Chain-growth Copolymerization Research Articles

High‐Density Polyethylene with In‐Chain Photolyzable and Hydrolyzable Groups Enabling Recycling and Degradation

AbstractPolyethylenes endowed with low densities of in‐chain hydrolyzable and photocleavable groups can improve their circularity and potentially reduce their environmental persistency. We show with model polymers derived from acyclic diene metathesis polymerization that the simultaneous presence of both groups has no adverse effect on the polyethylene crystal structure and thermal properties. Post‐polymerization Baeyer–Villiger oxidation of keto‐polyethylenes from non‐alternating catalytic ethylene‐CO chain growth copolymerization yield high molecular weight in‐chain keto‐ester polyethylenes (Mn≈50.000 g mol−1). Oxidation can proceed without chain scission and consequently the desirable materials properties of HDPE are retained. At the same time we demonstrate the suitability of the in‐chain ester groups for chemical recycling by methanolysis, and show that photolytic degradation by extended exposure to simulated sunlight occurs via the keto groups.

High-Density Polyethylene with In-Chain Photolyzable and Hydrolyzable Groups Enabling Recycling and Degradation.

Polyethylenes endowed with low densities of in-chain hydrolyzable and photocleavable groups can improve their circularity and potentially reduce their environmental persistency. We show with model polymers derived from acyclic diene metathesis polymerization that the simultaneous presence of both groups has no adverse effect on the polyethylene crystal structure and thermal properties. Post-polymerization Baeyer-Villiger oxidation of keto-polyethylenes from non-alternating catalytic ethylene-CO chain growth copolymerization yield high molecular weight in-chain keto-ester polyethylenes (Mn ≈50.000 g mol-1 ). Oxidation can proceed without chain scission and consequently the desirable materials properties of HDPE are retained. At the same time we demonstrate the suitability of the in-chain ester groups for chemical recycling by methanolysis, and show that photolytic degradation by extended exposure to simulated sunlight occurs via the keto groups.

Combining Polymerization and Templating toward Hyper-Cross-Linked Poly(propargyl aldehyde)s and Poly(propargyl alcohol)s for Reversible H2O and CO2 Capture and Construction of Porous Chiral Networks.

Two series of hyper-cross-linked microporous polyacetylene networks containing either -[CH=C(CH=O)]- or -[CH=C(CH2OH)]- monomeric units are reported. Networks are prepared by chain-growth copolymerization of acetal-protected propargyl aldehyde and acetal-protected propargyl alcohol with a 1,3,5-triethynylbenzene cross-linker followed by hydrolytic deprotection/detemplating. Deprotection not only liberates reactive CH=O and CH2OH groups in the networks but also modifies the texture of the networks towards higher microporosity and higher specific surface area. The final networks with CH=O and CH2OH groups attached directly to the polyene main chains of the networks have a specific surface area from 400 to 800 m2/g and contain functional groups in a high amount, up to 9.6 mmol/g. The CH=O and CH2OH groups in the networks serve as active centres for the reversible capture of CO2 and water vapour. The water vapour capture capacities of the networks (up to 445 mg/g at 297 K) are among the highest values reported for porous polymers, making these materials promising for cyclic water harvesting from the air. Covalent modification of the networks with (R)-(+)-3-aminopyrrolidine and (S)-(+)-2-methylbutyric acid enables the preparation of porous chiral networks and shows networks with CH=O and CH2OH groups as reactive supports suitable for the anchoring of various functional molecules.

Porous polymer networks cross-linked by novel copper Schiff base complex: From synthesis to catalytic activity

A new ethynylated Schiff base complex, [Cu(SALANI)2], in which two N-salicylidene(3-ethynylaniline) (SALANI) ligands coordinated one Cu2+ ion, was prepared and characterized by single-crystal X-ray diffraction, FTIR and 1H NMR spectroscopy. The 1H NMR spectra were obtained and interpreted (with the help of DFT calculation) despite the paramagnetic character of the [Cu(SALANI)2] complex. Chain-growth copolymerization of [Cu(SALANI)2] with 4,4′-diethynylbiphenyl and 1,4-diethynylbenzene provided polyacetylene-type micro/mesoporous organometallic networks with [Cu(N-salicylideneaniline)2] segments as network knots. Networks of this type were also prepared by postpolymerization metalation of polyacetylene networks containing N-salicylideneaniline segments as pendant groups. Postpolymerization metalation (leading to further cross-linking) enabled to transform nonporous parent networks into organometallic networks with permanent porosity. The new porous organometallic networks showed a specific surface area from 400 to 700 m2/g and a Cu2+ content of about 6 wt%. The networks prepared by both prepolymerization and postpolymerization metalation were active as heterogeneous catalysts of oxidation of linalool to linalool oxide.

