Monomer Conversion Research Articles

Inflammation-Responsive Micellar Nanoparticles from Degradable Polyphosphoramidates for Targeted Delivery to Myocardial Infarction.

Nanoparticles that undergo a localized morphology change to target areas of inflammation have been previously developed but are limited by their lack of biodegradability. In this paper, we describe a low-ring-strain cyclic olefin monomer, 1,3-dimethyl-2-phenoxy-1,3,4,7-tetrahydro-1,3,2-diazaphosphepine 2-oxide (MePTDO), that rapidly polymerizes via ring-opening metathesis polymerization at room temperature to generate well-defined degradable polyphosphoramidates with high monomer conversion (>84%). Efficient MePTDO copolymerizations with norbornene-based monomers are demonstrated, including a norbornenyl monomer functionalized with a peptide substrate for inflammation-associated matrix metalloproteinases (MMPs). The resulting amphiphilic peptide brush copolymers self-assembled in aqueous solution to generate micellar nanoparticles (30 nm in diameter) which exhibit excellent cyto- and hemocompatibility and undergo MMP-induced assembly into micron-scale aggregates. As MMPs are upregulated in the heart postmyocardial infarction (MI), the MMP-responsive micelles were applied to target and accumulate in the infarcted heart following intravenous administration in a rat model of MI. These particles displayed a distinct biodistribution and clearance pattern in comparison to nondegradable analogues. Specifically, accumulation at the site of MI competed with elimination predominantly through the kidney rather than the liver. Together, these results suggest this as a promising new biodegradable platform for inflammation targeted delivery.

Kinetic studies on the radical ring‐opening polymerization of 2‐methylene‐1,3,6‐trioxocane

AbstractRadical ring‐opening polymerization (RROP) of cyclic ketene acetals allows for the synthesis of functional and biodegradable polyesters. To gain a better understanding of RROP, kinetic studies of this reaction method are thus essential but still rare. In here we conducted kinetic experiments on RROP of 2‐methylene‐1,3,6‐trioxocan (MTC) for the first time. In line with earlier findings, the kinetic behavior could be distributed into a chain growth, stationary and step growth behavior probably caused by dominating branching and recombination reactions impacting the polymerization with increasing conversion. The impact of reaction conditions, such as monomer concentration, reaction temperature and source of energy input (Oil bath, microwave, UV light) were varied systematically. All of these factors were studied towards their influence on polymerization rate constant, density of branches (DB), polymer dispersity and molar mass. While each of these factors were impacted by the reaction conditions, the DB was only depending on monomer conversion. Elution fractionation of PMTC samples with high conversion proved decreasing DB with increasing molar mass. Altogether, this study gives a holistic insight into the kinetics of MTC under various means of free RROP, paving the way for developing a more hydrophilic polyester with adjustable DB and molecular weight.

A fast, efficient, inexpensive and green way to outdoor photopolymerization

A series of environmentally friendly photoinitiating systems operating under mild conditions of visible light (Vis-PIs) were tested for vinyl polymerization using sunlight as a free of charge radiation source. These Vis-PIs based on water soluble xanthene dyes showed good performances after deaerating with an inert gas, obtaining colorless polymers with gravimetric yields up to 80–90% after short irradiation times (2–15 min). Aqueous solutions of the materials were highly viscous and viscosimetric measurements yielded molecular weights up to 106. Surprisingly, the evaluated Vis-PIs also worked successfully under ambient air atmosphere, obtaining similar polymer yields in the same irradiation times. Photolysis experiments and transient spectroscopy were used to shed light on the mechanism of the process, allowing both triplets and radicals formation of the dyes to be identified even in the presence of air. The kinetics of photopolymerization was studied following the monomer conversion at several irradiation times by FTIR. The results were interpreted based on kinetic data collected as competitive quenching mechanisms between the co-initiator and oxygen for the excited dyes. The present report represents a breakthrough in the search for fast, efficient and inexpensive Vis-PIs with low ecological impact, which can be very useful in outdoor coating applications among others.

