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Polymers
Special Issues
Recent Developments in Polymerization Kinetics
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Recent Developments in Polymerization Kinetics

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Physics and Theory".

Deadline for manuscript submissions: 15 May 2024 | Viewed by 13791

Special Issue Editors

Dr. Katarzyna Szcześniak

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Guest Editor
Department of Polymers, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, PL-60965 Poznan, Poland
Interests: polymers; star polymer; ATRP; chemical physic; polymerization kinetics; photopolymerization; biopolymers; drug delivery systems
Special Issues, Collections and Topics in MDPI journals
Dr. Piotr Gajewski

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Guest Editor
Department of Polymers, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, PL-60965 Poznan, Poland
Interests: photopolymerization; polymer electrolytes - synthesis and application; ionogels; hydrogels; statistical analysis; kinetic of photopolymerization
Special Issues, Collections and Topics in MDPI journals
Dr. Agnieszka Marcinkowska

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Guest Editor
Department of Polymers, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, PL-60965 Poznan, Poland
Interests: photopolymerization; nanocomposites; hybrid polymeric materials; solid-state electrolytes; polymer gels; photocurable coatings; biomaterials; polymers in pharmacy
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Nowadays, with the development of technology, more and more world-class research laboratories and companies are engaged in the design and synthesis of more sophisticated polymeric materials. Scientists are looking for newer and newer monomers, initiators and all kinds of modifiers. However, preparation of new type of polymers needs the basic and advanced knowledge about the kinetics and reaction mechanism of their formation, i.e. mechanism of polymerization in different media, effect of the reaction conditions, effect of modifying additives, etc. All of the mentioned above factors have influence on final product which is a new polymer. Therefore, when the kinetics is known the new industrial process can be developed leading to formation of new polymers. Thanks to knowledge about this what is happening and in which way this process is going, conditions of it can be selected, such as temperature, monomers, solvents and many more. Polymerizations can be carried out under a wide range of conditions, including variations in monomer structures, the number and type of reactive functional groups, temperature, atmosphere and initiator type. Polymers are widely used in construction, building and infrastructure. Construction and utility parts in buildings are often partly or completely polymeric, they accompany us in everyday life. Polymers are developing especially in medicine and electronics and the automotive industry, as well as a highly developed packaging industry. Therefore, we want to encourage you to explore this extremely interesting world of hitherto unknown polymers and their kinetics.

Dr. Katarzyna Szcześniak
Dr. Piotr Gajewski
Dr. Agnieszka Marcinkowska
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • chain/step polymerization
  • photopolymerization
  • reversible deactivation radical polymerization
  • atom transfer radical polymerization
  • living/controlled polymerization
  • copolymerization
  • branching
  • kinetics of polymerization
  • reactivity coefficients

Published Papers (5 papers)

