA) miktoarm star copolymers with a reducible disulfide linkage. Using 2-((2-((2-hydroxymethyl-2-((2-bromo-2-methyl)propionyloxy)methyl)propionyloxy)ethyl)disulfanyl)ethyl 4-cyano-4-(phenylcarbonothioylthio)pentanoate (HBCP) as a heterotrifunctional initiator, consecutive ring-opening polymerization (ROP) of e -caprolactone (CL), reversible addition-fragmentation chain transfer (RAFT) polymerization of N -isopropy-lacrylamide (NIPAM) and atom transfer radical polymerization (ATRP) of tert -butyl acrylate ( t BA) afforded ABC1 star, and followed by a subsequent hydrolysis to give ABC2 star. 1H nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC) analyses revealed the desired stars and their precursors had well-controlled molecular weight and relatively low polydispersity (PDI￡1.12). As confirmed by GPC analysis, the disulfide linkage in ABC1 star could be efficiently cleaved upon reductive stimulus, during which the topology was converted from star terpolymer to mixtures of homopolymer (B) and diblock copolymer (AC1). In addition to acting as nanocarriers for stimuli-triggered drug delivery systems, ABC stars with terminal bromide, dithiobenzoate and hydroxyl functionalities are expected to form other reduction-cleavable multicomponent copolymers such as (BC- graft -A) m and dendritic graft copolymers via postpolymerization modification. Our research affords a straightforward “core-first” method to construct multifunctional star terpolymers with stimuli-responsive arms and reduction-labile linkage.

The relationship between oxygen permeability and phase separation morphology of the multicomponent silicone hydrogels.

In this article, the multicomponent copolymers were prepared by the copolymerization of two hydrophobic silicon-containing monomers bis(trimethylsilyloxy) methylsilylpropyl glycerol methacrylate (SiMA) and tris(trimethylsiloxy)-3-methacryloxypropylsilane (TRIS) with three hydrophilic monomers 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, and N,N-dimethyl acrylamide. The copolymers were hydrated to form transparent silicone hydrogels. The oxygen permeability coefficients (Dk) of hydrogels were measured, and their relationships with the equilibrium water contents (EWC) and the types and contents of silicon containing monomers as well as the phase separation structures of silicone hydrogels were analyzed in detail. The results showed that the EWC decreased as the increase of SiMA content. The relationship between Dk and SiMA content, as well as that between Dk and EWC, showed inverted bell curve distributions, which meant two main factors, i.e., silicon-oxygen bond in silicone and water in hydrogel, contributed to oxygen permeation and followed a mutual inhibition competition mechanism. The internal morphologies of the hydrogels were observed by transmission electron microscope, and the results showed that the hydrogels presented two different phase separation structures depending on the types of the silicon-containing monomers. The silicone phase in SiMA containing hydrogel presented to be a granular texture, while the silicone phase in TRIS containing hydrogel formed a fibrous texture which resulted in a higher Dk value. These results could help to design a silicone hydrogel with better properties and wider application.

Synthesis and white electroluminescent properties of multicomponent copolymers containing polyfluorene, oligo(phenylenevinylene), and porphyrin derivatives

AbstractTwo novel multicomponent copolymers (P1 and P2) containing polyfluorene (PF), oligo(phenylenevinylene) (OPV), and porphyrin (Por) derivatives were synthesized according to the Suzuki polymerization method. The structures, optical, and electrochemical properties of the two model compounds (OPV and Por) and multicomponent copolymers were characterized by 1H NMR, FTIR, elemental analysis, UV–vis spectroscopy, photoluminescence, and cyclic voltammetry, respectively. Both of the copolymers exhibit thermotropic liquid crystalline properties and represent the characteristic Schlieren textures in a wide temperature range. Electroluminescence spectra of these copolymers exhibit broadband emissions covering the entire visible region from 400 to 700 nm. The single layer polymer light emitting diodes device based on P2 with a configuration of indium tin oxide/poly(ethylenedioxythiophene):poly(styrenesulfonic acid)/polymers/Ca/Al emits white light with the Commission Internationale de l′Eclairage chromaticity coordinates of (0.29, 0.30), maximum brightness of 443 cd/m2. The white‐light‐emitting devices based on the novel multicomponent copolymers exhibit low turn‐on voltage, and good color stability at different driving voltages as well. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5291–5303, 2009