Sulfur-rich polymers from elemental sulfur-derived polysulfide salts and bisepoxides

The obtainment of polymeric materials out of green, renewable, or sustainable building blocks is an ongoing research area. Due to its large-scale derivation as a by-product of the petroleum industry and natural abundance, elemental sulfur is a prospect to ensure the sustainable production of diverse functional polymeric materials. In the present study a simple yet efficient synthesis of sulfur-rich polymers from elemental sulfur-derived polysulfide salts and bisepoxide monomers was reported. Nucleophilic ring opening step growth polymerization of bisepoxide compounds with bifunctional sulfur derivative sodium pentasulfide (Na2S5) allowed tailorable access to novel linear copolymers with polysulfide chains in the backbone and hydroxyl groups at the side chains. Functional copolymers in the range from 14.8 kDa to 24.5 kDa molecular weights (Mn) were obtained with relatively high monomer conversions (69–91 %). By simple alteration of employed bisepoxide monomers, structurally diverse copolymers were obtained. The polymerizations were efficiently conducted at ambient temperature without the need of any catalyst. Obtained copolymers incorporated alternating hydroxyl functionalities at polymer side chains which were employed as reactive handles for post-polymerization modification. By employing a multifunctional epoxide crosslinker, chemically crosslinked polymers were also fabricated. These crosslinked polymers were shown to be utilized as adsorbents for mercury removal from water. The obtained results in this study demonstrated that the proposed methodology can be employed to synthesize and fabricate structurally diverse sulfur-rich polymers that might find potential use in various material applications.

A systematic study of tert‐butylacrylamide‐methyl acrylate‐acrylic acid radical solution terpolymerization

AbstractMulti‐functional polymers used for personal care products can be synthesized by radical polymerization of acrylic acid (AA) in alcohol/water solutions with non‐functional monomers such as methyl acrylate (MA) and N‐tert‐butylacrylamide (t‐BuAAm). However, solvents capable of forming or disrupting hydrogen bonds cause the polymerization kinetics of these monomers to deviate from their polymerization behaviour in bulk and non‐polar solvents. In this work, a previous mechanistic model developed for MA/t‐BuAAm copolymerization is extended to represent the terpolymerization system MA/t‐BuAAm/AA. The additional kinetic coefficients required for the system are estimated from fitting to AA homopolymerizations and AA/MA and AA/t‐BuAAm copolymerizations conducted in an ethanol/water solution. In‐situ nuclear magnetic resonance (NMR) spectroscopy is used to follow monomer conversions and composition drift behaviour, with the molar mass distributions of the polymer products characterized by size‐exclusion chromatography. Although AA is more reactive than MA in non‐polar solvents, the reactivities of the two monomers equalize under the experimental conditions examined. Thus, the batch and semi‐batch terpolymerization data collected are represented equally well by a reduced acrylate/t‐BuAAm copolymerization model and the full terpolymerization implementation.

Modelling and parameter estimation of trans‐β‐farnesene coordination polymerization

Abstracttrans‐β‐Farnesene is a bio‐derived terpene monomer that can polymerize, generating polymers with properties that can be similar to the properties of conventional petroleum‐derived polymers. For this reason, in the present study, several coordination polymerizations of trans‐β‐farnesene are carried out using the Ziegler–Natta catalyst system composed by neodymium versatate (), diisobutylaluminum hidride (DIBAH), and dimethyldichlorosilane (DMDCS) in order to evaluate the influence of key operation variables on the control of average molar masses and monomer conversion. A phenomenological model is proposed to describe the coordination polymerization of trans‐β‐farnesene, and the kinetic parameters required to simulate the reactions are estimated. The initial concentration of DIBAH used as a chain transfer agent (CTA) is calculated by a data reconciliation procedure since this very active compound can participate in undesired side reactions. It is shown that the initial monomer, DIBAH, and concentrations exert strong influences on the monomer conversion and average molar masses of (poly)farnese while the temperature effect is not so pronounced. The proposed kinetic mechanism was able to predict well the experimental data collected during the reactions, with the successful reconciliation of CTA concentrations and estimation of model parameters.