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Research

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10 pages, 2250 KiB  
Article
Kinetics of Polycycloaddition of Flexible α-Azide-ω-Alkynes Having Different Spacer Length
by Andrey Galukhin, Roman Aleshin, Roman Nosov and Sergey Vyazovkin
Polymers 2023, 15(14), 3109; https://doi.org/10.3390/polym15143109 - 21 Jul 2023
Viewed by 642
Abstract
Two flexible α-azide-ω-alkynes differing in the length of the hydrocarbon spacers (C8 vs. C12) between functional groups are synthesized. Their bulk polymerization kinetics is studied by differential scanning calorimetry (DSC) and parameterized with the aid of isoconversional methodology. The monomer [...] Read more.
Two flexible α-azide-ω-alkynes differing in the length of the hydrocarbon spacers (C8 vs. C12) between functional groups are synthesized. Their bulk polymerization kinetics is studied by differential scanning calorimetry (DSC) and parameterized with the aid of isoconversional methodology. The monomer with a shorter hydrocarbon spacer has somewhat greater reactivity. The effect is traced to a moderate increase in the effective value of the preexponential factor that arises from the fact that the respective monomer has a higher initial molar concentration in itself. The techniques of GPC and NMR provide additional kinetic and mechanistic insights into the studied reaction. Full article
(This article belongs to the Special Issue Recent Developments in Polymerization Kinetics)
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18 pages, 2698 KiB  
Article
Free-Radical Propagation Rate Coefficients of Diethyl Itaconate and Di-n-Propyl Itaconate Obtained via PLP–SEC
by Enno Meyer, Tobias Weege and Philipp Vana
Polymers 2023, 15(6), 1345; https://doi.org/10.3390/polym15061345 - 08 Mar 2023
Cited by 1 | Viewed by 1048
Abstract
The propagation step is one of the key reactions in radical polymerization and knowledge about its kinetics is often vital for understanding and designing polymerization processes leading to new materials or optimizing technical processes. Arrhenius expressions for the propagation step in free-radical polymerization [...] Read more.
The propagation step is one of the key reactions in radical polymerization and knowledge about its kinetics is often vital for understanding and designing polymerization processes leading to new materials or optimizing technical processes. Arrhenius expressions for the propagation step in free-radical polymerization of diethyl itaconate (DEI) as well as di-n-propyl itaconate (DnPI) in bulk, for which propagation kinetics was yet unexplored, were thus determined via pulsed-laser polymerization in conjunction with size-exclusion chromatography (PLP-SEC) experiments in the temperature range of 20 to 70 °C. For DEI, the experimental data was complemented by quantum chemical calculation. The obtained Arrhenius parameters are A = 1.1 L·mol–1·s–1 and Ea = 17.5 kJ·mol−1 for DEI and A = 1.0 L·mol–1·s–1 and Ea = 17.5 kJ·mol−1 for DnPI. Full article
(This article belongs to the Special Issue Recent Developments in Polymerization Kinetics)
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13 pages, 2170 KiB  
Article
Influence of Initiator Concentration on the Polymerization Course of Methacrylate Bone Cement
by Grzegorz Przesławski, Katarzyna Szcześniak, Piotr Gajewski and Agnieszka Marcinkowska
Polymers 2022, 14(22), 5005; https://doi.org/10.3390/polym14225005 - 18 Nov 2022
Cited by 2 | Viewed by 2384
Abstract
Background: The amount of oxidant (initiator) and reductant (co-initiator) and their ratio have a significant effect on the properties of polymethacrylate bone cement, such as maximum temperature (Tmax), setting time (tset) and compressive strength (σ). The increase in [...] Read more.
Background: The amount of oxidant (initiator) and reductant (co-initiator) and their ratio have a significant effect on the properties of polymethacrylate bone cement, such as maximum temperature (Tmax), setting time (tset) and compressive strength (σ). The increase in the initiating system concentration causes an increase in the number of generated radicals and a faster polymerization rate, which shortens the setting time. The influence of the redox-initiating composition on the course of polymerization (rate of polymerization and degree of double bond conversion) and the mechanical properties of bone cement will be analyzed. Methods: Bone cements were synthesized by mixing a powder phase composed of two commercially available methacrylate copolymers (Evonic) and a liquid phase containing 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), and triethylene glycol dimethacrylate (D3). As an initiating system, the benzoyl peroxide (BPO) as an oxidant (initiator) in combination with a reducing agent (co-initiator), N,N-dimethylaniline (DMA), was used. Samples were prepared with various amounts of peroxide BPO (0.05%, 0.1%, 0.2%, 0.3%, 0.5% and 0.7% by weight) with a constant amount of reducing agent DMA (0.5 wt.%), and various amounts of DMA (0.25%, 0.35% and 0.5% by weight) with a constant amount of BPO (0.3 wt.%). The polymerization kinetics were studied by differential scanning calorimetry (DSC). Doughing time and compressive strength tests were carried out according to the requirements of the ISO 5833:2002 standard. Results: The increase in polymerization rate was due to the increase in the amount of BPO. In addition, the curing time was shortened, as well as the time needed to achieve the maximum polymerization rate. The final conversion of the double bonds in the studied compositions was in the range 74–100%, and the highest value of this parameter was obtained by the system with 0.3 wt.% of BPO. The doughing times for each BPO concentration were in the range of 90–140 s. The best mechanical properties were obtained for the cement following the initiating system concentrations: 0.3 wt.% of BPO and 0.5 wt.% of DMA. Nevertheless, all tested cements met the requirements of the ISO 5833:2002 standard. Conclusions: Based on the conducted polymerization kinetic studies, the best reaction conditions are provided by an initiating system containing 0.3 wt.% of BPO oxidant (initiator) and 0.5 wt.% of DMA reductant (co-initiator). A decrease in the DMA amount caused a decrease in the polymerization rate and the amount of heat released during the reaction. The change in BPO and DMA concentrations in the composition had little effect on the doughing time of the studied bone cement. The cements showed similar doughing times, ranging from 90–225 s, which is comparable to the bone cement available on the market. Full article
(This article belongs to the Special Issue Recent Developments in Polymerization Kinetics)
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16 pages, 4605 KiB  
Article
Polymorphic Crystallization Behavior of a Poly(butylene adipate) Midblock within a Poly(L-lactide-butylene adipate-L-lactide) Triblock Copolymer
by Lei Hua and Xiaodong Wang
Polymers 2022, 14(22), 4902; https://doi.org/10.3390/polym14224902 - 13 Nov 2022
Viewed by 1551
Abstract
New biodegradable aliphatic PLLA-PBA-PLLA copolymers with soft poly(butylene adipate) (PBA) and hard poly(l-lactide) (PLLA) building blocks were synthesized via ring-opening polymerization (ROP). Proton nuclear magnetic resonance (1HNMR) was utilized to confirm the volume fraction of PBA (fPBA) within PLLA-PBA-PLLA. [...] Read more.
New biodegradable aliphatic PLLA-PBA-PLLA copolymers with soft poly(butylene adipate) (PBA) and hard poly(l-lactide) (PLLA) building blocks were synthesized via ring-opening polymerization (ROP). Proton nuclear magnetic resonance (1HNMR) was utilized to confirm the volume fraction of PBA (fPBA) within PLLA-PBA-PLLA. It was found that a PBA midblock (PBA-mid) within PLLA-PBA-PLLA-s (PLLA-PBA-PLLA triblock copolymer with a short PLLA block length) might display lamellar domain structure. However, PBA-mid within PLLA-PBA-PLLA-l (PLLA-PBA-PLLA triblock copolymer with a long PLLA block length) might locate itself as a nanoscale cylindrical domain surrounded by a PLLA continuous phase. Polymorphic crystals of PBA-mid within the PLLA-PBA-PLLA copolymers were formed after melt crystallization at the given temperatures, which were studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis. According to the WAXD and DSC analyses, it was interesting to find that the α-type crystal of PBA-mid was favorable to develop in the lower temperature region regardless of the state (crystallization or amorphous) of the PLLA component. Additionally, when the PLLA component was held in its amorphous state, it was easier for PBA-mid within the PLLA-PBA-PLLA copolymers to transform from the metastable β-form crystal to the stable α-form crystal. Furthermore, polarized optical microscopy (POM) photos provided direct evidence of the polymorphic crystals of PBA-mid within PLLA-PBA-PLLAs. Full article
(This article belongs to the Special Issue Recent Developments in Polymerization Kinetics)
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Review