Cascade Alternating Metathesis Cyclopolymerization of Diynes and Dihydrofuran.

Ruthenium alkoxymethylidene complexes have recently come into view as competent species for metathesis copolymerization reactions when coupled with appropriate comonomer targets. Here, we explore the ability of Fischer-type carbenes to participate in cascade alternating metathesis cyclopolymerization (CAMC) through facile terminal alkyne addition. The combination of diyne monomers and an equal feed ratio of low-strain dihydrofuran leads to a controlled chain-growth copolymerization with high degrees of alternation (>97% alternating diads) and produces degradable polymer materials with low dispersities and targetable molecular weights. When combined with enyne monomers, this method is amenable to the synthesis of alternating diblock copolymers that can be fully degraded to short oligomer fragments under aqueous acidic conditions. This work furthers the potential for the generation of functional metathesis materials via Fischer-type ruthenium alkylidenes.

Alternating Chain Growth Copolymerization of Isothiocyanates and Epoxides

A class of heteroatom polymers through anionic chain growth copolymerization of epoxides and isothiocyanates has been successfully obtained under mild conditions via initiation by a simple salt of ...

Quasi-Living Copolymerization of Aryl Isocyanates and Epoxides.

Nontraditional polyurethane (PU) has been successfully synthesized by anionic copolymerization of some typical aryl isocyanates and epoxides with ammonium halide onium salt (Lewis base) as the initiator and triisobutylaluminum (Lewis acid) as the activator and the synergistic coordinator. In contrast to the traditional step-growth approach, this chain-growth copolymerization can maintain the anionic propagation site and exhibit some living features with a high activity, by which the copolymers synthesized have narrow molecular weight distributions and discrete end groups. The copolymer is primarily constituted by a urethane linkage, and the byproducts of isocyanurate trimer and oxazolidinone can be effectively suppressed as the polymerization proceeds. Density functional theory (DFT) calculations were also performed to support the proposed reaction mechanism.

Alternating Cascade Metathesis Polymerization of Enynes and Cyclic Enol Ethers with Active Ruthenium Fischer Carbenes.

Ruthenium alkoxymethylidene complexes have rarely been demonstrated as active species in metathesis reactions and are frequently regarded as inert. Herein, we highlight the ability of these Fischer-type carbenes to participate in cascade alternating ring-opening metathesis polymerization through their efficient alkyne addition reactions. When enyne monomers are combined with low-strain cyclic vinyl ethers, a controlled chain-growth copolymerization occurs that exhibits high degrees of alternation (>90% alternating diads) and produces degradable poly(vinyl ether) materials with low dispersities and targetable molecular weights. This new method is amenable to the synthesis of alternating diblock polymers that can be degraded to small-molecule fragments under aqueous acidic conditions. This work furthers the potential of Fischer-type ruthenium alkylidenes in polymerization strategies and presents new avenues for the generation of functional metathesis materials.

Modeling of the Penultimate Unit Effect in Chain-Growth Copolymerizations

The present work addresses the modeling and simulation of the addition of copolymerizations of styrene and methyl methacrylate in batch mode, and the formation of tailored vinyl acetate/acrylic acid copolymers is evaluated through stochastic optimization procedures based on the Monte Carlo method. A kinetic model of the free-radical reaction was proposed in order to predict the behavior of the reaction system taking into consideration the presence of the penultimate unit effect. The profiles of conversion and copolymer composition were also evaluated considering the effect of the medium viscosity (kinetic phenomena related to gel and glass effects) on the reaction performance. It was shown that the proposed model for chain-growth copolymerization is able to describe strong nonlinear behaviors such as autoacceleration of the polymerization and drift of copolymer composition. It was also shown that copolymers with homogeneous composition can be successfully synthesized through manipulation of the monomer feed flow rate based on a stochastic optimization procedure.