Synthesis of 3-, 4-, and 6-arm star poly(ionic liquid)s

In this study, we report the synthesis of 3-, 4-, and 6-arm star poly(vinylbenzyl methylimidazolium chloride) via reversible addition-fragmentation chain transfer (RAFT) polymerization with a core-first approach, which results in uniform number and length of polymer arms. The effect of initial radical initiator concentration and number of functional groups per multifunctional RAFT agent on polymerization reaction kinetics was systematically investigated. Increasing the initial radical initiator concentration resulted in faster monomer conversion, while decreasing the number of functional groups per multifunctional RAFT agent resulted in a decrease in the initial rate retardation in reaction kinetics. This work demonstrates a facile method for synthesizing ion-containing star polymers, specifically star poly(ionic liquids) or star PILs, with uniform number and length of polymer arms, where star PILs may be a promising new material for electrochemical energy devices due to property enhancements associated with their star polymer architecture.

Features of Methyl Methacrylate Polymerization Mediated by Methylene Blue and Ethyl 2-Bromoisobutyrate under Photoirradiation Conditions

Using methyl methacrylate polymerization as an example, the features of polymer synthesis in the presence of the catalytic system [methylene blue + ethyl 2-bromoisobutyrate] at room temperature under visible light irradiation are investigated. The effect of polymerization conditions, including the light irradiation wavelength and various structure activators, on the monomer conversion and molecular weight characteristics of polymers is estimated. It is shown that polymerization can proceed in the controlled mode under mild temperature conditions according to the atom transfer mechanism (Metal Free Atom Transfer Radical Polymerization) to high conversions at low photocatalyst concentrations.

Optimal combination of UV‐induced cationic ring opening polymerization monomers for light‐weight automotive plastic coating

AbstractCROP reactivity of organic coatings composed of three structurally different monomers with epoxy or oxetane derivatives was investigated, focusing on rheological and surface mechanical properties. Real‐time crosslinking behavior of CROP monomers was monitored using a rotational rheometer. Results of differential scanning calorimetry with in situ UV irradiation revealed that the ring opening reactivity of CROP monomers protonated by a photoacid generator (PAG) was correlated with the heat released during the exothermic polymerization reaction. In addition, reaction conversions of monomers with epoxy and oxetane groups were compared using Fourier transform infrared spectroscopy (FT‐IR) under dark curing conditions. Surface and internal mechanical properties of coating films, including adhesion with polycarbonate substrate, were comprehensively evaluated by nano‐indentation, nano‐scratch, and surface and interfacial cutting analysis system (SAICAS) tests. By understanding the unique crosslinking characteristics of each CROP monomer, the ternary CROP monomer system, optimally containing with ECC of 53.6 wt%, DOX of 22.9 wt%, and DEO of 15.3 wt%, exhibited improved crosslinking density (G′ from 104 to 107 Pa) and exceptional mechanical (with scratch resistance increasing from 7.11 to 16.17 mN for Lc1), adhesion (with crosscut resistance increasing from 0 to 5B), and transparency properties, surpassing the performance of unitary ECC coating system.

Bio-Based Valorization of Lignin-Derived Phenolic Compounds: A Review.

Lignins are the most abundant biopolymers that consist of aromatic units. Lignins are obtained by fractionation of lignocellulose in the form of "technical lignins". The depolymerization (conversion) of lignin and the treatment of depolymerized lignin are challenging processes due to the complexity and resistance of lignins. Progress toward mild work-up of lignins has been discussed in numerous reviews. The next step in the valorization of lignin is the conversion of lignin-based monomers, which are limited in number, into a wider range of bulk and fine chemicals. These reactions may need chemicals, catalysts, solvents, or energy from fossil resources. This is counterintuitive to green, sustainable chemistry. Therefore, in this review, we focus on biocatalyzed reactions of lignin monomers, e.g., vanillin, vanillic acid, syringaldehyde, guaiacols, (iso)eugenol, ferulic acid, p-coumaric acid, and alkylphenols. For each monomer, its production from lignin or lignocellulose is summarized, and, mainly, its biotransformations that provide useful chemicals are discussed. The technological maturity of these processes is characterized based on, e.g., scale, volumetric productivities, or isolated yields. The biocatalyzed reactions are compared with their chemically catalyzed counterparts if the latter are available.