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58 pages, 6055 KiB  
Review
A Review on Modeling Cure Kinetics and Mechanisms of Photopolymerization
by Margit Lang, Stefan Hirner, Frank Wiesbrock and Peter Fuchs
Polymers 2022, 14(10), 2074; https://doi.org/10.3390/polym14102074 - 19 May 2022
Cited by 33 | Viewed by 7205
Abstract
Photopolymerizations, in which the initiation of a chemical-physical reaction occurs by the exposure of photosensitive monomers to a high-intensity light source, have become a well-accepted technology for manufacturing polymers. Providing significant advantages over thermal-initiated polymerizations, including fast and controllable reaction rates, as well [...] Read more.
Photopolymerizations, in which the initiation of a chemical-physical reaction occurs by the exposure of photosensitive monomers to a high-intensity light source, have become a well-accepted technology for manufacturing polymers. Providing significant advantages over thermal-initiated polymerizations, including fast and controllable reaction rates, as well as spatial and temporal control over the formation of material, this technology has found a large variety of industrial applications. The reaction mechanisms and kinetics are quite complex as the system moves quickly from a liquid monomer mixture to a solid polymer. Therefore, the study of curing kinetics is of utmost importance for industrial applications, providing both the understanding of the process development and the improvement of the quality of parts manufactured via photopolymerization. Consequently, this review aims at presenting the materials and curing chemistry of such ultrafast crosslinking polymerization reactions as well as the research efforts on theoretical models to reproduce cure kinetics and mechanisms for free-radical and cationic photopolymerizations including diffusion-controlled phenomena and oxygen inhibition reactions in free-radical systems. Full article
(This article belongs to the Special Issue Recent Developments in Polymerization Kinetics)
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