Programming chain-growth copolymerization of DNA hairpin tiles for in-vitro hierarchical supramolecular organization

Formation of biological filaments via intracellular supramolecular polymerization of proteins or protein/nucleic acid complexes is under programmable and spatiotemporal control to maintain cellular and genomic integrity. Here we devise a bioinspired, catassembly-like isothermal chain-growth approach to copolymerize DNA hairpin tiles (DHTs) into nanofilaments with desirable composition, chain length and function. By designing metastable DNA hairpins with shape-defining intramolecular hydrogen bonds, we generate two types of DHT monomers for copolymerization with high cooperativity and low dispersity indexes. Quantitative single-molecule dissection methods reveal that catalytic opening of a DHT motif harbouring a toehold triggers successive branch migration, which autonomously propagates to form copolymers with alternate tile units. We find that these shape-defined supramolecular nanostructures become substrates for efficient endocytosis by living mammalian cells in a stiffness-dependent manner. Hence, this catassembly-like in-vitro reconstruction approach provides clues for understanding structure-function relationship of biological filaments under physiological and pathological conditions.

Analytical and advanced kinetic models for characterization of chain-growth copolymerization: the state-of-the-art

A detailed overview is given on the currently developed analytical and advanced kinetic models to calculate the main bulk/solution chain-growth copolymerization characteristics.

Chain-growth copolymerization of functionalized ethynylarenes with 1,4-diethynylbenzene and 4,4′-diethynylbiphenyl into conjugated porous networks

We report the synthesis of conjugated highly cross-linked polyacetylene-type networks with a high content of functional groups (–CH2OH, –NO2, –Ph2N, content up to 3.9mmol/g) via a chain-growth copolymerization of either 1,4-diethynylbenzene or 4,4′-diethynylbiphenyl with functionalized mono- and diethynylbenzenes. The backbone of the networks consists of substituted polyene main chains that are cross-linked by arylene links. The optimized combinations of comonomers in the feed provide functionalized networks with a Brunauer–Emmett–Teller specific surface area up to 667m2/g and enhanced affinity for CO2 adsorption (compared to the non-functionalized hydrocarbon networks of the same type). The dependence of the specific surface area of the networks on the size and architecture of the comonomers used for the synthesis is discussed in the paper. The reported networks can be classified into the group of conjugated microporous polymers (CMPs). Contrary to the CMPs synthesized by step-growth couplings, significantly lower average comonomer functionality in the feed (f=1.5–2.0) is sufficient for the high specific surface area to be achieved in the reported polyacetylene-type CMPs.

Functional dye as a comonomer in a water‐soluble polymer

ABSTRACTIn many applications, a functional additive is blended into a polymer matrix to enhance its properties. However, when the polymer and functional additive are applied to a surface, the functional molecule may be easily lost. In favorable cases, it may be possible to incorporate the additive directly into the polymer as a comonomer. In this study, a functionalized polymer has been obtained through the combination of linking a photodynamic, antimicrobial dye, Rose Bengal, to vinyl benzyl chloride via etherification and then polymerizing this into a water‐soluble polymer using chain growth copolymerization. Characterization of the efficiency of synthesis, solubility of the final product, and singlet oxygen production rate has been performed. Dialysis was used to determine the extent of incorporation of the dye into the polymer. The chemical structure of the intermediate produced through etherification has been verified. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1594–1599

Synthesis of Hyperbranched Poly(phenylacetylene)s Containing Pendant Alkyne Groups by One-Pot Pd-Catalyzed Copolymerization of Phenylacetylene with Diynes

We report in this article the convenient synthesis of a class of hyperbranched poly(phenylacetylene)s (HBPPAs) containing various branching densities and different contents of pendant alkyne groups through one-pot chain-growth copolymerization of phenylacetylene (PA) with a diyne comonomer (1,3- or 1,4-diethynylbenzene (DEB)). The polymerization was facilitated with the use of an in situ generated cationic diphosphine-ligated Pd(II) catalyst system. Serving effectively as difunctional cross-linker in the polymerization, the diyne comonomer first undergoes monoinsertion to render pendant alkyne groups, which can be further enchained to generate branching structures. A systematic investigation has been undertaken to study the effects of various polymerization parameters, including diyne/PA feed ratio, diyne type, temperature, and solvent, on the polymerization, polymer structure and topology. With either 1,3- or 1,4-DEB, a convenient tuning of polymer topology from linear to hyperbranched can be achieved by...