Main approaches of biofilm formation in composite resins: a concise systematic review

Introduction: Composite resins are widely used in clinical dental practice to restore the structure lost by caries and dental defects, achieving aesthetic and functional results. Failures in the photoactivation process can cause problems in the mechanical resistance to wear in regions of direct occlusal contact on the restorative material. This occurs due to the reduction in the degree of conversion of monomers into polymers, compromising the clinical performance of the composite resin. Polymerization shrinkage leads to microleakage of the restoration, leading to staining and the development of bacterial biofilms. Objective: It was to carry out a systematic review of the main scientific evidence of biofilm formation on composite resin veneers, identifying potential predictors, as well as proposals to mitigate this problem. Methods: The systematic review rules of the PRISMA Platform were followed. The search was carried out from December 2022 to March 2023 in the Scopus, PubMed, Science Direct, Scielo, and Google Scholar databases, using articles from 2015 to 2022. The quality of the studies was based on the GRADE instrument and the risk of bias was analyzed accordingly, according to the Cochrane instrument. Results and Conclusion: A total of 125 articles were found, 25 articles were evaluated and 20 were included and developed in this systematic review study. Considering the Cochrane tool for risk of bias, the overall assessment resulted in 10 studies with a high risk of bias and 70 studies that did not meet GRADE. It was concluded that the surface properties of resin-based composite materials, as well as surface treatments, can strongly affect bacterial adhesion and biofilm formation. In addition, scientific evidence highlights that cariogenic biofilm formation can alter the surface properties of materials, thus stimulating bacterial adhesion and biofilm formation. Photoactivation allows the curing and crosslinking of polymer chains, essential for the clinical longevity of the composite resin. Insufficient photoactivation culminates in marginal microleakage in restorations and biofilm accumulation on surfaces exposed to the oral environment.

Shape-Controlled synthesis of conjugated microporous polymer nanotubes and their implementation in continuous flow polymerization

Flow reactors have materialized as a reliable and sustainable approach toward polymer production and processing to promote efficient and uniform irradiation pathways. However, the disadvantages of existing homogeneous photocatalysts including noxiousness, restricted photocatalytic activity and stability, and difficult separation and purification, still pose a great challenge to the advancement of this technique. Herein, conjugated microporous polymer nanotubes (hPorBDP NTs) were fabricated through Sonogashira-Hagihara cross-coupling polycondensation with silica nanorods as sacrificial templates, followed by etching of the inner cores. The hPorBDP NTs with a hollow nanostructure and a highly porous texture were demonstrated to facilitate the separation procedure and provide more accessible active sites for photocatalytic reactions. The hPorBDP NTs were employed as heterogeneous catalysts to activate photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization in batch and in continuous flow system. Screening of the initial monomer concentrations and pump flow rates, high monomer conversions (ɑ > 80%) and narrow dispersities (Đ < 1.15) were achieved in continuous flow system for upscaled production of polymers. Separation and reutilization of the catalyst-bound NTs were realized through facile centrifugation, which resulted in negligible leaching and maintenance of catalytic performance over multiple polymerization cycles. As such, the development of photosynthesis system using hPorBDP NTs as heterogeneous photocatalysts should broaden the application scope of these fascinating catalysts while benefiting synthetic upscaling by continuous flow polymerization.

Modelling of polymerization kinetics and molar mass development in the nitroxide‐mediated polymerization (NMP) of styrene in supercritical carbon dioxide using the PC‐SAFT equation of state

AbstractA mathematical model for polymerization kinetics and molar mass development in the nitroxide‐mediated polymerization (NMP) of vinyl monomers in supercritical carbon dioxide (scCO2) has been developed. The method of moments is used for molar mass development. The perturbed‐chain statistical associating fluid theory (PC‐SAFT) equation of state is used to estimate the number of stable phases present at equilibrium in the reaction mixture, critical number average chain length at which polymer particles are formed, and monomer concentration in each phase. Pure and binary PC‐SAFT interaction parameters are estimated from liquid–liquid equilibrium (LLE) and liquid–vapour equilibrium (LVE) experimental data at 60 to 129°C. The effect of pressure on monomer conversion and molar mass development in the polymerization of styrene (Sty) using benzoyl peroxide (BPO) and 2,2,6,6‐Tetramethylpiperidinyl‐1‐oxyl (TEMPO) at 120°C and 300–500 bar is studied. It was observed that increasing pressure increases polymerization rate without significantly affecting molar mass development.