Proton-conducting membranes based on multicomponent copolymers

Preparation of proton-conducting polymeric composites via copolymerization of multicomponent monomeric systems using the interpenetrating polymer network preparation procedure is studied. The products are characterized by the protonic conductivity, water-retaining capacity, and mechanical properties. The approach used allows fabrication of membranes with a reasonable protonic conductivity over the temperature range 20–90°C. A possibility of modification of the proton-conducting materials with small additions of hydrolyzable organosilicon comonomers is analyzed. The structure of the resulting systems is examined by small-angle neutron scattering.

Synthesis of novel macromonomeric peroxy initiators of styrene with the cationic copolymerization and the quantum chemically investigation of the initiation system effects

AbstractCationic polymerization of styrene (S) was performed with peroxy initiators synthesized from bis(4,4′‐bromomethyl benzoyl peroxide) (BBP) or bromomethyl benzoyl t‐butyl peroxy ester (t‐BuBP) and AgSbF6 or ZnCl2 system at 0 and −10°C to obtain macromonomeric peroxy initiators (poly‐S initiators). Kinetic studies were accomplished for poly‐S initiators. Poly(styrene‐block‐methyl methacrylate) block copolymers [poly(S‐b‐MMA)] were synthesized by bulk polymerization of methyl methacrylate (MMA) with poly‐S initiators. The quantum chemical calculations for the initiating systems of the cationic polymerization of S and poly(S‐b‐MMA) block copolymers were achieved using Hyperchem 7.5 program. The optimized geometries of the polymers were investigated with the quantum chemical calculations. Poly(S‐b‐MMA) block copolymers containing undecomposed peroxide groups were used to initiate thermal copolymerization of acrylic acid (AA) to obtain crosslinked poly(S‐b‐MMA‐b‐AA) multicomponent copolymers. The crosslinked multicomponent copolymers were investigated by sol–gel analysis. Swelling ratio values of the crosslinked multicomponent copolymers in CHCl3 were calculated. Poly‐S initiators having undecomposed peroxygen groups were used for graft copolymerization of polybutadien (PBd) to obtain crosslinked poly(S‐graft‐polybutadien) graft copolymers [poly(S‐g‐PBd)]. The characterizations of the polymers were achieved by FTIR, 1H‐NMR, GPC, SEM, and DSC techniques. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 348–357, 2006

Chemical composition distribution of multicomponent copolymer chains

AbstractProbability theory was used to model the microstructure of copolymer chains. Specifically, we derived analytical expressions to describe the chemical composition distribution of multicomponent random copolymers and the longest monomer sequence length distribution of binary copolymers. The results agree with Stockmayer's distribution for binary copolymers and with Monte Carlo simulations for multicomponent copolymers.

高分子科学最近の進歩 多成分ブロック共重合体の相挙動および構造形成

高分子科学最近の進歩 多成分ブロック共重合体の相挙動および構造形成

Chemical Composition Distribution of Multicomponent Copolymers

AbstractThe number and weight chemical composition distributions in random terpolymers were derived using a statistical approach. The solution was then generalized to comprise higher multicomponent copolymers. The analytical solution was verified with Monte Carlo simulations and by considering limiting cases. Chemical composition distributions for fractions of random terpolymers of various kinetic chain lengths were also investigated. In a similar way to the results for binary copolymers described by Stockmayer's distribution, broadening of the distribution is observed for low‐molecular‐weight chains.Comparison of chemical composition distributions from Stockmayer (Equation (3)) and statistical approach (Equation (4)).imageComparison of chemical composition distributions from Stockmayer (Equation (3)) and statistical approach (Equation (4)).