A new general approach to determine more accurate comonomer reactivity ratios in controlled/living radical copolymerization systems

In controlled/living radical copolymerization (atom transfer radical copolymerization in this study) and in any other living chain-growth copolymerization, the possible preferential addition of one of the comonomers onto the (macro)initiator-derived (macro)radical can affect the copolymer composition, especially at low conversion; this results in inaccurate comonomer reactivity ratio estimation by the classic approach. A new general approach is introduced in this article, which allowed us to exclude the influence of the possible preferential addition of one of the comonomers onto the (macro)initiator-derived (macro)radical on the copolymer composition at any conversion. According to this approach, copolymer chain grown during time t (t ≠ 0) is considered to be, in fact, the macroinitiator terminated with one of the comonomers under study, which will further grow during the time interval Δt′ = t′ − t [where any reaction time t′ is considered to be grater than reaction time t, i.e. t′ > t] from a comonomer mixture with composition of f(t) [where f(t) is the molar ratio of comonomer i to comonomer j in the comonomer mixture] at time t. In such a situation, it is possible to obtain individual comonomer conversions [xi(Δt′) and xj(Δt′)], the overall comonomer conversion [xov(Δt′)], and the cumulative average copolymer composition for the copolymer formed during Δt′, from which more accurate comonomer reactivity ratios can be calculated by the various low- or high-conversion methods, depending on the overall comonomer conversion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Metal-Catalyzed Simultaneous Chain- and Step-Growth Radical Polymerization: Marriage of Vinyl Polymers and Polyesters

All polymerization reactions are categorized into two large different families, chain- and step-growth polymerizations, which are typically incompatible. Here, we report the simultaneous chain- and step-growth polymerization via the metal-catalyzed radical copolymerization of conjugated vinyl monomers and designed monomers possessing unconjugated C horizontal lineC and active C-Cl bonds. Especially, almost ideal linear random copolymers containing both vinyl polymer and polyester units in a single polymer chain were formed by the CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine- or RuCp*Cl(PPh(3))(2)-catalyzed copolymerization of methyl acrylate (MA) for the chain-growth polymerization and 3-butenyl 2-chloropropionate (1) for the step-growth polymerization. In contrast, other transition metal catalysts, such as CuCl with tris[2-(dimethylamino)ethyl]amine or N,N,N',N'',N''-pentamethyldiethylenetriamine and FeCl(2)/PnBu(3), resulted in branched structures via the concomitant chain-growth copolymerization of 1 with MA. The polymerization mechanism was studied in detail by NMR and MALDI-TOF-MS analyses of the polymerizations as well as the model reactions. Furthermore, a series of copolymers changing from random to multiblock polymer structures were obtained by varying the feed ratios of the two monomers. These copolymers can be easily degraded into lower molecular weight oligomers or polymers via methanolysis of the ester-linkages in the main chain using sodium carbonate.

Copolymerization kinetics of styrene/vinyl‐ester systms: Low temperature reactions

AbstractVinyl‐ester (VE), synthesized by the addition reaction of methacrylic acid and diglycidyl ether of bis‐phenol A (DGEBA) epoxy, and styrene react via bulk free radical chain growth copolymerization to form a crosslinked network polymer. Vital clues regarding the development and the structure of the network were obtained from the study of copolymerization kinetics of styrene/VE systems. Fourier transform infrared (FTIR) spectroscopy was used to obtain the individual fraction conversion rates of both the monomers. The conversion versus time data for both styrene and VE was fit to an autocatalytic kinetic model. The autocatalytic model was found to adequately replicate the kinetic data over the entire life of cure. In this investigation, the effects of styrene concentration, temperature, catalyst concentration, and initiator concentration on cure kinetics of styrene/VE systems were studied. The conversion profiles of both styrene and VE were used to obtain the reactivity ratios of the two monomers. The reactivity ratios were evaluated to be close to zero, suggesting that initially alternating copolymerization is favored over homopolymerization. The cure behavior of vinyl‐ester resins is affected not only by the chemical reactivity of the monomers toward the free radicals, but also by diffusion effects, phase separation, and microgel formation. The interplay of these factors controls the kinetics of cure, thereby affecting the physical and chemical properties of the resulting polymer.

Representation of Chain-Growth Copolymerization in Terms of Active Centers

Abstract The nearest-neighbor, chain-growth copolymerization equation is expressed in terms of active center concentrations and active center reactivity ratios, Ri = kii/kji. Alternate but equivalent derivations of the conventional version and the new version of the copolymerization equation are presented and discussed. Some active center reactivity ratios are calculated from data previously reported, and contrasting trends between these and monomer reactivity ratios are found. The Alfrey-Price scheme for predicting monomer reactivity ratios is adapted to the prediction of active center reactivity ratios.