Investigation and optimization of polyolefin elastomers polymerization processes using multi-objective genetic algorithm

The aim of this research is to develop continuous reactor network models to determine the reactor configuration and corresponding optimal operating conditions of a polyolefin elastomers polymerization process. To achieve this objective, a modified vapor-liquid equilibrium model is integrated with both the continuous stirred tank reactor (CSTR) model and the plug flow reactor (PFR) model to accurately predict the vaporization rates of liquid. The multi-objective problem is formulated to maximize the monomer conversion and minimize the total annualized cost simultaneously. To solve the multi-objective problem, the genetic algorithm is utilized to identify the optimal operating conditions. Furthermore, the impact of the reactor combination mode is analyzed by varying the number and sequence of CSTR or PFR. The research findings reveal that a multi-phase CSTR without circulating stream followed by a PFR is the optimal reactor configuration. The proposed configuration can enhance reactor productivity and reduce the total annualized cost simultaneously while meeting the desired polymer properties.

Modelling of a continuous kneader reactor for the polymerization of partially neutralized acrylic acid

AbstractA mathematical model and analysis of the continuous polymerization of partially neutralized acrylic acid (AA) in a continuous kneader reactor is presented here as an initial attempt to simulate the synthesis of a superabsorbent polymer. A detailed kinetic model has been used to describe the copolymerization of AA and sodium acrylate (NaA) in aqueous medium. This model is used to describe batch and continuous operations. The polymerization is initiated by a mixture of potassium persulphate (K2S2O8, KPS) and hydrogen peroxide (H2O2) as oxidizing agent and ascorbic acid (AsA) as reducing agent. A novel set of kinetic parameters has been estimated by fitting experimental data from different literature sources. The operation of a continuous kneader reactor modelled as a plug‐flow reactor with axial dispersion is theoretically investigated to predict temperature profile, total and individual monomer conversion, consumption of KPS, H2O2, and AsA, and polymer average molecular weights. The simulation results show the presence of a hot spot close to the reactor entrance that could be potentially severe during startup and could have a detrimental impact on polymer quality. This model is a first step in the direction of achieving optimal operating protocols and exploring improved polymerization reactor designs.

Greening Biobased Polybenzoxazine Network: Three Benefits in One Go

Eco-friendly initiators and environmentally safe flame-retardant (FR) adhesives are highly desired to empower sustainability in polymers. However, incorporating all of the properties simultaneously in a single step is challenging to achieve high-performance biomass sourced polymers. Herein, biobased benzoxazine monomers sourced from agro-waste phenol (cardanol, C) were synthesized using a facile solventless catalyst-free approach. Owing to their requirement of high ROP temperature (∼ 250 °C), prolonged polymerization cycle, issues of high flammability, and poor adhesive strength of the resultant polybenzoxazines limit their applications. To alleviate these issues, blends of naturally occurring phytic acid (PA) with the monomers resulted in fast polymerization kinetics (∼90% monomer conversion in 1 h) with the formation of hybrid polybenzoxazine networks at a mild temperature (∼100 °C). PA enacted as a green initiator and reactive halogen-free biobased FR and revealed favorable interactions across the polymer framework. Benefitting from the design, physical, ionic, and covalent cross-linking network of polymers with PA accounted for the extra-strong adhesive strength (71.1 kg/cm2, nearly 3.7 times higher than that of the pristine polybenzoxazine). Upon burning, the hybrid polybenzoxazines exhibited extremely low flammability, superior smoke suppression and formed intumescent char as supported by the limiting oxygen index, vertical burning, and cone calorimetry measurements. The present study indicated that the benign by design approach is a way forward to green thermosets offering excellent combination properties and potential applications in the future.

An in-solution snapshot of SARS-COV-2 main protease maturation process and inhibition

The main protease from SARS-CoV-2 (Mpro) is responsible for cleavage of the viral polyprotein. Mpro self-processing is called maturation, and it is crucial for enzyme dimerization and activity. Here we use C145S Mpro to study the structure and dynamics of N-terminal cleavage in solution. Native mass spectroscopy analysis shows that mixed oligomeric states are composed of cleaved and uncleaved particles, indicating that N-terminal processing is not critical for dimerization. A 3.5 Å cryo-EM structure provides details of Mpro N-terminal cleavage outside the constrains of crystal environment. We show that different classes of inhibitors shift the balance between oligomeric states. While non-covalent inhibitor MAT-POS-e194df51-1 prevents dimerization, the covalent inhibitor nirmatrelvir induces the conversion of monomers into dimers, even with intact N-termini. Our data indicates that the Mpro dimerization is triggered by induced fit due to covalent linkage during substrate processing rather than the N-terminal processing.