Initiation system effects in the cationic copolymerization of tetrahydrofuran (THF)

Macromonomeric peroxy initiator, poly tetrahydrofuran (poly-THF=inimer) were synthesized via cationic polymerization of THF by the mono- (t-BuBP) and tetra-bromo methyl benzoyl peroxides (BDBP)/ZnCl 2 initiating system. The macromonomers were characterized by 'H-NMR, IR, and GPC techniques. Methyl methacrylate (MMA) polymerization initiated by poly-THF inimers at 80°C and different times in bulk gave crosslinked poly-THF-b-polymethyl methacrylate block copolymers. Swelling ratios of the crosslinked block copolymers obtained by taking in same amounts of poly-THF inimer and MMA monomer in CHCl 3 were decreased versus time. It was compared the results obtained from t-BuBP-, BDBP-ZnCl 2 initiating systems with t-BuBP-, BDBP-AgSbF 6 initiating systems for THF monomer. Poly(THF-b-MMA) crosslinked block copolymers containing undecomposed peroxide groups initiated the thermal polymerization of styrene , S, were used to obtain poly(THF-b-MMA-b-S) crosslinked multicomponent copolymers at 90°C. The crosslinked multi component copolymers were investigated sol-gel analysis and swelling ratios in CHCl 3 . Active poly(THF-b-MMA) having peroxygen group were used in the free radical coupling reaction of poly butadien (Poly Bd). Poly(THF-b-MMA)-polybutadien crosslinked blend soluble graft copolymers were obtained.

Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide

AbstractMultiblock copolymers of ethylene oxide, with four and five different blocks, were synthesized by the sequential anionic polymerization of styrene, isoprene, 2‐vinyl pyridine, t‐butyl methacrylate, and ethylene oxide with benzyl potassium as an initiator. The monomer sequence was based on the relative nucleophilicity of the active centers. Characterization of the multiblock copolymers by size exclusion chromatography (with refractive‐index and UV detectors), membrane osmometry, and NMR spectroscopy confirmed that benzyl potassium is an efficient initiator for the synthesis of well‐defined multiblock multicomponent copolymers of ethylene oxide. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2166–2170, 2002

Enzymatic synthesis of multi-component copolymers and their structural characterization.

The use of enzymes in synthetic applications has increased dramatically in the recent years and the field of polymer science is part of this trend. Synthesis of a variety of polymers using lipase catalyzed (Candida antarctica) polymerization reactions has led to a variety of new materials with interesting properties in our laboratories. This paper describes the synthesis of multi-component polyesters and mixed polymers having polyester and polyamide linkages under solvent-less conditions using Candida antarctica lipase B. The effect of a third component, i.e. a series of 1,omega-alkanediols (1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol and 1,16-hexadecanediol) on the copolymerization reaction of dimethyl 5-hydroxyisophthalate with poly(ethylene glycol 600) has been studied and the mechanism for the incorporation of the third component is proposed. We have also studied the effect of different functional groups during terpolymerization reaction of dimethyl 5-hydroxyisophthalate with poly(ethylene glycol) by adding a third component having different functionalities (1,6-hexanediol, 1,6-hexanediamine or 1,6-hexanedithiol) and compared the effect of hydroxyl, amine and thiol groups on the polymerization reactions.

Structural Characterization of Multicomponent Copolyesters by Mass Spectrometry

The structural characterization and composition of five random copolyesters, originating from 1,4-butanediol and mixtures of succinic, adipic, sebacic, and terephthalic acids, were obtained by analysis of their fast atom bombardment (FAB) and their matrix-assisted laser desorption ionization (MALDI) mass spectra. Multicomponent condensation copolymers may sometimes prove difficult to characterize by conventional techniques, whereas mass spectrometry is able to handle them. Once the choice between Bernoullian or Markoffian models has been made, the determination of copolymer composition, number-average sequence length, and related quantities can be achieved by applying well-defined analytical equations. The theoretical mass spectra of multicomponent copolymers are remarkably simple, and the number of peaks appearing in each copolymer mass spectrum is easily predictable. Different kinds of spectral fitting algorithms may help in the actual computations, and it has been shown that the apparent complexity of mass spectra of copolymers is due to the presence of mass series bearing different end groups. By selecting a single mass series, one obtains an experimental spectrum immediately comparable to the theoretical one. Detailed examples, together with a discussion on the reliability of results, are given to apply the computation procedures and to gain proper understanding of the concepts involved.