Removable Pressure-Sensitive Adhesives Based on Acrylic Telomer Syrups

Removable pressure-sensitive adhesives (PSAs) are used in the production of self-adhesive materials such as protective films, masking tapes or biomedical electrodes. This work presents a new and environmentally friendly method of obtaining this type of adhesive materials, i.e., photochemically induced free radical telomerization. Adhesive binders to removable PSAs, i.e., the photoreactive acrylic telomer syrups (ATS) were prepared from n-butyl acrylate, acrylic acid, and 4-acrylooxybenzophenone. Tetrabromomethane (CBr4) or bromotrichloromethane (CBrCl3) were used as the telogens. ATS was modified with unsaturated polybutadiene resin and a radical photoinitiator. Adhesive compositions were coated onto a carrier and UV cross-linked. The effects of the chemical nature of telomers (i.e., terminal Br or Cl atoms) and their molecular weight (K-value), as well as the cross-linking degree on adhesive properties of PSAs, were studied. It was found that with the increase in telogen content in the system, the dynamic viscosity of ATS and K-value of acrylic telomers decrease, and the conversion of monomers increases. CBr4 turned out to be a more effective chain transfer agent than CBrCl3. Moreover, telomers with terminal Br-atoms (7.5 mmol of CBr4), due to slightly lower molecular weights and viscosity, showed a higher photocrosslinking ability (which was confirmed by high cohesion results at 20 and 70 °C, i.e., &gt;72 h). Generally, higher values of the temperature at which adhesive failure occurred were noted for PSAs based on ATS with lower telogen content (7.5 mmol), both CBr4 and CBrCl3. The excellent result for removable PSA was obtained in the case of telomer syrup Br-7.5 crosslinked with a 5 J/cm2 dose of UV-radiation (adhesion ca.1.3 N/25 mm, and cohesion &gt; 72 h).

Free‐radical propagation rate coefficients

AbstractThe pulsed laser polymerization‐size‐exclusion chromatography (PLP‐SEC) technique has become the International Union of Pure and Applied Chemistry (IUPAC)‐recommended method for the accurate determination of propagation rate coefficients, kp, for radical polymerization. The fundamental insight provided by Heuts, Gilbert, and Radom into the relevance of transition state dynamics allows for an adequate understanding of the dependence of kp on radical chain length, solvent environment, and monomer conversion. The associated entropic effects are particularly pronounced in aqueous solution, but are also found in less polar media and with non‐polar monomers. Moreover, these arguments are applicable towards the interpretation of copolymerization reactivity ratios. The addition of sodium hydroxide to aqueous solutions of (meth)acrylic acid yields partially and even fully ionized systems with clearly reduced kp, which indicates the action of repulsive forces between the equally charged monomer and radical species. Increasing the concentration of monomer as well as the addition of salts may reverse this effect and increase kp due to counterion activity.

Development of a fluorescent PMMA-based polymer material through in-situ incorporation of curcuma extract

In the present work, the in situ incorporation of curcumin was carried out in a polymer matrix through bulk polymerization to improve its photostability. It was found that extraction of curcumin from turmeric extract by the precursor monomer methyl methacrylate (MMA) can be performed immediately before the polymerization in order to reduce the degradation of the fluorescent species by the initiator system, although the obtained results also showed that incorporation of the turmeric extract into monomer can retard the polymerization kinetics. Despite that, the fluorescence properties of curcumin were preserved after incorporation in a solid polymeric matrix, which also enhanced the fluorophore photostability, avoiding the rapid degradation of the fluorophore observed when it is dispersed in solvents. Furthermore, it was also observed that addition of acrylic acid (AA) as a comonomer enhanced the photochemical stability of the turmeric extract incorporated into the polymer matrix and promoted the bathochromic effect, when compared to the spectroscopic behavior of the extract obtained from MMA, both in solution and solid state. It was possible to optimize the synthesis condition with help of a standard factorial experimental design, allowing the simultaneous attainment of high monomer conversion and fluorescence properties of the obtained material.